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Synthesis of silver hollow nanoparticles and observation of photoluminescence emission properties

Synthesis of silver hollow nanoparticles and observation

of photoluminescence emission properties

H.S.Desarkar,P.Kumbhakar n,A.K.Mitra1

Nanoscience Laboratory,Department of Physics,National Institute of Technology Durgapur,Mahatma Gandhi Avenue,West Bengal713209,India

a r t i c l e i n f o

Article history:

Received21April2012

Received in revised form

22September2012

Accepted5October2012

Available online16October2012

Keywords:

Hollow nanoparticles

Laser ablation in liquid

Silver nanoparticles

Surface plasma resonance

Interband transition

Photoluminescence

a b s t r a c t

Preparation of hollow silver nanoparticles(HSNs)along-with solid silver nanoparticles are reported by

Nd:YAG laser ablation of solid silver target immersed in water medium with a laser ablation time(LAT)

duration of50min and with the incident laser?uence of151J/cm2.It is found that only solid silver

nanoparticles are produced when the experiment is carried out with smaller values of LAT duration.

The synthesized samples are characterized by using transmission electron microscopy and UV–Visible

absorption spectroscopy.The UV–Visible absorption spectra of the samples show sharp absorptions in

the ultraviolet and in visible regions due to interband transition and surface plasmon resonance

oscillations in Ag nanoparticles,respectively.It is found that all samples exhibit photoluminescence

(PL)emission,at room temperature,in the UV–Visible region peaked at$346nm,due to the

recombination of electrons with holes from sp conduction band to d band of Ag.The sample containing

HSNs exhibits strong PL emission and the value of peak PL emission intensity is enhanced by the factor

of2.4in comparison to that obtained from the sample synthesized with LAT duration of20min.The

synthesized HSNs may?nd applications in catalysis and in chemical sensing.

&2012Elsevier B.V.All rights reserved.

1.Introduction

In the last two decades,noble metal nanoparticles have

attracted attention of the researchers because of their size

dependent electronic,catalytic,magnetic and optical properties

[1–3].And recently,a lot of focuses on research activities on Ag

nanoparticles have been given as its bulk counterpart has the

highest electrical and thermal conductivities in comparison to

those of all other noble metals[4].The properties of nanoparticles

are strongly dependent on its size and shape.Hence,by precise

control of the size and shape it is possible to tune the chemical

and physical properties of materials and some unique properties

of nanomaterials can be explored.Shape-controlled synthesis of

different nanostructures of Ag,such as cubes[5],rice[6]and wire

[7],have been reported earlier by using various synthesis

techniques.

Recently,hollow nanoparticles have attracted tremendous

attention of the researchers because of their speci?c structures

and properties.Due to their high surface to volume ratio and

low density they are widely desirable in drug delivery system[8],

biotechnology[9]and as photo catalyst[10].Hollow

nanoparticles offer some advantages over their solid counterparts

in terms of their light weight and reduced cost,as fewer amounts

of materials are required[11].The fabrication of hollow Ag

spheres at room temperature has been reported by Chen et al.

by using the convenient and versatile wet chemical method[4].

Another most popular method of synthesizing hollow nanoparticle

is template mediated approach.In the template mediated approach,

the surface of the template is coated with the desired material and

then the template is removed by a post treatment to produce hollow

nanoparticles[12].

Laser ablation in liquid(LAL)is a highly promising and recent

technique for preparing solid nanoparticles from solid targets

[13–15].Also by using LAL technique,the shape and size of the

nanoparticles can be modi?ed by varying the incident laser

wavelength,?uence,ablation time as well as the liquid environ-

ment.During laser ablation experiment,ejection of particles from

the target is occurred followed by the formation of the bubbles.As

the laser radiations are incident on the metal target,the surface

temperature of the target may increase even above the boiling

temperature of the liquid.Thus the formation of bubbles takes

place at the solid–liquid interface.The laser induced bubbles trap

the produced nanoparticles,which results in the formation of

hollow nanoparticles.Yan et al.has reported the preparation of

platinum[16],Al2O3[17]and Zn[18]hollow nanoparticles by

utilizing such mechanism.But in most of the earlier reports the

size of the prepared hollow nanoparticles are larger than100nm

Contents lists available at SciVerse ScienceDirect

journal homepage:https://www.doczj.com/doc/8912250805.html,/locate/jlumin

Journal of Luminescence

0022-2313/$-see front matter&2012Elsevier B.V.All rights reserved.

https://www.doczj.com/doc/8912250805.html,/10.1016/j.jlumin.2012.10.007

n Corresponding author.Tel.:t913432546808;fax:t913432547375.

E-mail addresses:nitdgpkumbhakar@https://www.doczj.com/doc/8912250805.html,,

pathik.kumbhakar@phy.nitdgp.ac.in(P.Kumbhakar).

1Presently retired.

Journal of Luminescence134(2013)1–7

and preparation of hollow nanoparticles with size smaller than 100nm are rarely reported[16,17].

However,here we have reported the preparation of hollow silver nanoparticles(HSNs)having sizes(diameters)lying in 15–60nm range along-with solid silver nanoparticles having average size(diameter)of$11nm by laser ablation of Ag target kept in water medium.The wavelength of the used laser radiation is1064nm,emitted from a Q-switched Nd:YAG laser source, having pulsed duration of10ns.The used value of the laser ablation time(LAT)and the laser?uence are50min and151J/ cm2,respectively.We have performed the experiment also with the LAT durations of20and40min with the same laser?uence of 151J/cm2and in these cases the formations of HSNs are not observed,but solid nanoparticles with broader size distributions are found.The reason for not creation of HSNs at lower values of LAT durations has been explained later.The UV–Visible spectra of all the samples show the appearances of strong and sharp interband absorption in the ultraviolet region at$260nm ($4.77eV)as well as SPR absorptions in the visible region (391–400nm).Photoluminescence(PL)emissions from noble metal nanoparticles have received less attention because most of the emission processes have low ef?ciency[19].Visible PL from gold and copper nanoparticles are?rst observed by Mooradian [19].Boyd et al.have reported single and multiphoton PL spectra from clean samples of gold,silver and copper with both smoothed and rough surface[20].However,here we have reported PL emissions characteristics of all samples and it is found that all samples exhibit PL emissions covering the whole visible region peaked at an UV wavelength of$346nm which is attributed to recombination of electrons from sp conduction band to d band of Ag.The PL peak emission intensity at$346nm is enhanced by the factor of$2.4in the sample prepared with50min of LAT in comparison to that obtained in the sample prepared with20min of LAT.Despite the complex mechanism of laser-matter interac-tion,laser ablation in liquid technique provides a simple,?exible and less expensive way for formation of HSNs.

2.Experimental details

A solid Ag target of$10mm thick and of purity of99.99%is kept in a Petri dish containing10ml of water.The laser radiation at1064nm wavelength coming from a Q-switched Nd:YAG laser is focused using a lens of30cm focal length.The laser source is operated at a repetition rate of10Hz and having pulse duration of 10ns.In order to avoid formation of craters[21]we have translated the Petri dish containing the Ag target during the laser ablation experiment.The morphology and structure of the synthesized samples are characterized with a transmission elec-tron microscope(TEM,FIB-20),selected area electron diffraction (SAED)and energy-dispersive X-ray analysis(EDXA).UV–Visible absorption characteristics have been recorded in the range of 200–800nm with the help of UV–Visible spectrophotometer (Hitachi,U3010)and for these measurements nanocolloids are kept in a quartz cuvette of path length of10mm.Photolumines-cence(PL)emission spectra from all samples are collected at room temperature by using a luminescence spectrometer(Perkin Elmer LS55)and by keeping the nanocolloids in a four side polished PL cuvette of path length of10mm.

3.Results and discussions

Fig.1(a)and(b)shows the TEM images taken at two different regions of the same sample S1.The sample S1has been prepared with50min of LAT with the laser?uence of151J/cm2.For obtaining TEM image,the sample is dried on a TEM grid consisting of copper meshes with a heavy layer of carbon?lm.It is found from Fig.1(a)that the majority of the particles are solid nanospheres and a small proportion of the particles are HSNs as indicated by arrows.From Fig.1(b)it is found that some bigger size HSNs are also present in the sample S1.The contrast variations in the center of particles indicate the presence of hollow particles.Beside spherical shape,oval shaped and irregular shaped HSNs are also observed in the synthesized product, indicated by arrows in Fig.1(b).Fig.1(c)shows the size distribu-tions of all particles(solid and hollow ones)as obtained by analyzing TEM images as shown in Fig.1(a)and(b).It is found from Fig.1(c)that the average size of the prepared solid nanoparticles is$11nm whereas the size of the hollow nano-particles varies between15and60nm and the proportion of HSNs is increased with the increase in size of the synthesized particles,https://www.doczj.com/doc/8912250805.html,rger particles are more likely to become hollow. The magni?ed images of some selected HSNs present in the sample S1are also shown in the inset of Fig.1c,which clearly demonstrates the formation of hollow nanoparticles.The EDXA spectrum of the sample S1is shown in Fig.1d,which shows the presence of Ag as a principal element.

Structural information from an assembly of HSNs is obtained using a SAED pattern as shown in Fig.1e,viz.,for sample S1.From Fig.1e it is found that the SAED pattern consists of six concentric rings.The lattice spacing from the six different rings in the SAED pattern are calculated and compared with the standard lattice spacing of Ag(JCPDS04-784)and Ag2O(JCPDS43-0997)along with their respective(hkl)indices and the results are summarized in the Table1.From the Table1it is found that our calculated values matches exactly well with those of standard values of Ag and Ag2O and this proved the coexistence of both Ag and Ag2O in the sample.In order to clarify the fact that if there is any increase in Ag2O formation with increase in LAT,we have carefully studied the SAED patterns taken for all the samples.It is found by analyzing the SAED patterns(not shown here)of the samples produced with LAT of20and40min that all diffraction rings those are appearing in these samples are due to Ag only.Weak oxidization of Ag during this smaller LAT duration may be possible but we could not identify it experimentally here.Actually due to strong con?nement effect of water with increase in LAT, nanoparticles which are ejected from the Ag target are accumu-lated near the laser spot.When the number of these accumulated nanoparticles is suf?ciently large and reaches a certain critical value,they shield the incident laser radiation.As a result,the incident laser light is now incident on the nanoparticles prepared in earlier steps and causes fragmentation and melting of nano-particles.Melting may increase the tendency of the nanoparticles to get oxidized at longer values of LAT.

The oxidation of Ag nanoparticles generated by laser ablation in water is usually inherent due to soluble oxygen or reaction of Ag with water.Agtions are also generated during laser ablation of bulk Ag.Photo-ionization of Ag clusters in water[22]can be described as

Agàà!

h n Agtteà:

The dissociated electrons may recombine with Agtions to form Ag atoms or may produce OHàfrom water molecule as described below

H2Oteà-OHàtHt:

TheAg2O molecule is formed by the following reaction[22]: 2AgteaqTt2OHà-Ag2OesTtH2O:

A bright?eld(BF)HRTEM image of an isolated Ag nanoparticle is shown in Fig.1f,in which the formations of lattice fringes are

H.S.Desarkar et al./Journal of Luminescence134(2013)1–7 2

clearly observed.The calculated value of the distances between two adjacent planes is measured to be 0.144nm,which corre-sponds to (220)planes of Ag.

The formation of HSNs strongly depends on LAT duration.In order to study the effect of LAT duration on the preparation of

HSNs we have also performed the LAL experiment with smaller LAT durations of 20and 40min and the prepared samples are named as S2and S3,respectively.During the preparation of S2and S3samples the laser ?uence is kept constant at 151J/cm 2.Fig.2a and b and Fig.3a and b show TEM images (corresponding particle size distributions)of the sample S2and S3,respectively.It is found from Fig.3(a)and (b)that no HSNs are produced but there are solid silver nanoparticles with broad size distribution.Also in S2and S3samples some particles are present having sizes as large as 40–50nm.However,the average sizes of the prepared nanoparticles are almost constant (i.e.$11nm),perhaps due to the fact that the incident laser ?uence has been kept same in preparation of all samples.But due to fragmentation number of nanoparticles with smaller diameter is found to be increased in S3which is prepared with longer time duration.Deviations from spherical symmetry are also observed in a minor fraction of prepared nanoparticles in both S2and S3samples.Some of the nanoparticles are loosely agglomerated,and some others also have formed a chain of particles.However,the mechanism of formation of HSNs is described

below.

Fig.1.Images marked as (a)and (b)show the TEM micrographs of the sample S1.The particle size distribution of all particles (solid and hollow)is shown in (c)and its inset shows some magni?ed images of some selected hollow nanoparticles.A representative EDXA spectrum of sample S1is shown in (d).The SAED pattern and the BF HRTEM image of the sample S1are shown in (e)and (f),respectively.

Table 1

Measured lattice spacing d (nm)from the SAED pattern (Fig.1e)and standard lattice spacing for Ag (JCPDS 04-784)and Ag 2O (JCPDS 43-0997)along-with their respective (hkl )indices.Ring

Lattice spacing (hkl )

Measured d (nm)

Standard d Ag (nm)d Ag2O (nm)10.2060.206(200)20.1980.198(200)30.1440.144(220)40.1240.123(311)50.0930.094(332)6

0.081

0.083

(422)H.S.Desarkar et al./Journal of Luminescence 134(2013)1–73

There are several reports for the preparation of hollow nano-particles using different techniques [16–18,23–25].The most popular method for the synthesis of hollow nanoparticles of ceramic and polymeric materials is the template mediated approach,in which surface of the particles is coated with desired material followed by selective removal of colloidal templates [23].Another important method is galvanic replacement [24],which provides a simple and versatile tool for the synthesis of hollow nanoparticles.In this method reaction takes place when metal nanoparticles are in contact with another metal ion of higher reduction potentials.In our experiment we have not used any template and also the synthesis has been carried out by laser ablation of a single solid metal target.Therefore,none of the above mentioned techniques [23–24]can be assigned as the reason for the formation of HSNs.

Recently,hollow nanoparticles of oxide,sul?des,selenides and phosphides have been reported by simply laser ablating metal targets through Kirkendall effect (KE)[25].However,KE cannot be the reason for the formation of hollow nanoparticles in our case,as there are two prerequisites to prepare hollow nanoparticles by laser ablation through KE [25].First,the band gap of the material of the shell must be larger than the laser photon energy;otherwise,the shell can be heated and destroyed by the laser irradiation.Second,the melting point of the material of shell should be higher than the boiling point of the material of core,so that the shell is not damaged by the laser-induced metal vapor [25].In our case,the ?rst condition is satis?ed as the band gap of Ag 2O (1.4eV)is slightly greater than incident photon energy (1.17eV).But the second condition is not satis?ed as the boiling point of the Ag (21631C)is much higher than the melting point of Ag 2O (2801C).The formation of metal hollow nanoparticles by laser ablation of a single solid metal target placed in a liquid has also been reported earlier by other researchers [16–18].In these cases [16–18]laser-produced bubbles are responsible for the formation of hollow nanoparticles and we have also associated this as the mechanism for the formation of hollow nanoparticles in the present experiment.The mechanism of formation of hollow nanoparticles by this process is described below,brie?y.

As the laser radiation is incident on the solid Ag target placed at the beneath of a water medium a plasma plume is generated,which is condensed thereafter and nanoparticles are formed.At the same time,due to effect of high temperature small amount of surrounding water medium is vaporized to form a bubble.Such bubble ?rst expands and then collapse after reaching to a maximum size.As the pressure inside the bubble is lower than the water pressure,except during laser ablation and bubble collapse,the prepared nanoparticles are gradually transported into the bubble.The expanding surface of the bubbles also traps the nanoparticles.Due to strong con?nement of the water medium,the expansion of the plasma plume is restricted and the growth of the nanoparticles inside the bubble is most rapid than in the water medium.However,the expansion of the bubble is adiabatic so temperature inside the bubble decreases immedi-ately after laser ablation.As the temperature inside the bubble is not uniform,the growth of the nanoparticles takes place in the boundary of the bubble favorably and remains attached to the bubble interface [26].The energy needed for the detachment of nanoparticles from the bubble interface is given by,E ?p r 2g (1àCos y )2,where r is radius of the nanoparticles,g is surface tension of surrounding liquid,y is the angle of contact of the nanoparticles with liquid [18].Taking the value of r ?1

nm,

Fig.2.Images marked as (a)and (b)show the TEM micrographs and corresponding particle size distributions of the sample

S2.

Fig.3.Images marked as (a)and (b)show the TEM micrographs and corresponding particle size distributions of the sample S3.

H.S.Desarkar et al./Journal of Luminescence 134(2013)1–7

4

g?0.072N/m and y$391[27],it is found that the value of E?0.18eV,which is much greater than the thermal energy of the nanoparticles.As a result,prepared nanoparticles remains attached to the bubble interface and hollow nanoparticles are formed.

Moreover,in our experiment it has been found that hollow nanoparticles are not formed when the laser ablation is carried out with smaller values of LAT.The reason for this is presented below.All the bubbles which are produced during laser ablation experiment do not induce formation of hollow https://www.doczj.com/doc/8912250805.html,ser-induced bubbles must trap enough nanoparticles to form hollow particles and also the nanoparticles should have enough time to diffuse to the bubble interface,which in turn requires a long lifetime of the bubble.The lifetime of the bubble T c is given by Rayleigh formula[28]

T c?1:83???????????????????????????r=PàP v R max

p

e1There,R max is the maximum radius of the bubble,r is density of the liquid,P is ambient pressure,P v is the vapor pressure.Thus from Eq.(1)we see that the collapse time of a bubble depends on the density of liquids i.e.the concentration of nanoparticles in liquid. Therefore,with smaller values of LAT duration,the probability for formation of hollow nanoparticles is reduced and no hollow nanoparticles are formed with LAT of20and40min.Some non-spherical structures of hollow nanoparticles are also seen in Fig.1b which are produced due to interaction of bubbles with the target surface.Due to an asymmetry such as presence of a solid boundary causes one side of the bubble to accelerate inward most rapidly than opposite side and result in re-entrant jet that penetrate the bubble and lead to such non-spherical structure[28].

Fig.4a shows the UV–Visible absorption characteristics of all samples.In Fig.4a solid,short-dotted and short dashed curves correspond to the samples S1,S2and S3,respectively.From Fig.4a it is seen that two absorption peaks are appearing in all samples,one in the visible region due to the well known SPR absorptions,which is the characteristics absorption of metals and another in the UV region due to interband transitions.The appearance of sharp and strong interband transition in the UV region is an important observation in this work.The inset of Fig.4a shows the variations of absorbance of the SPR and UV peaks with LAT duration.It is observed that as LAT duration is increased,the absorbance peak intensity is increased slowly at ?rst and then it becomes constant.Actually when laser ablation experiment is carried out,at?rst more numbers of nanoparticles are produced then produced nanoparticles get accumulated near laser spot and shield the incident laser radiation.Therefore,at larger values of LAT the value of the incident laser intensity which is reached to the solid target is decreased,causing no further increase in the number of nanoparticles,and so the peak value of absorbance becomes constant.

The absorption peak in the UV region appeared in all prepared samples are due to interband transitions between the sp conduc-tion band and d band.The interband transition in UV region has been reported rarely in chemically prepared Au and Ag nano-particles and in Au nanoparticles deposited in a quartz substrate by RF sputtering[29,30].The surfactants and capping molecules have also been observed to in?uence the intensity and width of the interband absorption peak[31].Also it has been reported theoretically that there is a considerable contribution of inter-band transition to the absorption spectra of Au and Ag nanopar-ticles at UV wavelengths[32].In the present work,no surfactant or capping molecules have been used and so the intense inter-band absorptions are observed and also its intensity varies with LAT duration.However the position of peak absorption remains almost constant.Rao et al.reported that due to the quantum size effects of the careers,the energy levels are discrete and this can result in a sharp and an intense absorption features correspond-ing to interband transitions in nanoparticles[33].

Photoluminescence emission spectra of the samples,prepared by using the incident laser?uence of151J/cm2but with varying LAT durations,are shown in Fig.4b.The PL emission spectra of the sample prepared with LAT duration of20min but with different laser?uence are also shown in Fig.4c.Photoluminescence emission spectra of all samples have been collected under excitation wavelength of220nm.It is found from Fig.4b and c that all samples exhibit PL emissions in the UV–Visible region peaked at$346nm.It is found further that peak PL emission intensity has been enhanced with increase in values of LAT and laser?uence but the PL peak positions remains almost unaltered. This result might be due to increase in concentration of nano-particles prepared with longer LAT duration and with higher values of laser?uence.Photoluminescence emissions from noble metals in the visible and infrared region have been reported earlier by several authors in the past[34–36].There is also report on Stokes and anti-Stokes emission of Au nanoparticles sus-pended in pure methanol and methanol solution of rhodamine 6G dye at the excitation of light of wavelength of354.6nm[37]. Photoluminescence emissions from Au surfaces and nanoparticles with the emission wavelength maximum ranging between500 and590nm have been reported by several authors,recently [34,35].Blue–green PL emission from Ag nanowire has also been reported due to electron–hole recombination[38].Photolumines-cence properties of different nanophosphors are also reported [39,40].Also Smitha et al.reported PL emission at332nm from Ag nanocolloids and observed that PL peak emission wavelength is independent of the particle size while the intensity increases sharply with decreasing particle size[41].They attributed such PL emission to radiative recombination of an electron from an occupied sp band with the hole[41].

The details of the excitation and recombination mechanisms, leading to PL emissions in our samples,are shown in Fig.4d, where the band structure for a typical noble metal is represented by a simple model which includes an s-p conduction band and two sets of d bands.When the excitation energy is high enough, the electrons in the d-bands have a probability to be excited if the vacant states in the conduction band exists and holes are created in d-bands[19].However if the recombination process occurs later,these holes?rst move closer to the conduction band electrons near the Fermi surface.Subsequent electron–phonon and hole–phonon scattering process leads to an energy loss and ?nally recombination of an electron from an occupied sp band with a hole in the d-band takes place.The line width of the SPR curves and PL spectra are also calculated and the corresponding variation of the line width of SPR curve and PL spectra with LAT is shown in Fig.4e.From Fig.4e it is found that the variation of line width of SPR and PL emission peaks with LAT duration takes place in the similar manner.

4.Conclusions

In summary,in this work we have reported preparation of silver hollow nanoparticles(15–60nm in sizes)along-with the solid silver nanoparticles($11nm in average size)by laser ablation of silver target in water medium with laser ablation time duration of50min and with the laser?uence of151J/cm2.A Q-switched Nd:YAG laser has been used as the source of laser radiation having wavelength of1064nm and pulse duration of 10ns.It has been found that with smaller laser ablation time duration of20and40min but with the same laser?uence,only solid nanoparticles are produced.Oval and irregular shaped hollow silver nanoparticles are produced due to interaction of

H.S.Desarkar et al./Journal of Luminescence134(2013)1–75

the laser produced bubbles with the rigid targets.The UV–Visible absorption spectra of all the samples show the presence of absorption peaks in the visible ($400nm)due to SPR and in the UV ($260nm)due to interband absorptions in Ag nanopar-ticles.The sharp absorption in the interband region is observed due to the absence of any capping agent or surfactants molecules.All samples prepared with different LAT durations exhibit PL emissions with a peak at $346nm under the excitation of 220nm wavelength.The PL peak emission intensity at $346nm has been found to be enhanced by the factor of $2.4in the sample prepared with 50min of laser ablation time in comparison to that obtained in the sample prepared with 20min

of laser ablation.The observed PL emissions peaked at $346nm have been attributed to recombination of electrons with holes from sp conduction band to d band of Ag.Hollow nanoparticles synthesized by the presented method may have potential appli-cations in catalysis,biomedical,and chemical sensing.

Acknowledgment

Authors are grateful to DST,Grant No.SR/FTP/PS-67/2008,Govt.of India (GOI)for the partial ?nancial support.Authors are also grateful to TEQIP (Phase-I),NIT Durgapur,GOI,for the

partial

Fig.4.(a)Variation of absorption spectra with LAT of various Ag nanocolloids prepared in water with the laser ?uence of 151J/cm 2.The solid,short-dotted and short-dashed curves correspond to the LAT duration of 20,40and 50min,respectively.The variations of peak absorbance of surface plasmon resonance (SPR)peak and UV peak with the LAT are shown in the inset of (a).PL spectra obtained at room temperature from the different samples S1,S2and S3are shown in (b).Solid,dotted and dashed curves correspond to the sample S1,S2and S3,respectively.PL spectra obtained at room temperature from the different samples prepared with different laser ?uencies are shown in (c).During preparation of these samples LAT is kept constant at 20min and here solid,dotted and dashed curves correspond to laser ?uence of 121,151and 181J/cm 2,respectively.Schematic band structure showing the excitation and recombination transitions are shown in (d).Variations of line width of the SPR and PL emission spectra with LAT are shown in (e).

H.S.Desarkar et al./Journal of Luminescence 134(2013)1–7

6

?nancial support.We are also grateful to the referee for providing critical suggestions in improving the manuscript.

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继续上黑白照,估计上面张彩色的里的车是给人收藏了,至今保养貌似很好 Silver ghost在国内通常翻译成银魅,银鬼等,是1910年(原本是1906年,但是因为10HP 车型因素,推迟到1910年上市) 《不列颠百科全书》里记载----Silver Ghost(1906年- 1925年)为公司带来了极大的赞誉。它使用六缸发动机,共生产了6173辆。1921年,公司第二家工厂在美国马萨诸塞州斯普林菲尔德开张,以满足当地的销售需求。共有1701辆“斯普林菲尔德魅(Springfield Ghosts)”

在那里生产。1931年,工厂在运转了10年之后被关闭。在银魅的底盘基础上生产出了英国第一辆装甲车并装备到了二次世界大战之中。 Silver ghost虽然稀有昂贵,但是并不是网上谣传的价值几十亿,几亿英镑。也并非只有一辆停在城堡里。《国家地理之超级工厂2-劳斯莱斯》里就提到了银魅,至今仍然有60%的现车在路上跑。至于网上说的那些都是谣传,更是拿2003年宝马推出的幻影来冒充Silver ghost,其实银魅是辆老爷车。

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