Braid-Delta Deposits from a Broad Shallow-Marine Setting： the Middle Member of the Kalpingtag F

High power pulsed magnetron sputtering:A review on scienti fic and engineering state of the artK.Sarakinos a ,⁎,1,J.Alami b ,1,S.Konstantinidis c ,1a Materials Chemistry,RWTH Aachen University,52074Aachen,Germanyb Sulzer Metaplas GmbH,Am Böttcherberg 30-38,51427,Bergisch Gladbach,GermanycLaboratoire de Chimie Inorganique et Analytique,Universitéde Mons,Avenue Copernic 1,7000Mons,Belgiuma b s t r a c ta r t i c l e i n f o Article history:Received 31March 2009Accepted in revised form 6November 2009Available online 19January 2010Keywords:HPPMS HiPIMSIonized PVDHigh power pulsed magnetron sputtering (HPPMS)is an emerging technology that has gained substantial interest among academics and industrials alike.HPPMS,also known as HIPIMS (high power impulse magnetron sputtering),is a physical vapor deposition technique in which the power is applied to the target in pulses of low duty cycle (b 10%)and frequency (b 10kHz)leading to pulse target power densities of several kW cm −2.This mode of operation results in generation of ultra-dense plasmas with unique properties,such as a high degree of ionization of the sputtered atoms and an off-normal transport of ionized species,with respect to the target.These features make possible the deposition of dense and smooth coatings on complex-shaped substrates,and provide new and added parameters to control the deposition process,tailor the properties and optimize the performance of elemental and compound films.©2009Elsevier B.V.All rights reserved.Contents 1.Introduction ..............................................................16622.HPPMS:power supplies and processes .................................................16623.Plasma dynamics in HPPMS ......................................................16643.1.On the HPPMS plasma .....................................................16643.2.Determination of plasma properties:a theoretical overview ....................................16653.3.The HPPMS plasma properties ..................................................16663.3.1.The effect of the pulse on/off time con figuration on the plasma properties .........................16683.3.2.Rarefaction in the HPPMS plasma ............................................16693.4.Instabilities in the HPPMS plasma ................................................16713.4.1.Plasma instabilities:an overview ............................................16713.4.2.Plasma initiation and the relationship between plasma instabilities and the chargetransport in the HPPMS plasma .....16714.Plasma-surface interactions and deposition rate .............................................16734.1.Non-reactive HPPMS ......................................................16734.1.1.Target-plasma interactions and target erosion rate ....................................16734.1.2.Transport of ionized sputtered species ..........................................16754.2.Reactive HPPMS ........................................................16755.Growth of thin films by HPPMS ....................................................16765.1.HPPMS use for deposition on complex-shaped substrates .....................................16765.2.Interface engineering by HPPMS .................................................16775.3.The effect of HPPMS on the film microstructure .........................................16785.4.Phase composition tailoring of films deposited using HPPMS ...................................16796.Towards the industrialization of HPPMS ................................................16816.1.Examples of industrially relevant coatings by HPPMS .................................. (1681)Surface &Coatings Technology 204(2010)1661–1684⁎Corresponding author.Tel.:+492418025974,+492204299390,+3265554956.E-mail address:sarakinos@mch.rwth-aachen.de (K.Sarakinos).1All authors have contributed equally to the preparation of themanuscript.0257-8972/$–see front matter ©2009Elsevier B.V.All rights reserved.doi:10.1016/j.surfcoat.2009.11.013Contents lists available at ScienceDirectSurface &Coatings Technologyj o u r n a l h om e p a g e :w w w.e l s ev i e r.c o m /l o c a t e /s u r fc o a t6.2.Up-scaling of the HPPMS process (1682)6.3.Positioning HPPMS in the coating and components market (1682)Acknowledgements (1682)References (1682)1.IntroductionThinfilms are used in diverse technological applications,such as surface protection and decoration,data storage,and optical and microelectronic devices.The increasing demand for new functional films has been a strong incentive for research towards not only understanding the fundamentals and technical aspects of thinfilm growth,but also developing new deposition techniques which allow for a better control of the deposition process.Among the various methods employed forfilm growth,Physical Vapor Deposition(PVD)techniques, such as magnetron sputtering,are widely used[1].Magnetron sputtering is a plasma-based technique,in which inert gas(commonly Ar)atoms are ionized and accelerated as a result of the potential difference between the negatively biased target(cathode)and anode.The interactions of the ions with the target surface cause ejection(sputtering)of atoms which condensate on a substrate and form afilm[1,2].The condensation and film growth processes frequently occur far from the thermodynamic equilibrium,due to kinetic restrictions[2,3].Thus,a good control of both the thermodynamic and the kinetic conditions has implications on the growth dynamics and enables the tailoring of the structural,optical, electrical,and mechanical properties of thefilms[4].One way to control the growth dynamics is by heating the substrate during the deposition [2].The magnitude of the deposition temperature affects the energy transferred to thefilm forming species(adatoms)[2].This energy is,for instance,decisive for the activation of surface and bulk diffusion processes[5,6]and enables control over thefilm morphology[7–10]. Another source of energy are the plasma particles that impinge onto the growingfilm transferring energy and momentum to the adatoms[4,5]. The bombardingflux consists both of neutral and charged gas particles,as well as sputtered species.Numerous studies have shown that the energy, theflux,the angle of incidence,and the nature of the bombarding species are of importance for the properties of the depositedfilms[4,5,11,12].In general,the plasma particles exhibit a relatively broad energy distribu-tion with a mean value of several eV[13].The particle energy,andflux are affected by the target-to-substrate distance and the working pressure[1]. When the particles are charged the control of their energy can additionally be achieved by the use of electricfields,e.g.by applying a bias voltage to the substrate[4,14],while theirflux depends on a number of factors including the plasma density,the target power,and the magneticfield configuration at the target[4,14].It is therefore evident, that a high ion fraction in a depositingflux facilitates a more efficient and accurate control of the bombardment conditions providing,thus,added means for the tuning of thefilm properties.In magnetron sputtering processes the degree of ionization of the plasma particles is relatively low[13],resulting in a low total ionflux towards the growingfilm[13].As a consequence,in many cases bias voltage values of several tenths or even hundreds of V are required in order to increase the average energy provided to the deposited atoms and significantly affect thefilm properties[5].Moreover,the degree of ionization of sputtered species is typically less than1%[13,15,16].As a result,the majority of the charged bombarding particles is made of Ar+ions[13].This fact in combination with the relatively high bias voltages may cause subplantation of the Ar atoms in thefilm[17,18], leading to a generation of lattice defects,[18,19]high residual stresses [20–23],a deterioration of the quality of thefilm/substrate interface [21],and a poorfilm adhesion[24].Thus,the increase of the fraction of the ionized sputtered species has been an objective of many research works during the recent decades.Some of the approaches that have been demonstrated include the use of an inductively coupled plasma (ICP)superimposed on a magnetron plasma[25],the use of a hollow cathode magnetron[25],and the use of an external ion source[26]. Parallel to the above mentioned approaches Mozgrin et al.[27], Bugaev et al.[28]and Fetisov et al.[29]demonstrated in the mid90s that the operation of a conventional sputtering source in a pulsed mode,with a pulse duration ranging from1µs to1s and a frequency less than1kHz,allowed for pulsed target currents two orders of magnitude higher than the average target current in a conventional sputtering technique,such as direct current magnetron sputtering (dcMS)[27–29].These high pulse currents resulted,in turn,in ultra-dense plasmas with electron densities in the order of1018m−3[27–29],which are much higher than the values of1014–1016m−3 commonly obtained for dcMS[13,30].A few years later,Kouznetsov et al.[31]demonstrated in a publication,that received much acclaim,the high power pulsed operation of the sputtered target showing that in the case of Cu the high plasma densities obtained using this pulsed technique resulted in a total ionflux two orders of magnitude higher than that of a dcMS plasma,and a sputtered material ionization of ∼70%.The new deposition technique was called High Power Pulsed Magnetron Sputtering(HPPMS).In the years after Kouzsetov's report, HPPMS received extensive interest from researchers and led to a substantial increase of the HPPMS-related publications(Fig.1).Later, several research groups[25]adopted the alternative name High Power Impulse Magnetron Sputtering(HiPIMS)for this technique.The aim of this review paper is to describe the scientific and engineering state of the art of HPPMS.For this purpose,the principle and the basic structure of the existing HPPMS power supplies are described and the various existing approaches to produce high power pulses are demonstrated.The spatial and the temporal evolution of the HPPMS plasma and its interactions with the target and the growingfilm are discussed both from a theoretical and an experi-mental perspective.Furthermore,the effect of the HPPMS operation on the deposition rate and thefilm properties is presented.Finally,the use of HPPMS in industry and the challenges that the latter faces regarding the use of HPPMS are briefly addressed.2.HPPMS:power supplies and processesThe experimental realization of HPPMS requires power supplies different than those used in conventional magnetron sputtering processes. Those power supplies must be able to provide the target with pulses of high power density(typically in the range of a few kW cm−2),while maintaining the time-averaged target power density in values similarto Fig.1.Number of HPPMS-related publications in the period1999–2008.1662K.Sarakinos et al./Surface&Coatings Technology204(2010)1661–1684those during dcMS (i.e.a few W cm −2).The low average target power density is necessary to prevent overheating of the cathode and damage of the magnets and the target.A number of research groups and companies have developed HPPMS arrangements for both laboratorial and industrial use.These devices exhibit similarities in their basic structure which is schematically depicted in Fig.2.A dc generator is used to load the capacitor bank of a pulsing unit,which is connected to the magnetron.The charging voltage of the capacitor bank ranges typically from several hundreds of V up to several kV.The stored energy is released in pulses of de fined width and frequency using transistors with a switching capability in the µs range,located between the capacitors and the cathode.The pulse width (also referred to as pulse on-time)ranges,typically,from 5to 5000µs,while the pulse repetition frequency spans from 10Hz to 10kHz.Under these conditions,the peak target current density may reach values of up to several Acm −2,which are up to 3orders of magnitude higher than the current densities in dcMS [25].The high target current densities during the pulse on-time are accompanied by differences in the electrical characteristics of the discharge,as manifested by the current –voltage (I –V )curves of a magnetron operating in a dcMS and an HPPMS mode (Fig.3).According to Thornton [32]the target and the voltage of the magnetron are linked by the power law I ∝Vnð1ÞIn dcMS processes the exponent n in Eq.(1)ranges from 5up to 15(Fig.3).In HPPMS the exponent n changes from values similar to dcMS at low target voltages to values close to the unity when high voltages are applied (Fig.3)[33,34].Despite their common basic architecture,the available HPPMS power supplies exhibit differences primarily in the width and the shape of the pulses they can deliver,and in whether they can sustain a constant voltage during the pulse on-time.Arrangements able to provide high power pulses were already developed in the mid 90s,in order to explore the feasibility of producing high-current quasi-stationary magnetron glow discharges for high rate deposition [27–29].However,it was in 1999when Kouznetsov et al.[31]emphasizedthat the high power pulsing could allow for a high ionization degree of copper vapor (70%)as well as a homogeneous filling of 1:2aspect ratio trenches (see Fig.4).The time-dependent target current and target voltage curves of the HPPMS power supply developed by Kouznetsov et al.[31]are plotted in Fig.5where it is shown that the ignition of the plasma is accompanied by a drop of the voltage from ∼1000V to ∼800V,as the current increases to its peak value ranging from 200to 230A at the highest applied working pressure [35,36].A characteristic of this power supply is that the loading voltage is not maintained constant during the pulse on-time,and its temporal evolution is rather determined by the size of the capacitor bank and the time-dependent plasma impedance.Other power generators were designed to deliver voltage pulses with a rectangular shape (see Fig.6),i.e.a constant voltage value during the pulse on-time [34,37–39].It is to be noted that pulses with widths larger than about 50µs allow for a saturation of the discharge current and establishment of a steady-state plasma [40]provided that enough energy is stored in the capacitor bank.A common problem encountered in sputtering processes is the occurrence of arcs.This phenomenon is particularly pronounced during the deposition from conducting targets covered by insulating layers and can be detrimental for the quality of the films,due to the ejection of µm sized droplets from the target [41,42].The high peak target currents during the HPPMS operation may enhance the frequency of the arc events [43].Therefore,sophisticated electronics can be used in conjunction with the HPPMS power supplies to limit their effect if formed [43].An alternative way to alleviate this problem is to operate HPPMS using short pulses with widths ranging from 5to 20µs [44].A waveform during this mode of operation is presented in Fig.7.Within this short period of time,the glow discharge remains in a transient regime [40](as manifested by the triangular form of the target current)so that an eventual glow-to-arc transition is prevented.These short pulses have been,for instance,shown to allow for a stable and an arc-free reactive deposition of metal oxide films [45,46].However,in order to eliminate the time lag for plasma ignition which would allow for the production of high-current pulses within this short period of time,a pre-ionization stage has to be implemented [44,47].The pre-ionization of the discharge ensures that a low density plasma is maintained between the pulses as the charge carriers are already present before the voltage is turned on.The plasma pre-ionization step may be achieved by super-imposing a secondary plasma (such as a dc,a microwave,or an inductively coupled plasma)on the HPPMS plasma or by running the discharge at relatively high frequencies [44,47–49].The latter pre-ionization method is extensively implemented in mid-frequency pulsed plasmas [50–53].In contrast to the short pulses described above,long pulses with a width of several thousands of µs can also be used [54](Fig.8).In this case the pulse is composed of two (or more)stages.TheFig.2.Basic architecture of an HPPMS power supply.The dc generator charges the capacitor bank of a pulsing unit.The energy stored in the capacitors is dissipated into the plasma in pulses of well-de fined width and frequency using ultra fastswitches.Fig.3.Current –voltage curves of a magnetron during operation in dcMS and HPPMS mode.The change of the slope from 7to 1at a voltage value of 650V indicates loss of the electron con finement (data taken from [33]).Fig. 4.Cross-section SEM image of two via holes with an aspect ratio 1:2homogeneously filled by Cu using HPPMS (reprinted from [31]after permission,1999©Elsevier).1663K.Sarakinos et al./Surface &Coatings Technology 204(2010)1661–1684first step of the discharge is made of a weakly ionized regime,while the second part of the pulse brings the glow discharge to the high ionization state.The weakly ionized regime allows for the formation of a stable discharge prior to entering the highly ionized regime which helps to suppress the arc formation during the high power mode of operation [54].3.Plasma dynamics in HPPMS 3.1.On the HPPMS plasmaPlasmas are partially ionized gases characterized by,for example,the charge (electron)density or the electron energy distribution function [55].A classi fication of different plasmas could be based on the charge density as shown in Fig.9,where the magnetron sputtering plasmas are shown to exhibit densities ranging from ∼1014up to 1020m −3.It is known that high density plasmas such as arc plasmas exhibit high ionization fractions [25,31].This is not the case for conventional magnetron plasmas where the electron density does not exceed the value of 1016m −3,penning ionization is the main ionization mechanism [30]and therefore the ionization of the sputtered species is at the best of few percent [13].In order to achieve a high ion fraction in a discharge it is necessary to promote the electron impact ionization [55]which is best realized by increasing the electron density and temperature.Different approaches have been made to achieve this,for example by using an electron cyclotron resonance (ECR)plasma as a plasma electron source [56],or by employing an inductively coupled plasma (ICP)[57,58].A higher frequency of electron impact ionization collisions can alsobeFig.5.Target current and voltage waveforms produced by the power supply developed by Kouznetsov et al.at working pressures of (a)0.06Pa,(b)0.26Pa,(c)1.33Pa and (d)2.66Pa.The charging voltage of 1000V drops down to 800V and the plasma is ignited.Peak target currents of up to 230A are achieved.The time lag for the ignition of the plasma decreases when the pressure is increased (reprinted from [35]after permission,2002©Elsevier).Fig.6.Rectangular shape voltage waveforms generated by the HPPMS power supply developed by MELEC GmbH.The data were recorded from an Ar –Al HPPMS discharge operating at pulse on/off time con figuration 25/475µs (K.Sarakinos,unpublisheddata).Fig.7.Temporal evolution of target voltage and current during operation using a 10µs long pulse.The target current is interrupted before the plasma enters into the steady-state regime.The data were recorded from an Ar –Ti HPPMS discharge (S.Konstantinidis unpublished data).1664K.Sarakinos et al./Surface &Coatings Technology 204(2010)1661–1684achieved by increasing the power to the sputter source and therewith the electron density.This approach is,however,limited since a power excess can result in an overheating of the target or an exceeding of the Curie temperature of the magnetron's magnets.Thus,the work of Kouznetsov et al.[31]opened a new era of magnetron sputtering deposition and plasma studies,since it allowed for the generation of highly ionized plasmas using a conventional magnetron source.The early analyses of the HPPMS plasma showed that its temporal characteristics are complex and unique [35,59,60].Understanding the discharge evolution and the mechanisms that take place in the plasma is therefore of utmost importance as this sheds light on the growth conditions during the thin film deposition.To achieve this,modeling and a number of analytical studies have been carried out,using Langmuir probes as well as optical emission,mass,and absorption spectroscopy techniques.These studies are reviewed in the following chapters and the basic properties of the HPPMS plasma are thus outlined.3.2.Determination of plasma properties:a theoretical overview Plasmas are commonly modeled as fluids,and each species is described with its fluid equation [61].The fluid approximation is suf ficiently accurate to describe the majority of observed plasma phenomena.When this is not viable,the accumulated behavior of anensemble of charged particles is described using a statistical approach,in the form of the velocity distribution function which is given as f (r,u,t )d 3r d 3u ,i.e.the number of particles inside a six-dimensional phase space volume d 3r d 3u at (r ,u )and time t [55].Here,r is the position vector and u is the speed vector.Knowing the distribution function,fundamental features of a large ensemble can be quanti fied,i.e.by integrating over the velocity,the average (macroscopic)quantities associated with the plasma are de fined as:n ðr ;t Þ=∫f ðr ;u ;t Þd u plasmanumber ðion ;electron ;orneutral Þdensityð2Þu Àðr ;t Þ=1n∫u f ðr ;u ;t Þd u plasmabulkfluid velocity ð3ÞεÀðr ;t Þ=m 2n∫ðu À−u Þ2f ðr ;u ;t Þd u plasmameankineticenergy ð4Þwhere m is the particle (ion,electron,or neutral)mass.This procedure of integrating over velocity space is referred to as taking velocity moments,with each one yielding a physically signi ficant quantity.Knowledge of the electron energy (velocity)distribution function (EEDF)permits us to determine important parameters.The EEDF can be measured using a Langmuir probe,as was demonstrated by Druyvesteyn [55]:g e ðV Þ=2m e A pr 2eV m12d 2I edV ð5Þwhere A pr is the probe area,I e is the electron current,m is the electronmass,and V =V pl −V b is the potential difference between the plasma potential and the probe potential.With the change of variables ε=eV ,the electron density n e is determined as:n e =∫∞0g e ðεÞd εð6ÞPlasma parameters,such as the electron density,are easily obtained if the mathematical description of the EEDF is Maxwellian.The Maxwellian distribution is characterized by its single temperature and is obtained when plasma electrons undergo enough collisions and are in equilibrium with other plasma components and with the electron ensemble itself.At a low pressure,the EEDF is generally non-Maxwellian,and the electron temperature is thought of as aneffectiveFig.8.Target voltage and current waveforms during the long-pulse operation.In the first 500µs a weakly ionized plasma is generated which is followed by a highly ionized steady-state plasma (reprinted from [54]after permission,Society of Vacuum Coaters ©2007).Fig.9.Plasma density is used in order to classify plasmas.The HPPMS plasma spans over a large density range depending on the pulse on/off time con figuration used for a process and presents therefore a tool for better choosing the plasma dynamics needed for the deposition process.The abbreviation ECR stands for Electron Cyclotron Resonance (taken from [36]).1665K.Sarakinos et al./Surface &Coatings Technology 204(2010)1661–1684electron temperature,T eff∼23〈ε〉,representing the mean electron energy determined from the EEDF according to[55]:〈ε〉=1n e ∫∞εg eðεÞdεð7Þ3.3.The HPPMS plasma propertiesOne of the earliest works related to the study of the properties of the HPPMS plasma was carried out by Gudmundsson et al.[35,59]. Using a Langmuir probe[62]in an Ar–Ta plasma,they measured the temporal behavior of the EEDF by recording the time-dependent probe current curves.It was shown that the EEDF evolved from a Druyvesteyn-like distribution with a broad energy distribution(high average energy)during the pulse to a double Maxwellian distribution (i.e.a distribution that is composed of two-distinct energy-distribu-tions)toward the end of the pulse,andfinally a Maxwellian-like distribution hundreds ofµs after the pulse had been switched off.This is shown in Fig.10,where the temporal evolution of the EEDF is also seen to be affected by the working pressure[35].Similar results were obtained by Pajdarova et al.[63],although the double Maxwellian distribution was observed from the beginning of the pulse,which could be explained by the nature of the target material(Cu in this case)and the HPPMS parameters used in the experiments.Further-more,it was found that the effective electron temperature peaked a fewµs after the pulse start,and at the same time,independent of measurement position[35].This is indicative of the existence of high energy electrons accelerated by the target voltage,and thus escaping the confinement region in the vicinity of the cathode[35].InaFig.10.The EEDF(electron energy distribution function)for an HPPMS plasma with a100µs on-time and a50Hz frequency at three chamber pressures(a)0.25,(b)1.33,and(c) 2.66Pa.The distribution function changes during the pulse from a Druvesteyn distribution to a double-Maxwellian distribution(reprinted from[35]after permission,Elsevier©2002).1666K.Sarakinos et al./Surface&Coatings Technology204(2010)1661–1684different study by Seo et al.[64],Langmuir probes were utilized to determine the properties of a HPPMS plasma at a higher pulsing frequency of 10kHz and a duty cycle of 10%.By using such a high frequency,the electron density reached a value of 1.5×1017m −3,which could be seen as a relatively low density HPPMS plasma.The temporal evolution of the energy distribution in this plasma showed ef ficient electron heating,which took place within the first few µs from the pulse start.This work revealed that the plasma dynamics presented in the studies by Gudmundsson et al.[35,59]are to a large extent general features of the low duty cycle pulsed plasmas regardless of the frequency.The early studies on the HPPMS plasma characteristics also showed the potentially high ionization fraction of the sputtered material that could be achieved by using this technique [16,25,33,60,65,66].Spectroscopic analyses,such as optical emission spectroscopy [67–69],mass spectroscopy [69],and absorption spectroscopy [68,69]were,therefore,employed in order to better quantify and understand the average and time-dependent evolution of the ion population in the HPPMS plasma.The optical emission studies [33,65,70–72],were performed both for the HPPMS and the dcMS discharges and showed the much higher metal ion emission intensity in HPPMS (Fig.11).However,in order to better quantify these observations,absorption spectroscopy [70,71,73,74]and mass spectroscopy [75,76]studies were performed,con firming the much higher ionization of the sputtered material and of the sputtering gas achieved in HPPMS.One well studied material in this regard is Ti.Mass spectroscopy measurements of the peak ion compositions in an Ar –Ti discharge for the pulse on-time of 100µs and a frequency of 50Hz [75]showed that the ionized part of the plasma contained 50%of Ti 1+,24%of Ti 2+,23%of Ar 1+,and 3%of Ar 2+ions.When longer pulse on-times of several hundreds of µs were used even Ti 3+and Ti 4+could also be detected [77].It is deduced that for the formation of multiply charged ions certain conditions should be ful filled [77];(i)the discharge should contain a high enough number of metal ions,(ii)the pulse on-time should be long enough (and the capacitance of the used power supply should be large enough to store enough energy for the whole pulse),(iii)the self-sputtering yield (i.e.the sputtering yield of the target material from ionized target species)should be low,and (iv)the ionization energy of each ionization step should not be too high.These two examples show clearly that the HPPMS plasma properties depend not only on the plasma density and energy distribution but also,to a large degree,on the pulse on/off time con figuration.Since the introduction of the HPPMS technique,most of the discharge studies have been performed for pulses with pulses on-time longer than 50µs.Exceptions to this can be found in the works by Konstantinidis et al.[70,73],Ganciu et al.[44],and Vasina et al.[48],where shorter pulses ranging between 5and 30µs have been used,an example of which is shown in ing time-resolved optical emission spectroscopy in a Ti –Ar discharge,an increase in the line intensity ratio of the ion-to-neutral Ti and Ar species with increasing the pulse duration was observed [70].This means that the ionization degree increases with increasing pulse length,indicating the necessity for the sputtered atoms to reside a suf ficient time in the target vicinity for the vapor to become ionized.The increase of the AremissionFig.11.Optical emission spectroscopy from a typical HPPMS plasma.The emission from the Ti and Ar species increases greatly in HPPMS indicating the high ionization of the metal and gas species (data taken from [72]).Fig.10(continued ).1667K.Sarakinos et al./Surface &Coatings Technology 204(2010)1661–1684。

Chemical Engineering Science62(2007)1948–1957/locate/cesStructure and rate of growth of whey protein deposit from in situ electrical conductivity during fouling in a plate heat exchanger Romuald Guérin,Gilles Ronse,Laurent Bouvier,Pascal Debreyne,Guillaume Delaplace∗UR638,Génie des Procédés et Technologie Alimentaires,INRA,F-59651,Villenueve d’Ascq,FranceReceived7August2006;received in revised form13December2006;accepted15December2006Available online30December2006This paper is dedicated to the memory of Dr Jean-Claude LeulietAbstractThe influences of calcium concentrations(70.88mg/l),Reynolds number(2000–5000)and temperature(60.96◦C)upon the deposit structure and the rate of growth deposition have been investigated in a plate heat exchanger.This was done from in situ measurements of the deposit electrical conductivity via implementation of stainless steel electrodes in channels combined with assessments of deposit thickness.Calcium ions affect structures of deposits and increase the rate of deposit growth upon heated surfaces.This was attributed to the formation of weaker size aggregates at higher calcium concentrations and a higher number of calcium bindings,which reinforce adhesion forces between protein aggregates.Structures and appearances of deposits also were affected byflow rates whatever the calcium concentrations.Deposit growth rate was enhanced by increasingflow rate below a critical Reynolds number comprised between3200and5000.On the contrary,above the critical Reynolds number,a limitation of the deposit and/or an escape of the deposit from the fouled layer into the corefluid occurred,caused by the predominance of particle breakage on the deposit formation.Fouling tended to be reduced at higherflow rate.It was noteworthy that rates of growth decrease during fouling experiments which may be explained by an increase in local shear stresses leading to particle breakage.᭧2007Elsevier Ltd.All rights reserved.Keywords:Fouling;Whey protein;Calcium ions;Reynolds number;Shear stress;Deposit structure;Plate heat exchanger;Electrical conductivity1.IntroductionPlate heat exchangers(PHEs)are widely used in food indus-tries.Several advantages in using PHEs have been discussed elsewhere(Corrieu,1980;Bond,1981).The main problems en-countered by users of heat exchangers are linked to fouling,cor-rosion or mechanical resistance.Bott(1992)shows that fouling of heat exchangers,classically observed with dairy products, is in the front row of the industrial preoccupations.Fouling of heated surfaces directly contributes toward increased costs in production and energy losses,cleaning,and hinders a constant product quality and overall process efficiency(Yoon and Lund, 1989;Delplace et al.,1994;Jeurnink and de Kruif,1995;Visser and Jeurnink,1997).∗Corresponding author.E-mail address:delapla@lille.inra.fr(G.Delaplace).0009-2509/$-see front matter᭧2007Elsevier Ltd.All rights reserved. doi:10.1016/j.ces.2006.12.038In dairy industries,deposits consist of a layer of protein aggregates and minerals(Tissier and Lalande,1986).Among all milk proteins, -lactoglobulin has been identified as one of the major contributors to fouling as it undergoes thermal denaturation(Lalande et al.,1985;Lalande and Rene,1988; Gotham et al.,1989).Consequently,whey protein concentrate (WPC)solutions often have applied as a modelfluid to mimic fouling reactions during pasteurisation of milk both in the bulk and in the deposit at heat surfaces.There has been a considerable amount of work showing that fouling affects hydrodynamic and thermodynamic perfor-mances of heat exchangers.These studies,carried out with different dairy product compositions and process conditions, put forward the main parameters which interfere upon the foul-ing deposit mass(De Jong et al.,1992;Belmar-Beiny et al., 1993;Delplace et al.,1994;Delplace and Leuliet,1995;Fryer et al.,1996;Changani et al.,1997;Visser and Jeurnink,1997;R.Guérin et al./Chemical Engineering Science62(2007)1948–19571949Christian et al.,2002;Prakash et al.,2006).The main param-eters were for instance wall temperatures andflow rate as pro-cess parameters and ionic force,type of ions,pH and protein concentration as chemical composition parameters.All these works represent an important step forward in the generation of predictive models both on -lactoglobulin denatu-ration or global thermal performance degradation for the whole heat exchangers(Fryer and Slater,1985;De Jong et al.,1992; Delplace et al.,1994;Fryer et al.,1996;Visser and Jeurnink, 1997).Unfortunately,these models are not powerful enough to explain the distinct cleaning behaviours experimentally ob-served.For instance,Christian et al.(2002)showed that overall cleaning times and cleaning rates,under standard conditions, were dependant on the deposit composition.There is a lack of knowledge concerning the influence of deposit structure and kinetic of deposit mass upon the cleaning efficiency to get rid off the total mass deposit.To overcome these difficulties,stud-ies that report the effect of process parameters and composi-tion upon the structure of the fouled layer are required.The aim of this work was partly to contribute to thisfield.In par-ticular,various controlled conditions offlow rate and calcium concentration of a WPC solution in a PHE were carried out to determine the influence of these parameters upon the structure and the kinetic of fouled layers.The structure and the growth of the fouled layer were estimated in-line from in situ measurements of the electrical conductivity of the fouled deposit.This was done by the im-plementation of two opposite stainless steel electrodes in PHE channels.In the last section,the electrode system was imple-mented in various channels to determine the influence of the temperature upon the deposit.2.Materials and methods2.1.ModelfluidThe modelfluid used in this study was reconstituted from WPC75supplied by Armor Proteines(France).The compo-sition of the powder as given by the manufacturer is shown in Table1.Proteins are the main components of the WPC pow-der(76%w/w)in which -lactoglobulin and -lactalbumin represent63%(w/w)and11%(w/w),respectively.Minerals represented less than4%(w/w)of the total dry weight of the powder.To produce solutions with higher mineral concentra-tion,the powder was dispersed in controlled quality water. Water consisted of a mixture of tap water of Lille(France)and soft water using a water softener(HI-FLO1,Culligan, Purolite C100E resin,France).The calcium and sodium con-tents of tap water,determined by atomic absorption spectropho-tometry(Philips,Pye Unicam),varied in the range170–200 and44–64mg/l,respectively.The range of calcium and sodium contents of the soft water were1.0–3.0and304–341mg/l, respectively.The desired content of calcium of the fouling fluid was obtained by mixing raw water,soft water and afixed amount of powder(1%w/w).Water electrical conductivity var-ied from0.113to0.116S/m at20◦C for calcium concentration varying from35to55mg/l.The product electrical conductivity Table1Composition of WPC powder(Armor Protéines,France)and1.0%WPC solutionComponent WPC75powder(%w/w)1.0%WPC75solution(%w/w) Water 5.599.05Lactose100.1Lipids 3.70.037Protein760.76Casein––-lactoglobulin480.48-lactalbumin8.40.084Other19.80.198Minerals40.04Calcium0.450.007–0.00875 Sodium0.700.0277–0.0472 Potassium0.33N.D.Chloride0.40N.D. Phosphorus0.30N.D. Magnesium0.045N.D.Iron0.008N.D.Other 1.77N.D.Other0.8N.D.:Not determined.Fig.1.Schematic of the experimental setup.varied from0.142to0.146S/m at20◦C for a range of calcium of70–90mg/l.The addition of protein powder to the mixing of water modified the electrical conductivity value of20%. The pH of the modelfluid remained between7.3and7.7.2.2.Fouling experimentThe experimental set-up of pilot plant scale is shown in Fig.1.Although there are two heat exchangers(model V7 plates,Alfa-Laval Vicarb,France)in the setup,the fouling1950R.Guérin et al./Chemical Engineering Science 62(2007)1948–1957ELECTRICAL CONDUCTIVITY SENSOR TEMPERATURE PROBE Pi PLATE NUMBERCi RODUCT CHANNEL NUMBERHOT WATER HOT WATER Fig.2.Heating plate heat exchanger flow arrangement and implementation of stainless steel electrodes inside channels.observations were focused on the second.The first one was used only to pre-heat the model fluid up to 60◦C where fouling was negligible.Water was used as the heating medium.The model fluid was heated from 60to 96◦C in a countercurrent mode.The choice of temperatures was made taking into account the value of the denaturation temperature of the -lactoglobulin protein.Temperature value for the denaturation of -lactoglobulin is 74.76◦C (Matsudomi et al.,1991;Xiong,1992;Gotham et al.,1989;Liu et al.,1994).PHE setup consisted of 13plates form-ing six passes of one channel for the two sides (Fig.2).The equivalent space between two consecutive plates was 3.93mm.In order to keep the feed composition constant,the fluid was not re-circulated once it was heated through PHEs.During ex-periments,the inlet temperature of hot water was adjusted to ensure a constant outlet model fluid temperature close to 96◦C and a constant profile of product temperature along the PHE as a function of time (i.e.,constant heat flux).The fluid foul-ing layer interface temperature in each channel was assumed constant during fouling runs.In the beginning,the PHE was brought to thermal equilibrium and desired process temperature using reverse osmosis (RO)water.The feed was switched from RO water to model fluid and the experimental run was contin-ued for 330min.After the fouling experiment,model fluid was replaced by cold RO water to bring the temperature of PHE and deposits to ambient temperature.Experiments were performed for various calcium concentrations and Reynolds numbers as shown in Table 2.Reynolds numbers were computed based on physical properties of water,assuming that the presence of 1%WPC in water does not modify them significantly.Average Reynolds number for the clean heat exchanger was determined from the distribution of Re along the PHE (Re =2 Q/ w ).Inlet and outlet model fluids and hot water temperatures were measured with platinum resistance probes (type pt100)with a precision of 0.1◦C.Bulk and wall temperatures in chan-nels were measured from J-type thermocouples with a preci-sion of 0.5◦C.Flow rates were measured using electromag-netic flowmeters (Krohne IFM,Germany).All parameters were collected via a data acquisition system (Agilent Technologies 34970A,USA)with an acquisition period of 30s.2.3.Measurements of fouled layer thicknessDeposit thickness on the different plates was obtained by two ways:•Using a pneumatic lifting device of a uniaxial compres-sion machine (DY30Model,Adamel Lhomargy,TMI,USA)which allows to determine the distance between the support of the device and the upper of the fouled or cleaned plate as shown in Fig.3.The precision of the measurement was 0.01mm.The assessments were performed at nine positions on the plate surface.The average value of the deposit thick-ness was computed from the nine positions.•By weighing plates before and after fouling runs using a Mettler apparatus (PM3000,Switzerland)with a preci-sion of 0.1g.From a wet deposit density value equal to 1000kg /m 3(Lalande et al.,1985),the average deposit thick-ness upon each plate was obtained.Of course,this method assumes that the deposit occurs uniformly upon the plate surface.2.4.Electrical conductivity of the depositTwo AISI 304L stainless steel electrodes 0.015×0.01m were implemented in channels C3,C5and C6(Fig.2).Elec-trodes were connected to a commercial conditioning system (STRATOS 2402Cond,Knick,Germany).Electrodes were electrically insulated from metal plates using an insulating stick (Araldite A V138M-HV998,USA).The cell constant of the de-vice was determined with salt solutions whose electrical con-ductivity value was known with precision.The stainless steel electrodes provide an indication of the equivalent electrical resistance R eq through the channel (Fig.4).For fixed operating conditions,the Kirchhoff’s rule allows decoupling the equivalent electrical resistance in terms of fouling fluid electrical resistance (R p )and deposit electrical resistance (R d )as follows:R eq =R p +2R d .(1)R.Guérin et al./Chemical Engineering Science 62(2007)1948–19571951T a b l e 2S u m m a r y o f m e a s u r e d a n d c a l c u l a t e d p a r a m e t e r s d u r i n g h e a t t r a n s f e r t o s t u d y f o u l i n g b e h a v i o u r o f 1%W P C s o l u t i o nR u n M e a n R e (–)C a 2+(m g /l )N a +(m g /l )i ,p (◦C ) o ,p (◦C ) i ,h w (◦C ) o ,h w (◦C )M a s s o f d e p o s i tt =0t ft =0t f t =0t f t =0t fi n c h a n n e l 5(g )A 200072.9344.062.360.096.897.2102.5104.572.873.471.9B 200378.9303.260.059.796.596.6102.6107.771.976.0118.6C 204082.2280.061.561.397.196.3102.7107.973.479.1147.1D 204085.6277.460.461.595.896.9102.0109.271.980.4180.6E 339470.0323.663.863.995.595.7102.0107.475.080.8100.3F 322076.3472.061.361.395.795.5101.7115.973.489.1170.0G 321478.0364.962.662.295.095.0100.0112.374.083.9201.2H 323286.5331.262.763.694.694.6101.4121.773.293.2240.6I 493874.6329.060.861.495.495.2103.4110.974.383.490.2J 492077.4303.061.360.896.296.0103.1113.574.084.994.2K 494277.8340.063.263.995.495.1103.0111.875.286.8116.6L 492687.4306.061.261.495.995.7103.5121.374.393.3190.5R u n¯e d (M D -5)(m m )¯e d (U C M )(m m )w *(◦C ) b (◦C ) e q *(S /m ) p a t b (S /m ) p a t 100◦C (S /m ) d *a t w (S /m )d *a t 100◦C (S /m )k ×104(S /m m i n )A 0.480.4097.991.10.3030.3600.3880.2080.2101.90B 0.800.61101.990.60.3030.3730.4030.2630.2612.33C 0.980.92102.491.60.3070.3710.3980.2850.2832.82D 1.201.16105.490.10.2970.3720.4040.2750.2703.57E 0.670.69103.689.70.2480.3610.3940.1700.1673.96F 1.201.28112.289.70.2840.4720.5040.2510.2408.19G 1.341.42108.889.30.2320.3750.4090.2240.2166.50H 1.601.55118.789.80.3320.4770.5090.3370.3206.88I 0.600.59105.289.80.2460.3910.4230.1470.1425.67J 0.630.63108.590.10.2250.3600.3920.1410.1335.60K 0.780.75106.889.50.2130.3690.4020.1510.1454.75L 1.271.37121.189.80.2730.3790.4110.2280.2096.70p , d a n d e q :f o u l i n g p r o d u c t ,d e p o s i t a n d e q u i v a l e n t e l e c t r i c a l c o n d u c t i v i t y ,r e s p e c t i v e l y ; i ,p a n d o ,p :i n l e t a n d o u t l e t t e m p e r a t u r e o f t h e p r o d u c t ; i ,h w a n d o ,h w :i n l e t a n d o u t l e t t e m p e r a t u r e o f t h e h o t w a t e r ; w a n d b :w a l l a n d b u l k t e m p e r a t u r e i n c h a n n e l 5;¯ed (U C M ):a ve r a g e d e p o s i t t h i c k n e s sf r o m t h e u n i a x i a l c o m p r e s s i o n m a c h i n e ;e d (M D -5):d e p o s i t t h i c k n e s s f r o m m a s s d e p o s i t i n c h a n n e l 5;k :r a t e o f c h a ng e o f th e e q ui v a l e n t e l e c t r i c a l c o n d u c t i v i t y .∗A t330m i n .1952R.Guérin et al./Chemical Engineering Science 62(2007)1948–1957Based on the general relationship linking the electrical resis-tance to the electrical conductivity for a pair of electrodes [ =e E /(AR)with e E the length between the electrodes,A the cross-section and R the electrical resistance]and assuming that (i)the cross-section A is a constant value and (ii)the space of the fluid flow (e fl)is defined as the difference between thespace0.000 N0.005 N e 10.000 N0.005 N e 2Fouling layerStainless steel plateacbdFig.3.The thickness measurement technique using a pneumatic lifting device of a uniaxial compression machine (DY30Model,Adamel Lhomargy,TMI,USA).P 8P 9Isolating materia l Stainless steel electrodes Fluid flow Fouling layer R eqR dR dRp ABFlow directioneEFig.4.Schematic of the fouling layer and equivalent electric resistance diagram.separating the two electrodes (e E )minus the total deposit thick-ness (2e d )(Eq.(2)),the deposit electrical conductivity (DEC, d )can be expressed as a function of model fluid ( p )and equivalent ( eq )electrical conductivities as shown in Eq.(3).e fl=e E −2e d ,(2)d (t =t f )=e E2e d (t =t f ) 1eq (t =tf )−1p+1p−1.(3)At the beginning of the fouling experiment (i.e.,clean PHE),the value of the equivalent electrical conductivity,measured by the device,corresponded to the electrical conductivity of the model fluid ( p )at the product temperature.The electrical con-ductivity of the model fluid was invariant during fouling runs since the inlet temperature of hot water was adjusted to ensure a constant product temperature inside channels as a function of time.At the end of fouling runs (i.e.,fouled plates,t =t f )the deposit thickness was measured and the measurement of the equivalent electrical conductivity allowed to obtain the electri-cal conductivity of the deposit.In order to compare electrical conductivity values of each run,all conductivities were deter-mined at 100◦C as follows (Ayadi,2005): d(100◦C )= d( w )+0.0009×(100− w ), p(100◦C )= p( b )+0.0032×(100− b ),(4)where d(100◦C )represents the DEC value at 100◦C, d( w )is the DEC determined from Eq.(3)at the end wall tempera-ture w , p(100◦C )is the electrical conductivity of the fouling product at 100◦C, p( b )represents the value of the electrical conductivity of the product at the bulk temperature b .Considering a deposit temperature nearly constant and an invariant viscosity value for the product,the only parametersR.Guérin et al./Chemical Engineering Science 62(2007)1948–195719530.20.220.240.260.280.30.320.340.360.380.4Time, (min )E q u i v a l e n t e l e c t r i c a l c o n d u c t i v i t y , (S m -1)Fig.5.Equivalent electrical conductivity during fouling run using 1.0%WPC solution with calcium concentration 78.0mg /l at Re =3200.which affect DEC values are mobility and concentration of ions (Benoıˆt and Deransart,1976).However,considering a poor mobility and diffusion of ions from the bulk fluid through the fouled layers due to protein networks,the DEC values are affected in the majority by the concentration of ions embedded inside the protein structure.Thus,these values constitute a good indicator of the deposit structure.3.Results and discussion3.1.Effect of calcium content on foulingTypical equivalent electrical conductivity change as a func-tion of time,measured in-line from the electrodes in the fifth channel,is illustrated in Fig.5.After the switch from RO water to fouling fluid,the equivalent electrical conductivity reaches a maximum value at t =15min.This value corresponds to the electrical conductivity of the product at the bulk temperature.Data reported in Table 2show that product electrical conduc-tivity values at 100◦C are little affected by the modification of the ionic concentration (i.e.,calcium and sodium in the tested range of concentration)of the solution.At the beginning of fouling stages,very slow decreases in equivalent electrical conductivity are recorded with an initial rate k ∗(Fig.5).This region may be attributed to a homogeneous thin layer of irreversibly adsorbed individual protein molecules on clean metal surfaces (Arnebrant et al.,1985;Visser and Jeurnink,1997).Tissier and Lalande (1986)showed that this sublayer had a thickness of 0.02 m after only few minutes of contact;0.4and 1 m after 10and 30min of fouling run.This weak thickness may explain the slight decrease of the slope between t =15and 30min.The slightly decreasing slope (k ∗)indicates that the fouling mechanism starts immediately when fouling product is present in the heating zone,for a temperature higher than unfolding temperature of -lactoglobulin.After this period,the equivalent electrical conductivity decreases24681060657075808590Calcium content, (mg/l)k x 104, (S .m -1.m i n -1)parison of rates of deposit growth (k )as a function of calcium concentration in WPC solution for Re =2000,3200and 5000.(The trend lines represent the curve fit of data .)linearly with time.The rate of electrical conductivity changes k is relatively high (Fig.5).The second decrease in eq may be attributed to the growth and structure changes of fouled layers.Indeed,whatever the Reynolds number,it is observed that the rate of electrical conductivity changes k rises with in-creasing calcium concentrations (Fig.6).This observation is in agreement with Li et al.(1994)observing that calcium induces conformational changes of the -lactoglobulin,facilitating the protein denaturation,but also increases the kinetic of the aggregate formation.A small change in the calcium concen-tration has an important impact upon the kinetic parameter k ,i.e.,the formation of the fouled layer.Fig.7a illustrates the electrical conductivity values of the fouled layer (DEC)obtained at a wall temperature of 100◦C in the fifth channel for varying calcium concentrations at three Reynolds numbers.Whatever the Reynolds number,the DEC increases with the calcium concentration.Considering a low mobility of ions inside the deposit due to protein networks and a constant temperature in C5,this indicates that the DEC1954R.Guérin et al./Chemical Engineering Science 62(2007)1948–19570.10.20.30.4Calcium concentration,(mg.l -1)E l e c t r i c a l c o n d u c t i v i t y o f t h e d e p o s i t , (S .m -1)00.20.40.60.811.21.41.61.8Calcium concentration, (mg.l -1)F o u l e d l a y e r t h i c k n e s s e d , (m m )05001000150020002500300035004000Calcium content, (mg/l)A m o u n t o f d e p o s i t i n c h a n n e l 5, (g /m 2)parison of (a)deposit electrical conductivity at 100◦C,(b)fouled layer deposit and (c)amount of deposit in channel 5after 5.5h of heat transfer in PHE as a function of calcium concentration in WPC solution for Re =2000,3200and 5000.(The trend lines represent the curve fit of data.)is affected by the deposit thickness and its structure which depends on the calcium concentration (Fig.7b).A small change in the calcium concentration has an important impact upon the fouling behaviour.Figs.6and 7indicate that calcium ions (i)are essential in the growth of fouled layers as suggested by Xiong (1992)since amounts of deposit increase with calcium concentration (Fig.7c),(ii)modify the rate of protein aggregation and (iii)lead to a greater cohesion between protein aggregates modify-ing the deposit structure.Indeed,visual analysis of the deposit after fouling runs at Re 3200using 1.0%WPC solutions revealed that fouled layers formed with low calcium content(78mg/l)have a spongy and soft texture whereas deposits formed at higher calcium content (86.5mg/l)are denser and elastic.This observation is in agreement with Pappas and Rothwell (1991)who showed that -lactoglobulin completely aggregated to form compact structures when heated with cal-cium.Simmons et al.(2007)also showed that increasing the levels of calcium had a dramatic effect on the size of the aggre-gates produced,which decreased with increasing mineral con-centration.An explanation for the difference in structure and kinetic is that calcium ions,essentially present in the deposit solid (Tissier and Lalande,1986),lead to lower size aggregates in the range of calcium concentration (70–88mg/l)and favour the growth of fouled layers by formation of bridges between adsorbed proteins and the protein aggregates formed in the bulk (Fig.8).Bridges may be formed via carboxyl groups of amino acids of -lactoglobulin as suggested by Xiong (1992).In-creasing the level of calcium would lead in a higher number of bridges resulting in a bigger stabilisation of protein aggregates as interpreted by Daufin et al.(1987)and Xiong (1992),forming a narrow network which embed other ions present in the solution (i.e.,sodium,magnesium,phosphate,calcium,…),and reinforce the adhesion forces between proteins.3.2.Effect of hydrodynamics conditions on foulingFig.5shows that rates of equivalent electrical conductivity changes are not constant as function of time since the slope of equivalent electrical conductivity decreased after t =180min.This slope modification in eq may be due to a decrease of the aggregate deposit and/or an escape of the deposit from the fouled layer into the core fluid caused by particle breakage.This can be a consequence of an additional local shear stress as deposit thickness evolved (Fig.9).Indeed,shear stress in a channel is a function of channel section which is reduced with the growing fouled layer [ = .¯u. /(2(e E −2e d ))].This confirms the assumption of Kern and Seaton (1959)who were the first to underline that the formation of a fouled layer is a consequence of the rate of aggregate entry and the rate at which they escape.Fig.10illustrates the evolution of the kinetic parameter k during fouling with a 1.0%WPC solution at calcium concen-tration of 78mg /l as a function of Reynolds number.The in-crease of k between Re 2000and 3200can be explained by a weaker size of aggregates at higher shear rate for a fixed tem-perature (Simmons et al.,2007)favouring the growth of the deposit and resulting in a different deposit structures (Fig.8).Deposit masses in channel 5confirm this trend namely for a fixed calcium concentration,the amount of deposit in C5in-creases between Re 2000and 3200(Fig.7c).Nevertheless,the k parameter decreases between Re 3200and 5000at a fixed calcium concentration.Thus,the decrease of the rate of deposit is due to the increase of Reynolds number which may limit the deposit,compact the structure upon the heated surface and increase the rate of particle breakage.Visual analysis of the appearance of the deposit as a function of Reynolds number confirm the trends.Deposit formed after fouling with a calcium concentration close to 78mg /l at Re 2000has a granular aspectR.Guérin et al./Chemical Engineering Science 62(2007)1948–19571955Adsorbed protein AggregatesStainless steel electrodes Stainless steel plate With lower calcium concentraionEmbedded ionsCalcium bindingsWith higher calcium concentraionFig.8.Schematic illustration of the proposed formation of the deposit with lower and higher calcium concentrations of the WPC solution.0.20.40.60.811.21.47076.37886.5Calcium concentration, (mg/l)L o c a l s h e a r s t r e s s , (P a )20406080100120140160180200Shear stress for fouled channel (C5)Shear stress for cleaned channel (C5)Increase of shear stressI n c r e a s e o f s h e a r s t r e s s , (%)Fig.9.Increase in shear stresses due to fouled layer growth as a function of calcium concentrations in 1.0%WPC solutions at Re =3200.probably due to higher size aggregates whereas deposit formed at Re 3200appears more denser (i.e.,lower aggregates size).Finally,the deposit obtained after fouling at Re 5000appears more smooth and compact which may be the consequence of the increase of the local shear stress (Fig.9).Another way to underline the influence of shear stress upon the structure of the deposit is the measurement of the electri-cal conductivity of deposits according to Reynolds numbers for a fixed calcium content and temperature (Fig.7a–c).Fig.7a shows that DEC values are similar at Re 2000and 3200while amounts of deposit in C5,and so the thickness of the deposit (Figs.7b and c),are completely different with a scatter close to 35%.In the same order,amounts of deposit in C5are similar for Re 2000and 5000while the correspondingvalues of DEC1234567200032005000Reynolds number, (-)k x 104, (S m -1 m i n -1)Fig.10.Rates of deposit growth (k )as a function of Reynolds number during fouling runs with a 1.0%WPC solution with calcium concentration comprised between 76.0and 78.0mg /l.differ each other.Moreover,for a fixed calcium concentration,DEC values increase with a variation of Reynolds number from 2000to 3200while a decrease in DEC values can be observed above a critical Reynolds number,which could be comprised between 3200and 5000.Since calcium concentration and tem-perature are invariant and considering a poor mobility of ions due to protein networks,differences in the structure and/or the composition of the deposit can be explained by DEC variations.This indicates that shear stress has a dramatic effect upon the structure and the appearance of the deposit whatever the cal-cium concentrations.The differences in the structure of these。

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第 21 卷 第 12 期2023 年 12 月太赫兹科学与电子信息学报Journal of Terahertz Science and Electronic Information TechnologyVol.21，No.12Dec.，2023基于二氧化钒超材料的双窄带太赫兹吸收器曹俊豪，饶志明*，李超(江西师范大学物理与通信电子学院，江西南昌330224)摘要：提出一种基于二氧化钒(VO2)超材料的吸收器，由3层结构组成，从上往下分别为2个VO2圆、中间介质层和金属底板。

仿真数据表明，该吸收器有2个很强的吸收峰，分别为4.96 THz 和5.64 THz，相对应的吸收率为99.1%和98.5%。

利用阻抗匹配理论和电场分布进行分析，阐明了吸收的物理机制，并进一步分析了结构参数对吸收率的影响。

所提出的吸收器具有可调谐的特点，能够灵活调控吸收率，为太赫兹波的调控、滤波等功能的实现提供了良好的方案。

该吸收器在图像处理、生物探测和无线通信领域都有潜在的应用。

关键词：太赫兹；超材料；二氧化钒；吸收器中图分类号：TB34 文献标志码：A doi：10.11805/TKYDA2023148 Dual-narrowband THz absorber based on vanadium dioxide metamaterialCAO Junhao，RAO Zhiming*，LI Chao(College of Physics and Communication Electronics，Jiangxi Normal University，Nanchang Jiangxi 330224，China)AbstractAbstract：：A metamaterial absorber based on vanadium dioxide(VO2) is presented. This structure consists of three layers including two vanadium dioxide circles, intermediate dielectric layer, and metalsubstrate from top to bottom. The simulated data shows that the absorber has two strong absorption peaks,at 4.96 THz and 5.64 THz respectively, and the corresponding absorption rates reach 99.1% and 98.5%.The physical mechanism of absorption is clarified by using the impedance matching theory and theelectric field distribution. The effect of the structural parameters on the absorption rate is also analyzed.In addition, the proposed absorber can regulate the absorption rate flexibly, which provides a goodscheme for the realization of terahertz wave regulation, filtering and other functions. Therefore, thisabsorber has potential applications in image processing, biological detection, and wireless communication.KeywordsKeywords：：THz；metamaterial；vanadium dioxide；absorber太赫兹波是指频率为0.1~10 THz的电磁波，相应波长为30 μm~3 mm，它的电磁波谱左侧和右侧分别为电子学和光子学，因此也被称为太赫兹间隙[1]。

Appendix C：Glossary 附录C：名词解释α helixα螺旋A helical secondary structure in proteins. Pl.α helices. 蛋白质中一种螺旋形的二级结构。

复数：α helices。

α-amanitinα鹅膏蕈碱A toxin that inhibits the three eukaryotic RNA polymerases to different extents. Name derives from mushroom of genus Amanita in which toxin is found. 一种能不同程度地抑制三种真核生物RNA聚合酶的毒素。

名称来自于产生此毒素的Amanita属蘑菇。

β-galactosidaseβ-半乳糖苷酶Enzyme that cleaves lactose into galactose and glucose. Name origin: the bond cut by this enzyme is called a β-galactosidic bond. 将乳糖分解为半乳糖和葡萄糖的酶。

名称来源：该酶切割的键称为β-半乳糖苷键。

β sheetβ折叠A secondary structure in proteins, relatively flat and formed hydrogen bonding between two parallel or anti-parallel stretches of polypeptide. 蛋白质的一种二级结构，相对平坦，在两条平行的或反向平行的肽段之间形成氢键。

σsubunitσ亚基Component of prokaryotic RNA polymerase holoenzyme. Required for recognition of promoters. 原核生物RNA聚合酶全酶的组成成分。

The history and economics of gold mining in ChinaRui Zhang,Huayan Pian ⁎,M.Santosh,Shouting ZhangSchool of Earth Sciences and Resources,China University of Geosciences Beijing,29Xueyuan Road,Beijing 100083,Chinaa b s t r a c ta r t i c l e i n f o Article history:Received 23January 2014Received in revised form 4March 2014Accepted 5March 2014Available online 20March 2014Keywords:Gold deposits Geology History Economics ChinaAs the largest producer of gold in the world,China's gold reserves are spread across a number of orogenic belts that were constructed around ancient craton margins during various subduction –collision cycles,as well as with-in the cratonic interior along reactivated paleo-sutures.Among the major gold deposits in China is the unique class of world's richest gold mines in the Jiaodong Peninsula in the eastern part of the North China Craton with an overall endowment of N 3000tons.Following the dawn of metal in the third millennium BC in western China,placer gold mining was soon in practice,particularly during the Xia,Shang and Zhou dynasties.During 1096AD,mining techniques were developed to dig underground tunnels and the earliest mineral processing technology was in place to pan gold from crushed rock ores.However,ancient China did not witness any major breakthrough in gold exploitation and production,and the growth in the gold ownership was partly due to the ‘Silk Road ’that enabled the sale of silk products and exquisite artifacts to the west in exchange of gold prod-ucts.In the modern times,the proven reserves of gold resources in China have steadily increased from 4614.7tons in 2005up to 6864.79tons in 2010,with a growth rate of 48.76%.In the past ten years,the rate of production increased by 70%,launching China as the top producer of gold in the world in 2008when the produc-tion reached 300tons per year.The gross industrial output of gold industry in China increased sharply from 20.82billion Yuan up to 229.29billion Yuan between 2000and 2010,registering 9times growth,and breaking the world record.A simultaneous hike in the proportion of gross value in GDP from 0.21%in 2003up to 0.58%in 2010is also recorded.©2014Elsevier B.V.All rights reserved.1.IntroductionChina currently ranks as the largest producer of gold in the world.The country's gold reserves are associated with a number of major tectonic belts that traverse the junctions of ancient microblocks or were built along the craton margins during subduction –collision tecton-ics (Goldfarb and Santosh,2014;Zhai and Santosh,2013).Some gold deposits also occur within the interior of the cratonic block along reactivated paleo-sutures (Li and Santosh,2014).The gold deposits range in size from small (5–20tons Au),medium (20–50tons Au),and large (50–100tons Au)to super-large (N 100tons Au).Among the various gold belts,those in the Jiaodong Peninsula in eastern China,de-fine the country's largest gold province with an overall endowment es-timated as N 3000tons Au (Goldfarb and Santosh,2014,and references therein).Despite the leadership that China enjoys in world gold production,very little published information exists in international scienti fic literature related to the history and economics of gold mining in this country.In this paper,we attempt to trace the gold deposits and records of gold mining in ancient China from historical reviews and publications in Chinese literature.We also synthesize the updated information onthe economic aspects of gold production in China in relation to those in the rest of the world.2.Geological background of gold deposits in ChinaThe gold deposits in China and surrounding regions are distributed along several major belts including craton margins,intracratonic sutures and continental collision zones.In a recent overview,Goldfarb et al.(2014)presented the salient characteristics,ages and tectonic af finities of the major gold fields in East Asia,and the summary below on the gold deposits in China is largely based on this work.The Qilian and West Qinling orogenic belts in the southwestern margin of the North China Craton carry signi ficant gold resources,classi fied as orogenic gold deposits (Goldfarb et al.,2014).Those in the Qilian belt include the deposits hosted in Ordovician arc volcanic rocks of the North Qilian terrane and the Tanjianshan deposit occurring within Mesoproterozoic phyllite and felsic to intermediate igneous rocks of the North Qaidam block.The reported ages of the gold mineral-ization range between 214and 285Ma (Mao et al.,2000;Zhang et al.,2009).In West Qinling,both orogenic and Carlin-type gold deposits have been reported (Mao et al.,2000)and the ore formation dated at ca.216Ma is correlated to a transtensional event (Zeng et al.,2012).Goldfarb et al.(2014)considered the Late Triassic as an important phase of gold formation associated with the waning phases of NE –SWOre Geology Reviews 65(2015)718–727⁎Corresponding author.E-mail address:huayanpian@ (H.Pian)./10.1016/j.oregeorev.2014.03.0040169-1368/©2014Elsevier B.V.All rightsreserved.Contents lists available at ScienceDirectOre Geology Reviewsj o u r n a l h o m e p a g e :w ww.e l s e v i e r.c o m/l o c a t e /o r e g e o r e vdirected compression resulting from the collision of the North and South China blocks.The Xiaoqinling region in the south-western margin of the NCC has been well known for large scale mining for gold since the Ming Dynasty(AD1368–1644).According to Li and Santosh(2014), more than1200auriferous quartz veins have been explored in this region,among which about400tons of gold reserve has been proved and more than10large and super-large gold deposits are exploited.A number of large crypto-explosive-breccia type gold deposits occur in the Xiong'ershan region in eastern Qinling within the southern margin of the NCC(Chen et al.,2008).In the northern margin of the NCC, some large and super-large gold deposits occur in the Jibei region.In the Yangtze Block of South China,gold reserves are associated with the Jiangnan Orogen,a Neoproterozoic suture that resulted from the collision between the Yangtze and Cathaysia Blocks.Gold deposits in the Jiangnan Orogen occur along the inboard side of the orogen and continue into adjacent parts of the Paleozoic foreland basin(Goldfarb et al.,2014).The available ages show a broad range from514to 370Ma(Lu et al.,2005).The Jinshan gold deposit,the largest one in the area,occurs in the eastern part of the Jiangnan Orogen.Although debates surround the timing of gold formation in the Jiangnan Orogen, with ages ranging from Neoproterozoic to Jurassic,most workers correlate the metallogeny to the Caledonian event(Goldfarb et al.,2014).The Middle to Late Paleozoic units in the Central Asian Orogenic Belt are important hosts for gold.In the Northern Tien Shan region,several subduction and arc-related auriferous porphyry magmatic systems have been recognized(e.g.,Seltmann and Porter,2005;Shen et al., 2012).In the eastern part of Northern Tien Shan,in the western domain of Beishan suture(Xiao et al.,2010),more than100small gold deposits and prospects have been identified proximal to the east–west thrust faults and strike-slip faults.Their ages range between300and230Ma and broadly overlap with the Permian–Early Triassic accretionary deformation(Goldfarb et al.,2014).Gold deposits in the Cathaysialand region are mainly associated with subduction-related magmatism during the late Paleozoic closure of ocean basins between South China and Indochina–East Malaya (Goldfarb et al.,2014;Metcalfe,2011).Few hundreds of gold deposits occur in the large Permo-Triassic Youjiang Basin that represents a foreland basin of the accretionary margin of Cathaysialand.The Mesozoic gold deposits in the Central Asian Orogenic Belt include those contributing to the placer gold accumulations in northeast China(Goldfarb et al.,2014),such as the500km long ductile shear-zone hosted belt along the Erguna River along the Russia–China border(Wu et al.,2006).Some of the oldest known gold deposits in this region are distributed along the northern margin of the North China Craton,mostly within Late Archean and Paleoproterozoic basement uplifts(Goldfarb et al.,2014)located between Bayan Obo in the north and Baotou in the south.Some deposits in this belt are younger,such as the Saiyinwusu gold deposit with ages in the range of260–250Ma and the Dongping deposit with an age of ca.150Ma,suggesting that the orogenic deposits in this region might be of Triassic age(Hart et al.,2002).In northeastern China,north of the NCC,epithermal gold ores related to subduction and convergence occur within Middle to Late Jurassic andesites Other epithermal deposits,mostly volcanic-related also occur at the northeastern end of the Great Xing'an Range(Goldfarb et al.,2014).Gold mineralization also occurs in the interior domains of the NCC, particularly along the Trans-North China Orogen that welds the West-ern and Eastern Blocks of the craton(Li and Santosh,2014).Examples include the Shihu gold quartz-vein deposit in the west of Hebei Province within the central domain of the Taihang Mountains(Li et al.,2013)and the Yixingzhai auriferous quartz-vein in the northeast of Shanxi Province,at the northern domain of the Taihang Mountains(Li et al., 2012).The cryptoexplosive breccia-type and skarn-type gold deposit in the Luxi area,west of the Tan–Lu Fault are also some other examples (Guo et al.,2013).Forming part of the Jiao–Liao gold province distributed in Western Shandong,Jiaodong Peninsula and southeastern Liaoning(Yang et al.,2003),the gold deposits of Jiaodong in the eastern part of the NCC constitute one of the richest gold reserves in the world,and also define a unique class of gold mineralization(Goldfarb and Santosh,2014;Yang and Santosh,2014;Yang et al.,2013).Ranging in age from126to 120Ma,they constitute one of the major orefields for gold in East Asia(Goldfarb et al.,2014),and the largest gold province in China with an overall endowment estimated as N3000tons Au,accounting for more than25%of China's gold reserves(Guo et al.,2013).The gold mineralization in Jiaodong has been classified into the Linglong-type that occurs as extensional massive gold–quartz–pyrite veins,and Jiaojia-type forming disseminated veinlets and wallrock disseminations (Goldfarb and Santosh,2014;Li and Santosh,2014;Qiu et al.,2002). Both types of ores are principally hosted by NE-to NNE-trending brittle normal faults that parallel the margins of the Jurassic and Cretaceous granitoids,with the larger orebodies associated with dilational jogs (Goldfarb and Santosh,2014).Although the tectonic setting and ore genesis of the Jiaodong gold deposits have remained equivocal,it has been recently recognized that they constitute a unique class of gold de-posits associated with intraplate processes(Li and Santosh,2014;Zhai and Santosh,2013;Zhai et al.,2004a,b,c).Several gold-bearing skarn,porphyry and magmatic vein deposits with ages ranging from151to135Ma occur in the Lower to Middle Yangtze River province in South China(e.g.,Mao et al.,2011;Pang et al.,2013).The dominant deposits are Cu–Mo–Au-bearing porphyry deposits with bulk of the gold occurring within garnet-and pyroxene-rich copper skarns that developed in carbonate rocks(Goldfarb et al., 2014).Important gold resources also occur in the South China Fold Belt representing a classic late Mesozoic basin and range region(e.g., Pirajno and Bagas,2002).Similar to the Yangtze River province,the tectonics in this region is associated with the change from north–south convergence between the North and South China blocks in the Triassic to a NW–SE Pacific plate subduction below the South China block in the Jurassic(Goldfarb et al.,2014).Some of the gold deposits in this belt are argued to be part of the early Paleozoic Jiangnan gold belt(Goldfarb et al.,2014).The Mesozoic and Cenozoic deformation belt in the Tibetan–Himala-yan orogen marking the closure of the Tethys oceans associated with the collision between the Indian and Asian continents is also an important gold-bearing province.Numerous orogenic gold and gold-bearing porphyry provinces have been identified within the Himalayan orogen, including the Ailaoshan gold belt(Hou and Cook,2009).The Miocene (18–13Ma)Gangdese Cu–Au porphyry belt in South Lhasa(Li et al., 2004),the Yulong and the Bangongco(Li et al.,2005)define three major porphyry belts of gold associated with the Himalayan orogeny (Goldfarb et al.,2014).Gold also occurs in the alkali granite porphyries hosting skarn and polymetallic veins in the western Yunnan region, with ages in the range of ca.37–33Ma(Goldfarb et al.,2014).Among the major gold deposits in various provinces of China (Table1),at least seven super-large(N100tons Au),and twenty large(50to100tons Au)deposits have been identified based on the estimated ore reserves.There are also several medium to small(20to 50and b20tons Au)deposits(Fig.1).3.Historical sketch3.1.Gold production and development in ancient ChinaIn ancient China,the Bronze Age society(2000–771BC)was primarily engaged in agriculture with supplementary hunting andfishing,headed by regional leaders and supported by extensive kinship groups.Early in the preceding Neolithic period,jade,the locally available precious stone was awarded a pride place as the symbol of purity and prestige for the elite.The dawn of metal has been documented as early as the third millennium BC in some parts of western China,when small copper and bronze items have been recently unearthed(Bunker,1993).719R.Zhang et al./Ore Geology Reviews65(2015)718–727After the introduction of metal working into metropolitan China,bronze became the major material for the manufacture of ritual vessels and other paraphernalia.Together,jade and bronze were considered as the most valued artistic materials.In ancient metropolitan China,the precious metals like gold and silver were not important and did not re-flect status.Instead,gold and silver were first used primarily for their color to enhance artifacts made of other materials,such as bronze and lacquer.Although gold eventually represented many of their qualities,the yellow metal did not completely replace jade and bronze for the manufacture of artifacts which were considered as the primary symbols of immortality,prestige and power (Bunker,1993).During the Xia,Shang and Zhou dynasties (ca.2100–256BC),gold mining was mainly focused on placer deposits,where the miner pours material from a stream bed into a rocker box,which is rocked back and forth to separate gold dust from the sand and gravel.Although min-ing level of gold was relatively low,people of that time perfected the technique of making vessels and utensils by using gold.The archeological excavations show gold objects introduced by the Shang Dynasty including artifacts such as gold scepter,gold earrings and gold mask (Han et al.,2006).During the Spring –Autumn (770–476BC)and Warring States Period (475–221BC)(Primal trek,2013),China abounded with gold,as gold production was flourishing at this time through both mining and utiliza-tion.In the Xia,Shang and Zhou dynasties,the purposes of using gold were only for making utensils and decorations to human body,whereas in the Warring States Period,historical relics unearthed in Chu state demonstrate that the first gold coin was cast in Chinese history,expanding the scope of gold as a currency (Han et al.,2006).The only minted gold of this period known is Chu Gold Block Money,which con-sists of sheets of gold 3–5mm thick,of various sizes,with inscriptionsTable 1Major gold deposits in China.Source:Wang et al.(2008).DepositCountyProvince A.Super-large gold deposits (Au reserve N 100tons)Zijinshan Shanghang Fujian Jinshan Dexing Jiangxi Jiaojia Laizhou Shandong Linglong Zhaoyuan Shandong Wenyu Lingbao Henan Lannigou Zhenfeng Guizhou Yangshan Wenxian Gansurge gold deposits (Au reserve N 50–100tons)Dongping Chongli HebeiYuerya Kuancheng Hebei Shihu Lingshou Hebei Xiaotongjiabuzhi Fengcheng Liaoning Maoling Gaizhou Liaoning Jinchang Dongning Heilongjiang Tuanjiegou Jiayingou Heilongjiang Dayingezhuang Zhaoyuan Shandong Dongfeng Zhaoyuan Shandong Shuikoushan Changning Hunan Qiuluo Ganzhi Sichuan Dongbeizhai Songpan Sichuan Shuiyindong Zhenfeng Guizhou Jinlongshan Zhen'an Shaanxi Liba Lixian Gansu Dashui Maqu Gansu Zhaishang Minxian Gansu Tanjianshan Haixi Qinghai Dachang Qumalai Qinghai Axi YiningXinjiangFig.1.The distribution of major super-large,large and medium-type of gold deposits in China.After Wang et al.(2008).720R.Zhang et al./Ore Geology Reviews 65(2015)718–727consisting of square or round stamps in which there are one or two characters.They have been unearthed in various locations south of the Yellow River indicating that they were products of the State of Chu (Wikipedia,2014a,b,c).Archeological surveys led to the discovery of gold coins from the Chu State in many parts of China including Anhui,Shandong,Henan,Hubei and Jiangsu,suggesting widespread circulation of such coins at that time.However,gold was confined for circulation within certain states and areas,and also among rulers,and was not used as free and extensive as the copper coins or other form of coins in the market at that time (Han et al.,2006).In the‘Spring’and‘Autumn’Periods,gold expanded its horizon in Chinese civilization.The metal was still used for massive decorations.According to their surface decorative techniques these can be divided into gem inlay,gilding,gold and silver inlay,copper inlay,engraved decoration,surface tin-enrichment,mother-of-pearl inlay,burnished works with gold or silver inlay,surface coloring and cloisonnéenamel,etc.Casting gold coins achieved a major break-through(Tan and Lian,2011).In the mining side,skills for picking gold and mining gold steadily improved through practice and experience accumulated from three generations in the Xia,Shang and Zhou dynasties.Some of the criteria used in those days for prospecting gold include:(1)recognition of miner-alization from outcrop features and oxidation zone;(2)stratigraphic color;and(3)peculiar terrain features.Archeological records show the discovery of many marks of gold mines and the initiation of preparation of simple geological maps.In the mining sector,the high density of gold was employed for the gravitational method to wash out silt and pick gold.The development of dredging method made a great advance in processing placer deposits and enhancing gold production(Han et al., 2006).The Qin and Han dynasties(221BC–220AD)saw further progress in gold mining.The Qin Dynasty lasted only for14years,with only limited development in gold mining.However,the Hans existed for prolonged period of426years,when social stability and economic growth promot-ed gold production.This period was considered as one of the most prosperous periods in Chinese history.In the primary stage of the West Han Dynasty,the total volume of gold production reached more than one million jin,a unit of weight(=12kg).Based on Chinese metrology of the past,in the West Han Dynasty1jin goes to248g of the present,in the East Han Dynasty1jin goes to220g of the present, and thus,one million jin in West Han is equivalent to248tons of gold as on today(Qiu,1992).The estimated gold reserves in China during 2003were600tons,which means that the gold reserves in the West Han Dynasty has reached41.3%of the total amount of the present age (Newspaper of Gold in China,2004).Because of the rich gold reserves,the emperor of the Han Dynasty spared plenty of gold to reward his generals who have rendered great ser-vices to his state.In the early years of the Han Dynasty,the shape of gold unearthed resembled gold pie,which included rounded,irregular and persimmon gold(Han et al.,2006).In the stay society of the Han Dynasty, the demand for gold artifacts increased steadily.The gold artifacts unearthed show not only large quantities,but also higher craftsmanship.The years of war and chaos during the period of the Three Kingdoms (220–265BC),namely,Wei(220–265),Shu Han(221–263)and Wu (222–280)—the Jin Dynasty(265–420),the Northern and Southern Dynasties(420–589)(Xie,2011)—severely affected the economy causing a decline in gold production.The influence of this was also reflected in(1)change in the unit of measurement of gold from jin to liang(=50g),(2)imperial court stopping the grant of gold,and(3)a ban on use of gold for marriage.Eventually,the processing of gold and silver artifacts achieved a high degree of development.In the Tang Dynasty(618–906BC),gold and silver had made fairly great development.Many glittering and gleaming gold and silver crafts found in recent decades became one of the magnif-icent,dazzling sign for the prosperous andflourishing Tang Dynasty (Addison,2012).The nobles in the Tang Dynasty admired gold;during this time,the society was stable,economy was prosperous,and the emperor often bestowed gold and silver utensils on his generals who rendered great ernment officials in different levels also paid gold and silver utensils as tribute to the emperor,so the court and nobles valued improvements in the processing technology and craftsmanship of these artifacts.The society also treated gold and silver utensils as treasure and were exchanged as gifts and for trade,which enhanced the consumption of gold and silver.Gold production pros-pered and special organizations were established for the management and processing workshops.A royal workshop was set up for making gold and silver utensils during the Tang Dynasty named as“Wen Si Court”.These steps enormously promoted the development and crafts-manship of gold and silver artifacts in the Tang Dynasty(Han et al., 2006).The Song,Yuan,Ming and Qing dynasties(960–1912BC)ruled for more than800years.In the Song Dynasty,the government allowed free exploitation of gold mines for social stability and to strengthen the dominance of power.Until1033AD,exploitation of gold by common people was prohibited,and the development of gold and silver industry declined.In the Yuan Dynasty,to safeguard their dominant position and prevent rebellion from people of central China,the then governor divided people from all nations into different classes,where the gold miner was the lowest class,even below those of ordinary people.Therefore gold mining did not see much development in the Yuan Dynasty.In the Ming and Qing dynasties,the government adopted policy for mining surveillance and management,and heavy tax was levied that forced gold miners to revolt and escape.The kingdom's stability was threatened,and the development of gold mining industry remained stagnant.In the Qing Dynasty,although gold mining was allowed by government,a large-scale exploitation was prohibited.So exploitation of gold and silver did not develop very well.According to historical records,in the Song Dynasty the methods for gold mining were developed from traditional mining for placer gold into rock gold.Miners began to dig underground tunnels.They recognized“stone with gold”as a gold ore-hunting indicator.During 1096A.D.,they learned to crush gold ores to relative small particles and pan gold particles out of them,which is the earliest mineral processing technology.The exploitation of rock gold underground,emergence of mineral processing technology and employment of ore concept illustrate how the gold mining industry in ancient China had made periodic development and progress in the Song Dynasty(Han et al.,2006).3.2.Gold distribution in ancient ChinaThe earliest gold output in the world was920tons in3900–2000BC, which does not include the production from China.In2100–1200BC (equivalent to the Xia and Shang dynasties in China),the world gold output was2645tons,and the grand total added up to3565tons. During this period,China had its own gold output,which was20tons. This is the earliest recordedfigure in China as far as we know(Tu et al.,2002).According to historical records,gold was very popular in Chu(state) during the Zhou Dynasty(ca.1046–256BC).Gold coin wasfirst made during this period in Chinese history.There were various types of coins their sphere of circulation was broad,indicating that gold output was relatively higher in state,although no precise statistics are available.The‘Book of Former Han’,says that the gross reserves of gold in the Han Dynasty had reached up to one and a half millions Jin,which is equivalent to approximately372tons(Qiu,1992).Given that gold reserves of the People's Bank of China are600tons,the Han Dynasty gold is about41.3%of the present day reserve(Newspaper of Gold in China,2004).In the Tang Dynasty which was in existence for290years,the cumu-lative production of gold was approximately156tons.The gross output of gold production in the Song Dynasty was about52tons,that of the721R.Zhang et al./Ore Geology Reviews65(2015)718–727Yuan Dynasty was39tons,that of the Ming Dynasty was23tons,and the Qing Dynasty produced30.5tons(Han et al.,2006).The historical records show that the areas for gold mining in the early Qing Dynasty(1662–1795AD)included Qianan,Kuanhe,and Fengrun in Hebei Province;Wenshang,Zhaoyuan,Laiyang,Linqu,and Chuzhou in Shandong Province;Longquan in Zhejiang Province; Zhangye,Dunhuang,and Zamatu in Gansu Province;Tianzhu,Xinan, and Zhenyuan in Guizhou Province;Yicheng,Dazhi,and Shishou in Hubei Province;Jingzhou,Ruanling,and Yiyang in Hunan Province; Huaiji in Guangxi Province;Tacheng,Urumqi,and Yili in Xinjiang Autonomous Region;and Yongchang,Yongbei,and Kaihua in Yunnan Province(Xia,1980).A map showing the gold distributions in ancient China(after Tu et al.,2002)is presented in Fig.2.Gold placer was the major source for recognition and exploitation in the ancient time in China.Rock gold was found in the Han,Sui and Tang dynasties.From the regional distribution,it is clear that gold mines were extensively found in the middle or lower reaches of the Yellow River, such as the Shanxi,Henan,Shandong,and Hebei provinces,and several occurrences were also found in the middle and lower reaches of the Yangtze River.The Pearl River Basin including the Guangdong,Guangxi, Yunnan,and Sichuan provinces come second for gold mines compared with the regions in the Yellow River.From the Sui and Tang to Ming and Qing dynasties,gold mines were found and developed in the Liao-ning and Heilongjiang provinces of north-east China.The distribution of gold mines is in accordance with the level of economic and cultural development in different regions of China.In general,the exploitation of gold occurred earlier in the developed regions as compared to the de-veloping regions.Gold exploitation and utilization wereflourishing in the Xia,Shang and Zhou dynasties,and then came the golden age in the Han and the Three Kingdom dynasties.Thereafter it began to decline in the Sui and Tang dynasties,andfluctuated from time to time in the Yuan,Ming and Qing dynasties(Tu et al.,2002).3.3.The Silk Road and development of goldThe Silk Road,or Silk Route,is a series of trade and cultural transmis-sion routes that were central to cultural interaction through regions of the Asian continent.Extending6437km,it connected the East and West by linking traders,merchants,pilgrims,monks,soldiers,nomads and urban dwellers from China to the Mediterranean Sea(Fig.3).The Silk Road gets its name from the lucrative Chinese silk trade,and began during the Han Dynasty(206BC–220AD).The central Asian sections of the trade routes were expanded around114BC by the Han Dynasty,but earlier trade routes across the continents already existed (Wikipedia,2014a,b,c).Trade on the Silk Road was a significant factor in the development of the civilizations of China,the Indian subcontinent,Persia,Europe and Arabia(Wikipedia,2014a,b,c).Silk-like porcelain originated from China,and had become the symbol of prosperity and civilization in East Asia at that time.Caravans mostly exported silk,ironware,silver-ware,gold ware,mirror and other luxury products from China and imported rare animals and birds,plants,fur,herbs,spices,jewelers, etc.from the west(Li,1996).In the past few years,archeologists in China and abroad found many graves of different dynasties,and the most common character of these graves was golden funeral objects buried for emperors and noblemen in ancient times.This suggests that almost all the nations along the Silk Road adored gold and the circulation of gold was common and well-developed.Examples include the6ancient tombs full of gold found in Tilly-Then relics of Afghanistan(Li,1996).Gold wasalsoFig.2.The distribution of ancient gold workings in China.After Tu et al.(2002).722R.Zhang et al./Ore Geology Reviews65(2015)718–727。

Atomic Layer Deposited MoS 2as a Carbon and Binder FreeLi-ion BatteryDipK Nandi,UttamK Sen1,DevikaChoudhury,Sagar Mitra,Shaibal K Sarkar *Department of Energy Science and Engineering,IIT Bombay,Mumbai 400076,IndiaA R T I C L E I N F O Article history:Received 3June 2014Received in revised form 22August 2014Accepted 3September 2014Available online 22September 2014Keywords:Atomic layer deposition Molybdenum sul fideQuartz crystal microbalanceFourier transform infrared spectroscopy Lithium-ion batteriesA B S T R A C TMolybdenum sul fide is deposited by atomic layer deposition (ALD)using molybdenum hexacarbonyl and sul fide.Film growth is studied using in-situ quartz crystal microbalance,ex-situ X-ray flectivity and ellipsometry.Deposition chemistry is further investigated with in-situ Fourier transform spectroscopy.Self-limiting nature of the reaction is observed,typical of ALD.Saturated growth of 2.5Åper cycle at 170 C is obtained.As-deposited films are found amorphous in nature.As-grown lms are tested as lithium-ion battery anode under half cell con figuration.Electrochemical charge-discharge measurements demonstrate a stable cyclic performance with good capacity retention.Discharge capacity of 851mAh g À1is obtained after 50cycles which corresponds to 77%of capacity retention of the initial capacity.ã2014Elsevier Ltd.All rights reserved.1.IntroductionSimilar to other transition metals,Mo has multiple oxidation states leading to different sul fide like MoS 2,Mo 2S 3and MoS 3[1–4].Among the above,MoS 2was studied most due to its layered crystallographic assembly [5,6].A schematic of layered MoS 2structure is shown in Fig.1.Thin film MoS 2was demonstrated in a variety of electronic applications [7,8].Lately,MoS 2also drew considerable attention for its application as anode material in Li-ion battery [9–16].Theoretically MoS 2can accommodate 4Li ions through conversion reaction leading to a gravimetric capacity of 670mAh g À1.In literature,a reversible capacity in the range of 850to 900mAh g À1has been reported using bare MoS 2[9–16].As lithiation induced microstructural and chemical changes take place in MoS 2,the governing chemistry of MoS 2opens up the possibility of employing amorphous materials directly as an electrode for lithium ion battery application.It is expected that chemical and microstructural changes in amorphous materials during lithiation can be energetically preferred in comparison to its crystalline phase.Among several existing thin film deposition technologies,atomic layer deposition (ALD)has an advantage of conformal deposition on complex substrates [17].Surface bound self-limiting growth with precise thickness control ensures the applicability of ALD in variety of applications [18–21].Though the application of ALD in electrochemical storage is overwhelming,but till now the use is mostly limited to the protection layer to enhance the electrochemical performance of the electrode [22–27].In recent literature,ALD was used to produce thin films of active material for lithium ion battery application [28–32].TiO 2was mostly studied system in this category [28,31,32].Recently SnO 2[29]and V 2O 5[32]were also prepared by ALD technology and successfully used as active material for lithium ion batteries.In this paper,we report a new ALD chemistry to deposit amorphous molybdenum sulphide.Film growth was studied by in-situ quartz crystal microbalance (QCM),ex-situ X-ray re flectivity (XRR)and Ellipsometry measurements.A narrow ALD temperature window between 155–170 C with characteristic saturated growth of ca.2.5Åper cycle was observed under self-limiting condition.In-situ Fourier transform infrared spectroscopy (FTIR)was employed to understand the surface limited half-reactions.The as-deposited molybdenum sul fide films were found to exhibit good electrochemical activity as anode material in lithium ion battery.A stable electrochemical performance was achieved with 375nm of film thickness.Here we emphasize on a carbon and binder free electrode that showed a well comparable electrochemical performance at par with the existing literature.*Corresponding author.Tel.:+912225767846;fax:+912225764890.E-mail address:shaibal.sarkar@iitb.ac.in (S.K.Sarkar).1Contributed equally./10.1016/j.electacta.2014.09.0770013-4686/ã2014Elsevier Ltd.All rights reserved.Electrochimica Acta 146(2014)706–713Contents lists available at ScienceDirectElectrochimica Actaj o u rn a l h o m e p a g e :w w w.e l s e v i e r.c o m /l o c a t e /e l e c t a c t a2.Experimental Section2.1.Material SynthesisMoS2depositions were carried out in a custom-built hot-wall viscousflow ALD reactor,equipped with capacitance manometer and rotary vent pump.A constant pressure of1Torr was maintained byflowing ca.350sccm of high purity(99.999%) nitrogen gas during the reaction.The N2stream ensures laminar flow of the reactants over the substrate surface.Reactants were introduced into the reactor with the help of a combination of metered valves and computer controlled pneumatic valves connected in series.This arrangement ensured controlled dosage of the reactants into the reactor.The precursors were kept at room temperature but fed to the reactor along differentially heated channels.Mo(CO)6was dosed with an overhead N2flow arrangement.During the reaction,a minimum of15s purging time was maintained between two consecutive doses.2.2.Material characterizationsFilm deposition was monitored in-situ with quartz crystal microbalance(QCM).QCM measures change in the resonance frequency when mass is deposited on the crystal.The deposited mass was derived using Sauerbrey equation.We used6MHz AT cut QCM crystal with polished gold coating that was glued to the drawer and retainer assembly purchased from Inficon.Under steady state condition,a mass resolution of<1nm was obtained. Before any deposition,100cycles of ALD grown Al2O3was deposited to keep the starting surface similar during different reactions.In-situ Fourier transformed infrared spectroscopy was per-formed to determine the surface species during each ALD half reactions.KBr pellets were used as substrates for this in-situ FTIR measurement.The measurement was carried out in a different reactor with similar configuration apart from the ZnSe windows through which the IR beam was passed.The reactor was isolated from the window and the spectrometer by a combination of pneumatic gate valves.The transmitted beams were recorded with a liquid N2cooled MCT detector.The measurements were performed with Bruker Vertex-70FTIR spectrophotometer.X-ray reflectivity measurements were executed with Bruker D8Advanced diffractometer equipped with Cu-K a source.For reflectivity measurements,films were deposited on polished Si surface to minimize the interfacial roughness while for the diffraction measurements standard microscope glass substrates were used to eliminate any substrate effect.Experimentally obtained XRR data wasfitted with the help of commercially available software,Parratt32to get the thickness and the density of thefilm.The thickness measurements thus obtained from the XRR were further verified with spectroscopic ellipsometry(Sentech) measurements at an incident angle of70degree.All elemental analysis was performed with X-ray photoelectron spectroscopy measurements in Thermo VG Scientific photoelectron spectrome-ter(MultiLab)equipped with Al-K a source(1486.6eV).Polished Si was used as a substrate for preparing thefilms for XPS measure-ments.Peaksfitting and analysis was done using XPS peak 4.1software.Raman spectroscopy was performed in a Raman spectrometer(Jobin Yvon HR8000)having514.5nm laser tofind the different vibrational modes of the as depositedfilms.Films are grownon microscopic glass substrates for Raman spectroscopic measurements.2.3.Cell fabrication and electrochemical characterizationConventional charge-discharge measurements were performed under galvanostatic condition in a coin cell assembly with a cell configuration of Li/Electrolyte/MoS2.Thefilm was directly grown on a stainless steel substrate under saturated condition that was used as an anode without any further modifications.All cells were assembled under Argon atmosphere inside glove box(Mbraun, Germany).Thin Li foil was used for both reference and counter electrodes.A well-documented standard electrolyte consisting of 1M LiPF6in EC/DMC(1:1wt/wt)(LP-30,Merck,Germany)was used for all electrochemical measurements.Watman borosilicate glass microfiberfilters were used as a separator between the electrodes.Cyclic voltammetry was obtained with a scan rate of 0.2mV sÀ1using Biologic VMP-3within potential window3V to 0.01V vs.Li/Li+.Electrochemical impedance spectroscopy(EIS) measurements were carried out at open circuit voltage for the frequency range of1MHz to0.1Hz using Biologic VMP-3. Electrochemical charge-discharge measurements were performed with Arbin Instruments at constant current density of20m A cmÀ2. During all electrochemical measurements,a constant temperature of20 C was maintained.3.Results and DiscussionChemical vapor deposition(CVD)of molybdenum sulfide using Mo(CO)6and H2S was reported earlier[33].The thermal CVD reaction can be read as follows,Mo(CO)6+H2S!MoS2+n H2+m COFor atomic layer deposition,the above reaction can be split in to two separate half-reactionsMo(CO)x*+H2S!Mo-SH y*+n H2+m CO(A)Mo-SH y*+Mo(CO)6!MoS-Mo(CO)x*+n H2+m CO(B)Where*denotes the surface species.The above pair of surface reactions predicted at this point, however does not obsolete the possibilities of other reaction pathways.From the as predicted half reactions,it can be wellFig.1.Schematic of a layered MoS2structure.D.K.Nandi et al./Electrochimica Acta146(2014)706–713707understood that the ALD reactions are surface limited.Gaseous precursors are dosed into the reaction chamber that reacts with the surface species.Reactions continue till all the surface species gets converted to a newer functionality.The unconsumed reactants and the reaction products are simultaneously pumped out from the reaction chamber.The rate limiting surface reaction thus ensures the layer-by-layer growth of the material.As mentioned earlier,repeating the AB cycles sequentially felicitates MoS 2deposition.During the course of these reactions,the Mo(CO)6and H 2S exposures and purging time was maintained by time sequence n*1s-t 1-m*1s-t 2where n and m are the number of doses for Mo(CO)6and H 2S respectively while t 1and t 2are the purge times,which is invariably set for 15s,unless otherwise speci fied.The dose time for Mo(CO)6and H 2S were set for 1s,where n and m,the respective number of exposures were varied from 1to 5.To validate that the nature of growth follows the self saturating mechanism,mass change per cycle was measured using QCM with increase in the number of reactant doses.Mo(CO)6being the solid reactant,we preferred to vary the number of doses rather than the dose time.Fig.2a shows the deposition growth rate versus the number of Mo(CO)6precursor doses,measured in-situ with QCM and veri fied with ellipsometry and XRR measurements.For ellipsometry and XRR measurements,films were grown on Si wafer with native SiO 2.In case of the QCM measurements,the mass gain was calculated from the change in oscillation frequency of the quartz crystal using Sauerbrey's equation.The QCM was also calibrated with the known deposition of Al 2O 3using trimethyl aluminum (TMA)and H 2O prior to start all of our measurementsrelated to MoS 2deposition.The growth per cycle was observed to level off at 2.5Åper cycle corresponding to 3–4metal precursor doses that yielded a total dose of 18x106L where L stands for Langmur,the unit of precursor exposure into the reactor (1L is equivalent to the exposure of 10À6Torr during 1s).Further increase in the reactants above the limiting value did not provide any extra mass gain indicating the self-limiting behaviour in the growth,as found typically for ALD.Similar characteristic was observed with varied H 2S pulses that saturated from the first pulse itself (not shown here).The saturation dose for H 2S was found to be ca.2.5Â106L.The self-limiting nature of the ALD reaction from QCM was also veri fied independently by spectroscopic ellipsom-etry and XRR measurements.Experimentally obtained Kiessig fringes with fitting model that include 20ÅSiO 2and the metal sul fide layer is shown in the inset of figure 2a.The program fits individual densities and thicknesses of individual layer separately.The material density as calculated from the scattering length density was found to be 3.85g cm À3,which was substantially lower than the bulk value of MoS 2.This discrepancy can be attributed to the amorphous nature of the deposit,discussed below.Furthermore,the study was extended to understand the temperature dependence of the film growth with in-situ QCM.The ALD temperature window was found out by QCM measure-ments with the saturating pulsing condition (4*1s-15s-1s-15s)as observed from self-limiting growth (Fig.2a).A relatively narrow ALD temperature window was observed within the temperature range of 155–170 C,as shown in Fig.2b with an average growth rate of 2.4Åper ALD cycle.Similar temperature window was alsoFig.2.(a)Growth rate of film with the increasing number of Mo(CO)6precursor exposure measured by QCM,XRR and Ellipsometry (in inset XRR scan of MoS 2ALD film on a silicon substrate after 200cycles at 170 C that yields a film thickness of 10nm)and (b)Growth per ALD cycle with increasing substrate temperature.Fig.3.(a)Two complete ALD cycles showing the mass gain in two individual half reactions along with their corresponding precursor pressures;(b)Mass gain vs.ALD cycles monitored by QCM at a substrate temperature 170 C pulsing condition and corresponding film thickness calculated from mass gain (in inset).708 D.K.Nandi et al./Electrochimica Acta 146(2014)706–713obtained for an unsaturated pulsing condition (1s-15s-1s-15s)with a lower growth rate that ensured the independency of the temperature window with pulsing condition.Obtained narrow range of ALD window for molybdenum sul fide deposition was found to be similar to one reported earlier for oxides using the same Mo-hexacarbonyl precursor [34].Couple of representative ALD cycle is depicted in the Fig.3a to show how the mass gain and hence the growth rate was calculated using QCM measurements.The Mo(CO)6exposure resulted in a pronounced mass gain during the first half cycle.This mass gain was measured ca.18ng cm À2.The total mass change after H 2S exposure during the second half cycle of the reaction,was found to be ca.27ng cm À2.Considering the density of MoS 2found from the XRR measurements,explained later,as 3.85g cm À3,a growth rate of ca.0.5Åper ALD cycle was obtained that is consistent with the overall growth rate as shown in Fig.2a.Fig.3b shows the mass gain measured on Al 2O 3coated QCM crystal during first 50cycles of deposition at 170 C for 4*1s-15s-1s-15s pulse sequences.The film growth was found to be highly linear with the number of ALD cycles with an average growth rate of 2.4Åper cycle under saturated condition of growth for first 50ALD cycles as shown in Fig.3b.Highly linear growth was also observed under 1s-15s-1s-15s pulsing condition proving the linear growth of the film under both saturated and unsaturated condition.Absence of nonlinearity during the initial stages of growth indicated zero incubation period.The corresponding thickness with increase number of ALD cycles under this two different pulsing conditions are shown in the inset of Fig.3b.The linear growth characteristic was found similar to classic ALD growth chemistry.In-situ FTIR spectroscopy was carried out to validate the proposed deposition mechanism.It monitors the vibration spectra of the surface species during the molybdenum sul fide film growth.Differential FTIR absorption spectra were obtained by subtracting each spectrum from the previously recorded one.Fig.4represents the difference spectra obtained during each half reaction.Here the positive absorption represents the accumulated vibration from the surface bound chemical species,while the negative feature indicates the removal of the same.We performed all the experiments at 170 C in semi-static flow mode under surface saturated condition.Before recording the spectra,we deposited 50cycles of MoS 2on KBr palette.This replicates the reaction under the linear growth regime avoiding any unwanted substrate related effects.After saturated Mo(CO)6doses,the absorption peak corresponding to C=O stretch was found at around 2002cm À1[35].The C=O stretch is due to the dissosiatively chemisorbed metal-carbonyl species.An opposite but symmetrical signature peak due to the removal of carbonyl species was found after saturated H 2S doses.This clearly indicated a complete removal of the same.Thus the appearance-disappearance of the carbonyl peak during the two-half reactions cycles of the ALD,as shown in Fig.4,clearly con firms the proposed reaction mechanism.Chemical composition of the as deposited films was examined using X-ray photoelectron spectroscopy (XPS)equipped with Al-K a source.Fig.5shows the character-istic elemental peaks for Mo and S con firming the presence of both components in the as-deposited molybdenum sul fide film.As shown in Fig.5a,doublet peaks of Mo at 229.2and 232.3eV correspond to the binding-energy of 3d 5/2and 3d 3/2electrons respectively.For sulfur the binding energy of 2p 3/2and 2p 1/2electrons were obtained at 162.5and 163.4eV (Fig.5b).In addition to this 2p doublet,S2s peak was also observed at 226.9eV alongside the Mo3d peaks.The complete survey of the XPS in the binding range of 0-1000eV and the individual scan for C1s are given in the supporting information of this article (Fig.S1).The absence of C1s in the complete survey and a very small intense peak in the individual scan re flects the almost non-existence of C in the prepared film.Elemental analysis was obtained by calculating the relative atomic ratio from the normalized area under the peak dividedFig.4.FTIR difference spectra during first four alternate dosing of Mo(CO)6and H 2S showing the presence and removal of C=O surface species.Fig.5.XPS of the ALD grown MoS 2film on Si substrate at 170 C (a)Peaks correspond to S2p doublet and (b)Peaks correspond to Mo3d doublet and S2s.D.K.Nandi et al./Electrochimica Acta 146(2014)706–713709by the sensitivity factors.Elemental ratio of Mo:S was found to be1:2.1.This indicated that the resultant material was MoS2.Furthermore,as reported earlier,the peak positions of the constituent elements also confirmed that the chemical nature of the deposit was MoS2[36,37]. This was further verified with Raman spectroscopy.Fig.6 depicts the sharp Raman peaks at383cmÀ1and406cmÀ1 corresponding to E12g and A1g respectively.The said signature peaks occurred due to1st order Raman vibrational modes within the S-Mo-S layers[38,39]. Fig.7a and7b shows the cross-sectional SEM image and surface AFM image of the as-depositedfilm on Si wafer.The samples used for both these characterizations consisted a film of150cycles under saturated condition that should yield a thickness of ca.37.5nm according to the growth rate.The SEM showed a uniform thickness of40nm over the whole substrate and the surface AFM image RMS roughness of ca.0.65nm over1m m x1m m area was found.Similar to other transition metal oxides and sulfides,electro-chemistry of MoS2against lithium is also dominated by conversion reactions[40–42].During the reaction,four moles lithium were taken by one mole of MoS2as shown below[9,11,12], MoS2+4Li=Mo+2Li2SCyclic voltammogram,as shown in Fig.8a,demonstrated a stable electrochemical performance of MoS2electrode.During the cathodic process prominent peaks were observed at0.43V that characteristically corresponds to the conversion reaction with Li [9,10].During the anodic sweep,the formation of MoS x occurred via multistep reactions,which were observed at1.16V,1.4V and 1.8V vs.Li/Li+[10,43–45].A broad shoulder was also found at2.3V that was due to the formation of Li2S to S[10–12].From the2nd cycle onwards an extra peak at1.35V was observed during the cathodic sweep.The origin of this peak is the formation of Li2S/ Li2S2from the reaction between Li and sulfur[10–12].According to literature the formation of Mo-S bond(MoS x)during the delithiation process was not the prominent process[11–16]. However,small peaks observed at$1.5and$1.8V was also evident in earlier reports which are assigned for Mo-S bond formation [9,10,43–45].In this case the peak intensities of1.16,1.4,1.8V (associated for MoS x formation)were more prominent than literature work.The actual reason for such different behavior needs to be studied further.Solid electrolyte interface(SEI)formation is prominent for this electrode which was usually seen for nano-sized particle as reported earlier[46,47].Broad peaks at0.25V during cathodic sweep and at0.35V during anodic sweep was attributed due to formation and breakage of SEI layer.Formation of SEI layer was also supported by electrochemical impedance spectroscopy shown in figure8b.EIS was taken at OCV which was recorded at2.7V.Two semicircles were observed followed by a linear regime.The semicircle at high frequency regime can be ascribed to the surface film impedance,while the other semicircle at relatively lower frequency regime can be ascribed to the charge transfer resistance [48,49].The corresponding equivalent circuit is depicted in inset of figure8b.R1indicates the electrolyte resistance.R2and Q1 represent the resistance of the Li-ion migration process and capacitance of SEI layer respectively.Similarly R3and Q2are designated to the charge transfer resistance and double layer capacitance respectively.W4represents the diffusion controlled Warburg impedance.The excellent correlation between the simulated and experimentally obtained data indicated the accuracy of the model within the experimental error limit.Charge discharge profile was obtained at a constant current rate of20m A cmÀ2for the potential window of3.0to0.01V vs.Li/Li+.As shown in Figure9a the charge discharge profile are in good agreement with the cyclic voltammetry results.One prominent plateau(around0.5V)was observed during thefirst discharge process,which was denoted for conversion reaction of MoS2with Li.The plateau at ca.1.4V in the charge profile was due to the reverse reaction.During the2nd cycle another plateau was observed at ca.1.5V in the discharge process which was assignedFig.6.Raman shifts of the as-depositedfilm showing the characteristics peaks ofMoS2.Fig.7.(a)Cross-section SEM image of as deposited MoS2film on Si wafer showing an uniformfilm throughout the substrate and(b)Surface AFM image of the same to determine the RMS roughness of the depositedfilm.710 D.K.Nandi et al./Electrochimica Acta146(2014)706–713for Li/S reaction [50,51].A discharge capacity of 150m Ah cm À2(corresponding to 1110mAh g À1calculated based on mass gain approximated from QCM measurements)was achieved during the first discharge cycle that was reversible for the remaining cycles.At the end of 50cycles a discharge capacity of around 115m Ah cm À2(corresponds to 851mAh g À1)was achieved.Thus ca.77%of the initial capacity was retained at the end of 50charge-discharge cycles (Figure 9b).Often severe capacity fading is found in literature due to the volume change that occurs when a carbon and binder free pure material is used as an active electrode [52–54].However under present scenario minimal (only 23%)capacity fading was observed due to uniform deposition,low sample thickness (375nm)and more importantly the amorphous nature of the material.A coulombic ef ficiency in the range of 97to 98%was observed for initial 25cycles which came down to 94.4%at the end of 50cycles (Fig.9b inset).It is to be noted that in first two cycles there was a sudden change in the coulombic ef ficiency as some of the side reactions were prominent in first couple of cycles which were stabilized thereafter.The lower coulombic ef ficiency (or higher coulombic inef ficiency)could be due to the fact that the electrode used in this case is carbon and binder free electrode.Conductive carbon and polymeric binder plays an important role in lithium percolation and mechanical integrity of the electrode.As the present electrode does not contain any kind of conductive additive (such as carbon,CNTs or graphene)it is quite obvious that lithium percolation could be dif ficult upon cycling as more and more resistive interfaces will be included during cycling.Similar observations were also found in literature where free standing electrodes were used [55–57].To improve the coulombic ef ficiency of the electrode different kind of coating were reported in the literature [56]whereas the present work demonstrates theperformance of the as deposited pristine material without any further treatment.Though it is dif ficult to compare the obtained results with the literature,the current work highlights the use of ALD grown MoS 2as an active material for lithium ion battery anode.In present case a thin film electrode was used instead of conventional tape cast method of electrode preparation.There is no literature available on the use of ALD grown MoS 2electrode in lithium ion battery,as best of our knowledge MoS 2itself is deposited for the first time by ALD.In most of the literatures,the ALD technique was used to coat a protective layer on active material for Li-ion batteries [22–27].However,there are few reports on ALD grown materials used as electrodes in Li-ion batteries where template based (such as AAO,CNT,graphene etc.)synthesis approach has been adopted [28,29,31,32].Instead of having a carbon and binder free electrode the obtained results are very much comparable with the reported results that demonstrate a reversible capacity in the range of 850to 900mAh g À1using bare MoS 2[9–16].The higher achieved capacity can be explained by considering the other components of the electrochemical reactions.The theoretical capacity of 670mAh g À1is calculated based on the faradic reaction (diffusion controlled reactions)between Li and MoS 2where 4moles of Li reacts with MoS 2to form Li 2S and Mo.In practice,the obtained capacity from a lithium ion battery system not only comes from the faradic reactions but also from non faradic (capacitive reactions such as double layer capacitance and pseudocapacitance)[58–60]and side reactions (electrolyte decomposition and Li +adsorption on SEI layers)[61].Several researchers observed that the capacity contribution from capacitive reaction could be up to 30to 60%of the total capacity [60].In the current study we use the thin film electrode with very less electrode loading (0.144mg cm À2)Fig.9.(a)Charge-discharge pro file and (b)Cyclic performance of MoS 2electrode at a current density of 20m A cm-2within the potential limit of 3.0V to 0.01V.Fig.8.(a)Cyclic voltammogram of MoS 2at a scan rate of 0.2mV S À1within a potential window of 3.0V to 0.01V vs.Li/Li +and (b)Electrochemical impedance spectroscopy of MoS 2at OCV and corresponding equivalent circuit.D.K.Nandi et al./Electrochimica Acta 146(2014)706–713711whereas in case of conventional electrode higher electrode loading (2–5mg cmÀ2)was used.So it is expected that the capacitive contribution should be higher in present case.Apart from low material loading,a higher order of porosity was developed with charge-discharge cycling(shown in Fig.S3in supporting informa-tion)which can improve the Li+storage via capacitive reactions. Capacity contributions from side reactions are also expected to be significant as nanomaterials are known to possess catalytic effect in electrolyte degradation.Around15%of the total capacity is obtained from below0.2V region which occurs mainly due to Li+ adsorption in SEI layer along with irreversible solvent reduction processes.So,the capacity obtained in the range of3.0to0.2V is around723mAh gÀ1(at the end of50cycles)which is accounted for both MoS2/Li redox reaction and pseudocapacitance.Therefore, the capacity contribution only from MoS2/Li redox reaction would be lower than the theoretical capacity of670mAh gÀ1.4.ConclusionsIn this paper we successfully demonstrated amorphous Molyb-denum sulfide(MoS2)deposition by ALD using Mo(CO)6and H2S.A combination of complementary in-situ and ex-situ characterization techniques were employed to study the growth and self-limiting nature of the deposit.Saturated growth rate of2.5Åwas observed by QCM and verified by ellipsometry and XRR measurements.The as-deposited MoS2film was successfully tested as lithium ion battery anode.Stable electrochemical performance was demon-strated using binder and carbon free MoS2electrode.Discharge capacity of around851mA gÀ1was achieved after50cycles at a current density rate of20m A cmÀ2.The study indicated the importance of ALD grown ultra-thinfilm that could be considered as freestanding electrode for lithium ion batteries.AcknowledgmentThis work was supported by the National Centre for Photovol-taic Research and Education(NCPRE)funded by the Ministry of New and Renewable Energy,Govt.of India.Appendix A.Supplementary dataSupplementary data associated with this article can be found,in the online version,at /10.1016/j.elec-tacta.2014.09.077.References[1]Q.Q.Ji,Y.F.Zhang,T.Gao,Y.Zhang,D.L.Ma,M.X.Liu,Y.B.Chen,X.F.Qiao,P.H.Tan,M.Kan,J.Feng,Q.Sun,Z.Liu,Epitaxial Monolayer MoS2on Mica with Novel Photoluminescence,Nano Lett.13(2013)3870.[2]T.W.Lin, C.J.Liu,J.Y.Lin,Facile Synthesis of 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Common Vocabulary of Sedimentology堆积学常用词汇Aabandoned channel 荒弃河流abandoned delta 荒弃的三角洲ablation breccia 融化角砾岩abrasion terrace 海蚀阶地absolute age 绝对年纪absorpting 吸附性 absorption汲取性abundance of trace element 微量元素丰度abyss(deep sea) 深海abyssal basin 深海盆地abyssal deposit 深海堆积abyssal facies 深海相abyssal ooze 深海软泥abyssal plain 深海平原abyssal subcompensational basin 深海欠赔偿盆地accretion ripple 加积波痕accretion topography 加积地形accretional plain 加积平原accumulation terrace 聚积阶地ACD(aragonite compensation depth) 文石补偿深度acicular texture 针状结构 acidsialic stage 酸性硅铝阶段active continental margin 活动大陆边沿active crust 活动地壳adhesion ripple 粘附波痕adhesion wart 粘附瘤痕advanced dune 行进沙丘aeolian dune facies 风成沙丘相aeolian ripple marks 风成波痕aeolian rock 风成岩agglomerate 集块岩agglomeratic texture 集块结构agglutinated grain texture 胶粒结构aggradation 加积作用 air-heave structure 气胀结构 aleuropelitictexture 粉沙泥质结构algal mat 藻席algal mound 藻丘algal ooid藻鲕algal peloid藻球粒algal reef 藻礁algal reef limestone 藻礁灰岩alkali lake 碱湖 alkali-feldspar碱性长石 allitized stage 铝铁土阶段 allochem 异化颗粒allochemical limestone 异化颗粒灰岩allochemical phosphorite 异化磷块岩allochthonous limestone 异地灰岩allochthonous phosphorite 异地磷块岩alluvial apron 冲积裙alluvial facies 冲积相 alluvial fan冲积扇 alluvial plain 冲积平原alluvial terrace 冲积阶地 alteredtuff 蚀变凝灰岩 ammonoid 菊石类amorphous texture 胶状结构amphibian 两栖动物amygdaloidal structure 杏仁结构anadiagenesis 后生成岩作用analcimolith 方沸石岩analysis of rocks and minerals岩矿剖析angiosperm 被子植物angular 棱角状angular gravel 角砾angular unconformity角度不整合anhydrite 硬石膏 anhydrock硬石膏岩 anisotropic fabric异向组构 antecedent river先成河Anthichnium花趾迹antidune cross bedding 逆行沙丘交织层理apatite 磷灰石aphanitic texture 隐晶结构apparent age 表观年纪apposition fabric 同堆积组构aquatolysis 陆解作用aragonite 文石archaeocyathid 古杯类Archaeopteryx 鼻祖鸟Archean Era 远古代Arenicolites沙蚤迹arenite 砂屑岩，净砂岩argillite泥板岩arid climate干旱天气arkose 长石砂岩arsenopyrite 毒砂Arthropoda节肢动物ascending springy 上涨泉ash content 灰分ash fragment 灰屑asphalt 地沥青asphalt mound 沥青丘asphaltenes 沥青质assimilation同化作用asymmetrical ripple不对称波痕atoll环礁atmosphere 大气圈aulacogen 拗拉谷authigenic mineral 自生矿物autunite 钙铀云母 auxiliarymineral 次要矿物 axis 地轴BB-C sequence B —C 层序back reef facies 礁后相back arc basin 弧后盆地backshore zone 后滨带backshore facies 后滨相back swamp 河漫沼泽back swamp facies 河漫沼泽相backward erosion向源侵害backwash 回流bacteria 细菌bafflestone 障积岩baffling texture障积结构bahamite 巴哈马石ball and pillow structure砂球枕结构banded bedding 带状层理banded limestone facies 缎带灰岩相bank reef堤礁bank seismic facies 滩地震相barchan 新月型沙丘barite 重晶石barrier beach 障壁滩barrier bar 障壁沙坝barrier island障壁岛barrier island system 障壁岛系统barrier reef 障壁礁，堡礁basal arkose 基底长石砂岩basal cementation 基底式胶结basal conglomerate 底砾岩basalt 玄武岩baselap 底超basement 基底basic rock基性岩basinal lake 无口湖batholith岩基bathymetric map等深线图bauxitic rock铝土岩bauxitic rocks铝土岩类bayment 海湾bayment sediment 海湾堆积beach 海滩beach conglomerate 滨岸砾岩beach cusp 滩角beach environment and facies 海滩环境和相beach face 滩面beach facies 海滩相beach profile 海滩剖面beach ridge 滩脊beach ridge facies 海滩砂脊相beach rock 海滩岩 beachsystem 海滩系统Beaconites 灯塔迹bed 层bed load 床沙载荷bed migration 床沙迁徙bed thickness 层厚bedding 层理bedding plane structures 层面结构bedding structures 层理结构bedform 床沙形态benthos 底栖动物beryl 绿柱石biaxial crystal三轴晶bimodal cross bedding 双向交织层理bimodal current 双向流bimodal distribution 双峰散布 binding texture 粘结结构 bio-absorption 生物吸附bio-assimilation 生物汲取 bio-diagenesis生物成岩 bio-mineralization 生物成矿biochemical deposition 生物化学堆积biochemical transportation 生物化学搬运biochemical weathering 生物化学风化biochron 生物时bioclast 生物碎屑bioclastic limestone 生物碎屑灰岩bioclastic sparite 亮晶生物碎屑灰岩bioclastic micrite 生物碎屑微晶灰岩biodeposition生物堆积biofacies 生态相biofacies-paleogeographic map生物相古地理图biofixation 生物固定bioframework pore 生物骨架孔biogenic lamination structure 生物层理结构biogeochemistry(organic geochemistry) 有机地球化学bioherm生物层biohermal facies生物层相biohermal activity生物活动biohermal community生物群落biohermal marker生物标记化合物biohermal trail生物古迹biohermal weathering生物风化biomechanical deposition生物机械堆积biomechanical transportation生物机械搬运biophosphorite生物磷块岩biophysical weathering生物物理风化biosphere 生物圈biostratigraphic unit生物地层单位biostratigraphy生物地层学biosurface 生物面biota 生物群biotite黑云母bioturbation facies 生物扰动相bioturbation structure 生物扰动结构biozone 生物带bird fecal phosphorite鸟粪石磷块岩bird-foot delta鸟足状三角洲birdeye pore 鸟眼孔birdeye structure 鸟眼结构bitter lake 盐湖bitumen沥青bivalve 双壳类black shale 黑色页岩bladed 叶片状blister mat泡状藻席blue-green algae(cyanophyte) 蓝绿藻body fossils 实体化石boehmite 一水软铝石boehmitic rock 一水铝土岩boghead coal 藻煤 boracite方硼石 borax 硼砂boring 生物钻孔bottom cast 底模bottom current底流bottom current facies 底流相bottom mark 底痕bottom moraine facies 底积相bottom reef facies 礁底相bottom set 底积层 boulder 漂砾boulder conglomerate 漂砾砾岩Bouma sequence 鲍马层序boundstone 粘结岩 brachiopod腕足动物 brackish-water lake 半咸水湖 braid index 游荡性指数braided river 辫状河breaker zone 碎浪带breccia 角砾岩broken stage 破裂阶段brown algae 褐藻bruise 撞痕brush cast 刷模bryophyte苔藓植物bryozoan 苔藓虫类bubble impression 泡沫痕buildup岩隆bulkrock analysis全岩剖析burrow 潜穴CC14 age method C14 法caking property粘结性calcarenite 砂屑灰岩calcarenitic texture砂屑结构calcareous cement 钙质胶结物calcareous concretion 钙质结核calcareous quartzarenite 钙质石英岩calcareous shale 钙质页岩calcarenaceous turbidite facies 钙屑浊积岩相calcilutite泥屑灰岩calcilutic texture泥屑结构calcirudite砾屑灰岩calcirutidic texture砾屑结构calcisiltic texture粉屑结构calcisiltite粉屑灰岩calcite 方解石Caledonian movement 加里东运动caliche 钙结岩Cambrian Period寒武纪cap reef facies 礁盖相capillary action dolomitization毛细管浓缩白云化作用caprock 盖层captured river 袭夺河carbonhydrate 碳水化合物carbon isotope 碳同位素carbonaceous shale 炭质页岩carbonate flysch suite 碳酸盐岩复理石建筑carbonate grain 碳酸盐颗粒carbonate minerals 碳酸盐矿物carbonate platform碳酸盐台地carbonate rocks 碳酸盐岩类carbonatite 碳酸岩Carboniferous Period石炭纪carnallite 光卤石chemical structures 化学成因结构cast solution pore 铸模孔chemical weathering 化学风化cataclasite 碎裂岩chenier facies 千尼尔相catagenesis 后生作用chert 燧石岩catagenetic concretion 后生结核chevron mark 锯齿痕catagenetic conglomerate 后生砾岩chicken wire structure 鸡笼铁丝网结构catagenetic dolostone 后生白云岩Chirotherium 掌趾迹catagenetic mineral 后生矿物chlorite 绿泥石catastrophism 灾变论Chondrichthyes 软骨鱼类cathodoluminescence analysis 阴极发光剖析Chondrites 均分潜迹cave deposit 洞窟堆积chronostratigraphic unit 年月地层单位cave-collapse breccia 洞窟塌陷角砾岩chronostratigraphy 年月地层学CCD(calcite compensation depth) 方解石补chute 串沟偿深度chute cut-off 串沟截直CDT scale CDT 标准cirque 冰斗Ce anomaly 铈异样classic tectonics 经典大地结构学celestine 天青石clast 碎屑cement 胶结物clastic material 碎屑物质cement textures 胶结物结构clastic composition analysis 碎屑成分剖析cementation 胶结作用clastic mineral 碎屑矿物cementing zone 胶结带clastic model 碎屑模型Cenozoic Era 重生代clastic texture 碎屑结构center of subsidence 沉降中心clay 黏土cephalopoda 头足类clay mineral 黏土矿物chalcedony 玉髓claystone 黏土岩chalk 白垩climate 天气chalk carbonate suite 白垩碳酸岩建筑climatic arkose 天气长石砂岩chamosite 鲕绿泥石climbing ripple 爬生波痕channel-fill facies 河流充填相climbing ripple cross lamination 爬升沙纹层channel bar 心滩理chaotic carbonate facies 异地碳酸盐相clot 凝块石chaotic sediment 混淆堆积物cluster analysis 聚类剖析charophyte 轮藻CM plot C-M 图chemical analysis 化学剖析coal 煤chemical composition analysis 化学成分剖析coal geology 煤田地质学chemical sedimentary deposit 化学堆积矿床coal-accumulating process 聚煤作用chemical sedimentary differentiation 化学沉coal-forming process 成煤作用积分异coalification 煤化作用coaly monoterrigenous suite单陆屑含煤建筑coarse conglomerate 粗砾岩coarse sand 粗砂coarse silt 粗粉砂coarse siltstone 粗粉砂岩coast 海岸coast line 岸线coastal bay system 湾岸系统coastal lake area 滨湖区coastal lake facies 滨湖相coastal plain 海岸平原coastal reef 岸礁coastal topography 海岸地形coated grain 包粒coated grain phosphorite 包粒磷块岩cobble 粗砾coccolith颗石藻cock ’ s comb structure鸡冠状结构coefficient of the distribution 分派系数Coelenterata 腔肠动物 coking coal 焦煤coking property结焦性cold climate严寒天气cold water carbonate 冷水碳酸盐collapse breccia 滑塌角砾央colloform mat 胶状藻席 colloidsolution 胶体溶液 collophane 胶磷矿 compaction 压实作用 complexdelta 复合三角洲 compositionalmaturity 成分红熟度 compound ooid复鲕 compound ripple 复合波痕compound structures 复合成因结构comprehensive terms 综合术语concave flood plain 河漫滩concavo-convex contact 凹凸接触concretion 结核condensed section 凝缩层 cone-in-cone structure 叠锥结构conformity 整合conglomerate 砾岩conglomerates 砾岩类connecting texture 连生结构conodont 牙形石类consequent river 顺向河 consolidation固结作用 constructive delta 建设性三角洲 contact cementation 接触式胶结contact metamorphism 接触变质contemporaneous concretion 同生结核contemporaneous conglomerate 同生砾岩continental crust 陆壳continental drift hypothesis大陆漂移说continental glacier大陆冰川continental growth大陆增生continental rift大陆裂谷continental rise 陆隆continental slope陆坡contour current 等深流contourite 等深积岩（等深岩）contourite drift 等深岩丘contourite facies等深积岩相convergent margin 汇聚边沿convolute bedding 包卷层理coppery carbonate rock 含铜碳酸盐岩coppery conglomerate 含铜砾岩coppery rock 铜质岩coppery rocks 铜质岩类coppery sandstone 含铜砂岩coppery shale 含铜页岩coquina 介壳灰岩coral 珊瑚coral reef 珊瑚礁coral reef limestone 珊瑚礁灰岩coral reef facies 礁核相correlative analysis有关剖析coset 层系组Cosmorhaphe 丽线迹country rock围岩cover 盖层crack 裂隙crater lake 火口湖cratonic basin 克拉通盆地crawling trail爬行踪CRER(Cretaceous Events and Rhythms)白垩纪事件与韵律Cretaceous Period 白垩纪crevasse splay 决堤扇crevasse-splay facies 决堤扇相Crinoid海百合类cristobalite 方英石cross bedding 交织层理cross bedding orientation交织层理定向crude oil 原油Cruziana 克鲁兹迹Cruziana assemblage 克鲁兹迹组合cryptograin texture 隐粒结构Cryptozoic Eon 隐生宙crystal cast 晶体印模crystal fragment 晶屑crystal grain texture晶粒结构crystal optics 晶体光学crystal tuff 晶屑凝灰岩crystallized ooid 变晶鲕crystalline dolostone 结晶白云岩crystalline granular texture 晶粒结构crystallization differentiation 结晶分异作用crystallo petrology 结晶岩石学crystalloblastic texture 变晶结构cumulative frequency curve频次积累曲线cumulative probability curve概率积累曲线current mark 流痕current ripple流水流痕current ripple cross lamination 流水沙纹层理current rose 流水玫瑰花图curty bedding 卷曲层理curved ripple 歪曲波痕cuspate delta 鸟嘴状三角洲cut-off 裁弯取直cutoff basin 关闭盆地 cyclesequence 旋回层序cyclostratigraphy 旋回地层学Cylindrichnus 柱管迹Cylindricum 柱踪迹Ddammed lake 堰塞湖damp climate 湿润天气debris flow泥石流debris flow facies泥石流相decomposition分解作用dedolomitization去白云化作用deep lake area 深湖区 deeplake facies 深湖相 deepwater lagoon 深水泻湖 deep-water basin 深水盆地deep-water environment 深水环境deep-water shelf 深水陆棚 deep-water system 深水堆积系统deformation 变形deformation fabric 形变结构degradation 降解作用degypsification 去膏化作用dehydration 脱水作用delta 三角洲delta environment and facies三角洲环境和相delta front 三角洲前缘delta lobate 三角洲叶状体delta plain三角洲平原delta plain facies 三角洲平原相delta system 三角洲系统deluvial facies坡积相deluvial zone坡积带density current密度流denudation 剥蚀作用depocenter 堆积中心depositional bauxitic rock堆积型铝土岩depositional cycle堆积旋回depositional plain堆积平原depositional system 堆积系统depositional system analysis堆积系统剖析desert 荒漠desert environment and facies 荒漠环境和相desert facies 荒漠相desert lake 荒漠湖泊desert lake facies 荒漠湖泊相desert system 荒漠系统 desertvarnish 荒漠漆 destructivedelta 损坏性三角洲determination of rocks and minerals 岩矿判定deviation ooid 偏爱鲕development in sedimentology堆积学进展Devonian Period 泥盆纪diagenesis 成岩作用 diageneticconcretion 成岩结核 diagenetic conglomerate 成岩砾岩 diageneticcrack 成岩裂隙 diageneticdolostone 成岩白云岩 diagenetic environment 成岩环境 diageneticmineral 成岩矿物 diagenetic trap成岩圈闭 diagonal bar 斜列沙坝diagonal bedding斜层理diamictite混积岩diapiric structure底辟结构diara 沙洲diaspore一水硬铝石diastem 堆积停留diatactive varve粒度递变纹泥diatom 硅藻diatom ooze 硅藻软泥diatomite 硅藻岩diatreme breccia 迸发角砾岩dickite地开石Dictyodora网锥迹differential thermal analysis差热剖析differential weathering差别风化Dikaka 双叉迹dike 岩脉Dinosaur 恐龙dip 偏向Diplichnites双趾迹Diplocraterion双环迹direct runoff地表径流dirty sandstone 脏砂岩discriminant analysis鉴别剖析dish structure 盘状结构disorganized 乱杂型disorganized bedding杂乱层理dispersal system 分别系dissected basin 切割盆地dissolution溶解dissolved load 溶解载荷dissolved material 溶解物质dissolving zone溶解带distal bar 远砂坝distal bar facies 远砂坝相distal facies 远源相distal fan 外扇distal onlap 远端上超distal turbidite远源浊积岩distorted ooid变形鲕distributary分流distributary backswamp facies 分流河流河漫沼泽相distributary channel 分流河流distributary channel facies 分流河流相distributary levee facies分流河流堤岸相distributary mouth bar河口砂坝distributary mouth bar facies河口砂坝相distribution of REE稀土元素分派distribution of trace element 微量元素分派distrophic lake 缺养湖disturbed bedding 扰动层理dolarenite 砂屑白云岩doll concretion钙结核dololaminite纹层状白云岩dololutite泥屑白云岩dolomicrite微晶白云岩dolomite 白云石dolomitic limestone 云灰岩 dolomitic phosphorite 白云质磷块岩dolomitization 白云石化作用dolomitized limestone 白云化灰岩dolorudite 砾屑白云岩dolosiltite粉屑白云岩dolostone 白云岩dolostone evaporite suite 白云岩型蒸发岩建造dolostones 白云岩类domelike stromatolite 穹状叠层石dorag dolomitization 混淆白云化作用double mud drapes 双黏土层downcutting 下切作用downlap 下超downslope ripple下移波痕draa 臂状沙丘drainage basin 流域drainage system 水系drift dam冰碛坝drift plain冰碛平原drowned platform淹没台地drowned valley溺谷drusy texture 丛生结构dune 沙丘dune facies 沙丘相dwelling trail居住迹Eearly diagenesis 初期成岩作用earth 地球earth ’ s core地核earth ’ s crust地壳earth ’ s mantle地幔Echinoderm 棘皮动物Echinoid海胆类ecology 生态学economic geology 经济地质学edgewise structure 竹叶状结构effusive rock 喷出岩Eh value Eh 值electronic probe analysis 电子探针剖析elevated crust 抬生地壳eluvial breccia残积角砾岩eluvial facies残积相eluvial zone残积带embayment 海湾enclosed sea 关闭海end moraine facies 终冰碛相end peneplain 终期准平原endobiont 内栖动物endogenetic sediments 内成堆积物endogenic deposit 内生矿床endorheic basin 内流盆地Eocene Epoch 始新世eolian basin 风蚀盆地eolian cross bedding 风成交织层理eolian dune 风成沙丘eolianite 风成岩eonothem 宇epeiric sea 陆表海epibionts 底表生物epidiagenesis 表生成岩作用epidiagenetic environment表生成岩环境epigenesis 表生作用epigenetic concretion表生结核epigenetic deposit 后生矿床epiglyph顶面痕epimatrix外杂基epoch of mineralization成矿期epsilon cross bedding ε交织层理epsomite 泻利盐equant 等轴状erathem 界erosion 侵害作用erosional basis 侵害基准面erosional plain侵害平原erosional terrace 侵害阶地erosional topography 侵害地形escape structure 逃逸结构esker 蛇形丘essential mineral 主要矿物estuarine facies 河口湾相estuary 河口湾ething mark刻蚀痕eugeosyncline 优地槽euryhaline environment广盐度环境euryhaline lagoon 广盐泻湖euryhaline organism 广盐性生物eurythermal organism 广温性生物eutrophic lake兹养湖evaporation 蒸发生用evaporite 蒸发岩evaporite platform 蒸发盐台地evaporite-solution breccia 盐溶角砾岩evaporites 蒸发岩类evaporitive pumping dolomitization蒸发泵白云化作用excrement 排泄物exinite壳质组exogenetic sediments 表成堆积物experimental sedimentology 实验堆积学explanation for orientation 定向解说Ffabric 组构fabric of carbonate rock 碳酸盐岩组构fabric of claystone 黏土岩组构 facies相facies arrangement 相摆列facies association 相组合facies belt 相带facies change 相变facies fossil 指相化石facies group 相组facies map 相图facies mineral 指相矿物facies model 相模式facies province 相区facies sequence 相序列fan-shaped delta 扇形三角洲faro 小环礁fault 断层fault basin断陷盆地fauna 动物群fecal peloid粪球粒feeding trail进食迹feldspar 长石feldsparthic litharenite 长石岩屑砂岩feldsparthic quartzarenite 长石石英砂岩felty structure 毡状结构fenestral structure 窗孔结构ferroalumino suite 铝土铁质建筑ferrodolomite 铁白云石 ferromanganese concretion 铁锰结核 ferruginous cement 铁质胶结物 ferruginous quartzarenite 铁质石英砂岩 ferruginous rocks 铁质岩类ferruginous rock 铁质岩ferruginous shale 铁质页岩fibrous texture纤状结构filled valley冲淤谷filled-lake plain淤积湖平原film mat薄膜状藻席film texture薄膜结构fine conglomerate细砾岩fine sand 细砂fine silt细粉砂fine siltstone细粉砂岩finger bar 指状砂坝firth三角港fixed dune固定沙丘flame structure 火焰结构flaser bedding 脉状层理flat bedding平展层理flat mat 平展藻席flocculation 聚沉作用，絮凝作用flocculation by condensation 浓缩聚沉flocculation by electrolyte 电解质聚沉flood 洪水flooded lake 河漫湖flooded lake facies河漫湖泊相floodplain洪积平原floodplain facies洪积平原相flora 植物群flow system流动系fluid流体fluid dynamics流体动力学fluidized sediment flow液化堆积物流flume experiment 水槽实验fluorescence analysis 荧光剖析fluorite萤石fluroapatite氟磷灰石flute cast 槽模flute cast orientation槽模定向fluival environment and facies河流环境和相fluival system冲积系统fluival-dominated delta河控三角洲fluxoturbidite滑塌浊积岩flysch复理石flysch facies复理石相flyschoid类复理石flysch suite复理石建筑foliaton叶理footprint足印foraminifera reef limestone 有孔虫礁灰岩Foraminiferan 有孔虫类fore reef facies 礁前相forearc basin 弧前盆地foredeep basin 前渊盆地foreland basin 前陆盆地foreset 前积层foreshore facies 前滨相foreslope facies 前缘斜坡相forslope of platform 台地前缘斜坡formation 组fossil 化石fossil microtextures 生物显微结构fossil orientation 化石定向framework grain 骨粒francolite 碳氟磷灰石freeze thaw weathering 冻融风化frequency curve 频次曲线fresh water dolomitization 淡水白云石化作用fresh water dolostone 淡水白云岩 fresh-water lake 淡水湖freshened lagoon 淡化泻湖freshening environment 淡化环境front moraine facies 前积相front sand sheet facies 前缘席状砂相frost weathering 寒冻风化frost 霜面Froude ’ s Number 福劳德数fusulinid 蜓类fungi真菌Gganister 致密硅岩Gastropod 腹足类gelatinous mat 凝胶状藻席gelatinous phosphorite 胶状磷块岩geochemical methods 地球化学方法geochronologic scale 地质年月表geological record地质记录geomorphologic unit地貌单元geomorphology 地貌学 geopetalstructure 示底结构 geophysicalmethods 地球物理方法 geosuture 地缝合线geosyncline 地槽giant ripple巨波痕gibbsite 三水铝石gibbsitic rock三水铝土岩Gilbert type delta 吉尔伯特型三角洲glacial climate 冰川天气glacial environment and facies 冰川环境和相glacial erratics 冰川漂砾glacial morphology 冰川地貌glacial system 冰川系统glacial tongue 冰舌glacial valley冰蚀谷glacier 冰川glaciodelta 冰成三角洲 glaciodelta facies冰成三角洲相 glaciofluvial environment冰川冲积环境glaciofluvial facies 冰水冲积相 glaciofluvial terrace 冰水阶地 glaciolacustrine environment 冰川湖泊环境 glaciolacutrine facies 冰川湖泊相 glaciomarine environment 冰海环境 glaciomarine facies 冰海相glauconite 海绿石glauconitic quartzarenite海绿石石英砂岩global climate change 全世界天气变迁global rhythm and event 全世界韵律和事件global sea level fluctuation 全世界海平面起落global sedimentary geology program 全世界沉积地质计划global sedimentology全世界堆积学global volcanism 全世界火山作用 globigerina ooze 抱球虫软泥gneiss 片麻岩gobi 沙漠gobi facies 沙漠相Gondwana 冈瓦纳古陆 Gondwanaland bridge 冈瓦纳陆桥 grade scale粒级标准graded bedding 粒序层理grain dolostone 颗粒白云岩grain flow 颗粒流grain index 颗粒指数grain limestone 颗粒灰岩grain orientation 颗粒定向grain phosphorite 粒屑磷块岩grain size 粒度grain size analysis 粒度剖析grain size distribution 粒度散布grain size parameter 粒度参数grain supported 颗粒支撑grainstone 颗粒岩granite 花岗岩granular texture 粒状结构granule 细砾grapestone 葡萄石graptolite 笔石类gravel 砾gravel fabric砾石组构gravity cementation重力胶结gravity flow重力流greywacke 灰瓦克岩，硬砂岩，杂砂岩grazing trail 觅食迹green algae(chorophyte) 绿藻grey biterrigenous suite 灰色复陆屑建筑graywacke (greywacke) 硬砂岩greywacke suite 杂砂岩建筑groove cast 沟模group 群growth fabric生长组构guide fossil标记化石guyot 海底平顶山Gymnosperm 裸子植物gypsolith石膏岩gypsum 石膏gypsum evaporite suite 膏盐型蒸发岩建筑Hhail print雹痕halides 卤化物halite 石盐halloysite埃洛石halmyrolysis海解作用hardground structure 硬底结构heating stage 显微镜热台heavy mineral 重矿物heavy mineral analysis 重矿物剖析Helminthoida蠕踪迹Helminthopsis拟蠕踪迹helocline 盐度跃层hematite 赤铁矿hematitic rock赤铁岩hemipelagic carbonate facies 半远洋碳酸盐相hemipelagic environment半远洋环境hemipelagic facies model半远洋相模式hermatypic coral造礁珊瑚herringbone cross bedding 羽状交织层理heulanditic rock片沸石岩hiatus 堆积中断high moor 高位沼泽high water level 热潮面 high-angle cross bedding 高角度交织层理high-density current 高密度流 high-energy ooid 高能鲕 high-magnesian calcite 高镁方解石 high-ranksandstone 高级杂砂岩 high-sinuosity river 高弯度河highmoor peat 高沼泥炭highstand system tract 高水位系统域hill丘陵histogram 直方图history of sedimentology堆积学史Holocene Epoch 崭新世homopycnal flow等密度流honey comb structure 蜂窝状结构horizontal bedding 水平层理host rock 主岩hot sping 热泉hot water dolomitization热水白云石化作用hot water sedimentary rock热水堆积岩hot water sedimentation热水堆积作用HREE 重稀土元素humic acid腐殖酸humic substance 腐殖质humic-type kerogen腐殖型干酪根huminite腐殖组hummocky cross bedding丘状交织层理hybrid sediments混淆堆积物hydrated zone 水合带hydration 水合作用hydrocarbon烃hydrogen isotope 氢同位素hydrolysis水解作用hydrolysis zone水解带hydrosphere 水圈hydrothermal deposit热液矿床hydrothermally cemented rock热泉胶结岩Hyolithid软舌螺类hypabyssal rock 浅成岩hypergenic mineral 表生矿物Iice crystal cast 冰晶模ice sheet 冰盖ichnology古迹学ideal section 理想剖面igneous petrology火成岩石学igneous rock 火成岩illite 伊利石imbricated structure 叠瓦结构illite claystone 伊利石黏土岩immersion method 油浸法immersion oil 浸油indentation 凹坑index fossil 标准化石index of meandering 曲流指数index of sinuosity 弯度指数indication of oil and gas 油气显示Indo-China movement 印支运动inertinite 惰性组infrared absorption spectrum analysis 红外光谱剖析injective structure 注入结构inland basin 内地盆地 inlanddrainage 内地水系inland sabkha 内地萨勃哈inland sabkha facies 内地萨勃哈相inner bar 内沙坝inner bar facies 内沙坝相inner shelf内地棚inner shelf facies 内地棚相inter-reef facies 礁间相interarc basin 弧间盆地intercalated beds 隔层intercontinental rift 陆间裂谷interdistributary bay分流间湾interference colour干预色interference ripple干预波痕interference figure干预图interformational conglomerate 层间砾岩intergranular pore 粒间孔intergranular solution pore 粒间溶孔interlayered bedding 互层层理 intermittent suspended load 间歇悬浮载荷intermontane basin 山间盆地internal tide 内潮汐 internal-tidedeposits 内潮汐堆积 internalwave 内波 internal-wave deposits内波堆积International Association of Sedimentologists (IAS)国际堆积学家协会International Union of Geological Sciences (IUGS)国际地科联interstitial water孔隙水interstitial material填隙物interstitial zone潮间带intra-arc basin 弧内盆地intrabasinal environment and facies内源堆积环境和相intrabasinal lake 盆内湖intrabasinal rock 盆内岩intrabasinal sediment 内源堆积物intraclast 内碎屑intraclastic limestone 内碎屑灰岩intraclastic phosphorite 内碎屑磷灰岩intracratonic basin 克拉通内盆地intraformational breccia 层内角砾岩intragranular pore 粒内孔 intragranular solution pore 粒内溶孔 intramicrite 内碎屑微晶灰岩 intramontane basin 山间盆地intrasparite 内碎屑亮晶灰岩 iinversegraded bedding 逆粒序层理 ionabsorption 离子吸附作用ion exchange 离子互换作用isolated platform孤立台地isolated ripple孤立波痕isolithic map等岩性图isopach cementation 等厚环边胶结isopachous map 等厚线图Isopodichnus 等趾迹isotope abundance 同位素丰度isotope composition 同位素构成isotope dating 同位素定年isotope fractionation 同位素分馏isotope fractionation factor 同位素分馏系数isotope ratio 同位素比值 isotope standard 同位素标准isotopic age 同位素年纪isotopic geochemistry 同位素地球化学isotropic fabric 等向组构Jjasper rock 碧玉岩jasper suite 碧石建筑Jurassic Period 侏罗纪Kkame 冰碛kaolinic claystone 高岭石黏土岩kaolinite 高岭石karst breccia 岩溶角砾岩karst lake 岩溶湖karst morphology岩溶地貌kerogen 干酪根kidney-like hematitic rock 肾状赤铁岩kidney-shaped texture 肾状结构 knoband tail mark 丘尾痕kurtosis 尖度Llacustrine 湖泊的，湖成的lacustrine system 湖泊系统lag facies 滞留相lagoon 泻湖lagoon facies 泻湖相lake delta 湖泊三角洲lake delta facies 湖泊三角洲相lamellar fibrous texture 层纤结构lamina 细层laminar flow 层流laminated texture 片状结构landslide 滑坡late diagenesis 后期成岩作用lateral accretion 侧向加积lateral erosion 侧向侵害lateral facies change 侧向相变laterite 红土lateritic bauxitic rock 红土型铝土岩laterized stage 红土阶段lattice structure 晶格状结构lava fragment 浆屑layered moraine 层状冰积物leaching zone 淋滤带legend 图例lenticular bedding 透镜状层理lenticulite 扁豆状熔灰岩levee facies 堤岸相Liesegang banding 李泽冈环lime clast 灰屑lime dolostone 灰云岩lime mud 灰泥lime mudstone 灰泥岩lime-mud matrix 灰泥基质lime-mud mound 灰泥丘limestone 石灰岩limestones 灰岩类limnic basin 陆相含煤盆地limnogenic rock 淡水堆积岩limonite 褐铁矿limonite rock褐铁岩linear contact 线接触linear sand bar 线形砂坝lineation线理link single crystal texture 连生单晶结构litharenite 岩屑砂岩lithic arkose岩屑长石砂岩lithic fragment岩石碎屑lithic graywacke岩屑杂砂岩lithic quartzarenite岩屑石英砂岩lithic tuff岩屑凝灰岩lithofacies岩相lithofacies map岩相图lithofication石化作用lithoherm岩礁lithologic column 岩性柱状图lithologic section 岩性剖面lithosphere 岩石圈 lithostratigraphic unit 岩性地层单位 lithostratigraphy岩石地层学 lithotype 煤岩种类 littoral dune 沿岸沙丘littoral zone滨海带load cast 重荷模lobate bedding 叶状层理loess 黄土loess concretion 黄土结核loess facies 黄土相loess field 黄土原logging测井lognormal distribution 对数正态散布longitudinal bar 纵向砂坝 longitudinal section 纵剖面 longshore bar 沿岸砂坝 longshore current 沿岸流Lophocteniun 菊瓣迹 low moor 低位沼泽low water level低潮面low-angle cross bedding 低角度交织层理low-density current 低密度流low-density turbidity current 低密度浊流low-rank sandstone 初级杂砂岩low-sinuosity river 低弯度河lower flow regime 下部流态lowsand system tract 低水位系统域LREE 轻稀土元素lump 团块lump limestone 团块灰岩lump micrite limestone 团块微晶灰岩lump phosphorite 团块磷块岩lump sparite limestone 亮晶团块灰岩Mmacroclastic rock粗碎屑岩macrofossil 大化石macroid 大包粒magma 岩浆magmatic deposit 岩浆矿床magmatic rock岩浆岩magmatism 岩浆作用magnesite 菱镁矿magnetic element 地磁因素magnetic pole 地磁极magnetic pole wandering 地磁极游移magnetic stratigraphy 磁性地层学magnetite 磁铁矿magnetitic rock磁铁岩main river干流mammal 哺乳动物manganiferous carbonate rock 锰质碳酸盐岩manganiferous claystone 锰质黏土岩manganiferous concretion 锰结核manganiferous concretional rock 锰质结核岩manganiferous rock 锰质岩 manganiferous rocks 锰质岩类 manganiferous siliceous rock 锰质硅质岩manganiferous clastic rock 锰质碎屑岩manganite 水锰矿mantle convection 地幔对流marchasite 白铁矿marginal platform边沿台地marginal sea 陆缘海marine bench 海蚀台marine cliff海蚀崖marine diagenetic environment 海水成岩环境marine drift 漂流marine environment and facies 大海环境和相marine facies 海相marine phreatic zone 海水潜流带marine salina 滨海盐沼marine vadose zone 海水渗流带Markov chain analysis 马尔可夫链剖析marl 泥灰岩marsh 沼泽marsh environment and facies 沼泽环境和相massive bedding 块状层理 massive flow 块体流matrix杂基matrix supported 杂基支撑maturity analysis 成熟度剖析maturity index 成熟度指数mean 均值mean grain size 均匀粒度mean high water level 均匀热潮面mean low water level 均匀低潮面mean range 均匀潮差 mean sealevel 均匀海平面meander belt 曲流带meander scroll 曲流涡形坝meandering river蛇形河meandering river曲流河measured section 实测剖面mechanical sedimentary differentiation机械堆积分异mechanical transportation and deposition机械搬运和堆积medial moraine facies中碛相median grain size 中值粒度Mediterranean sea 地中海medium conglomerate 中粒砾岩medium of transportation and sedimenation搬运和堆积介质medium sand 中砂megaripple 大波痕meltout till融出碛member 段meniscus cementation 新月形胶结Merostomichnites肢口迹Mesozoic Era 中生代 metallicmineral 金属矿物 metallic ore 金属矿产 metallogenetic epoch 成矿时代metallogenic belt 成矿带metallogenic province 成矿区metamorphic age 变质年纪metamorphic belt 变质带metamorphic deposit 变质矿床metamorphic facies 变质相metamorphic grade 变质程度metamorphic petrology 变质岩石学metamorphic rock 变质岩metamorphism 变质作用meteoric diagenetic environment淡水成岩环境meteoric phreatic zone 淡水潜流带meteoric vadose zone 淡水渗流带meteoric water 大气降水mica 云母micrite微晶micrite cementation泥晶胶结micritic allochemical limestone泥晶异化粒灰岩。