The effects of preparation condition and dopant on the electrochemical property for Fe-substituted

电化学氢扩散科斯特电化学氢扩散的研究旨在探究氢在材料中的扩散规律、机理以及对材料性能的影响，从而解决氢在各种领域（如氢能、石油化工、材料科学等）中的应用问题。

科斯特效应是电化学氢扩散中一个重要的现象，指当氢在金属中扩散时，由于氢在金属中的溶解度与温度成反比，因此在恒定温度和氢化程度时，金属中的电导率会出现随时间而降低的现象。

本文将介绍科斯特效应的原理、形成原因以及对金属材料性能的影响。

科斯特效应是氢在材料中扩散时，由于氢与材料中的电子、离子、空穴等发生相互作用而导致的电学效应。

在外加电场的作用下，材料中的离子、电子等会向电极方向运动，促进氢的扩散。

同时，由于氢与材料中的载流子发生相互作用，会影响材料的电导率，使得电导率随时间而减小，这就是科斯特效应。

科斯特效应的主要机理是氢与材料中的载流子（如电子、空穴和离子等）发生化学反应，形成电离态的氢分子离子，并促进载流子的再结合和扩散。

因此，科斯特效应的大小与载流子的浓度、移动性以及氢浓度和温度有关。

科斯特效应的形成原因是氢的扩散速率受到材料中的物理和化学因素的影响。

在高温下，材料中的氢可以溶解并扩散，但是在低温下，氢的溶解度会减小，扩散速率也会降低。

而科斯特效应就是在低温下，氢的扩散速率受到材料电导率的影响，从而使其扩散速率下降。

科斯特效应的发现和研究始于20世纪50年代，当时科学家发现在氢电极电位保持不变的条件下，金属电导率会随时间而降低。

这个现象被称为氢诱导损伤（hydrogen-induced damage），当时研究人员认为这是氢对金属晶格的损伤导致的。

但是，随着对氢扩散机制的深入研究，科学家们逐渐认识到，科斯特效应才是导致电导率下降的主要原因。

科斯特效应对金属材料的影响主要表现在两个方面：一是降低了材料的电导率，影响电子、电离子等的传输和扩散，从而影响材料的电子器件和光电器件性能；二是产生了氢脆性（hydrogen embrittlement）等问题，导致金属材料的力学性能下降，缩短材料使用寿命。

Preparation and Characterization of Thin Film Li4Ti5O12Electrodes by Magnetron SputteringC.-L.Wang,a,b Y.C.Liao,a,c,z F.C.Hsu,a,b N.H.Tai,b and M.K.Wu a,c,da Materials Science Center,b Department of Materials Science and Engineering,andc Department ofPhysics,National Tsing Hua University,Hsinchu,Taiwand Institute of Physics,Academia Sinica,Nankang,Taipei,TaiwanThis paper reports that spinel-phase Li4Ti5O12thinfilms were successfully grown by radio frequency͑rf͒magnetron sputtering on an Au/Ti/SiO2/Si substrate.In this process,the buffer layer of gold serves as a template for the texture growth of Li4Ti5O12film. The growth temperature affects the microstructure and electrochemical characteristics of the depositedfilms.In our study,the spinel phase of Li4Ti5O12appears at deposition temperatures above500°C.The redox peaks in the cyclic voltammetry of the Li/Li4Ti5O12cell approach the typical value of1.55V as raising the deposition temperature.Moreover,the influences of the surface morphology of thefilm on the capacity were studied.They show that a columnar structure with high porosity was obtained in thefilm deposited above650°C.The columnar grains with good crystallinity of the deposited Li4Ti5O12enhance the capacity of the electrode.In this work,the capacity of53␮Ah/cm2␮m can be attained for thefilm with a thickness of230nm deposited at700°C.This study sheds light on the realization of a solid-state thinfilm battery and provides a possible solution of electrical power for a mobile integrated circuit chip.©2005The Electrochemical Society.͓DOI:10.1149/1.1861193͔All rights reserved.Manuscript submitted May17,2004;revised manuscript received September25,2004.Available electronically February10,2005.Solid-state thin-film rechargeable batteries have great advantages over other types of batteries due to theirflexibility,safety,and min-iaturization.There are many potential applications,such as smart cards,complementary metal oxide semiconductor͑CMOS͒-based integrated circuits,and microelectromechanical system͑MEMS͒de-vices.Lithium-transition-metal-oxide thinfilms have long been recognized as good candidates for battery electrode materials. For example,layered-phase LiCoO2,1LiNiO2,2and spinel-phase LiMn2O43with high voltage and stability were successfully used as the positive electrode in lithium ion batteries.Thackeray et al.4pro-posed that the ionic conductor Li4Ti5O12can also be a good elec-trode material for rechargeable lithium ion batteries.This material can be used as the negative electrode in the cell combined with other high voltage materials,such as LiCoO2and LiMn2O4.5,6The theo-retical capacity of Li4Ti5O12is175mAh/g͑60␮Ah/cm2␮m͒ac-cording to the following reaction suggested by Ohzuku et al.7͑Li͒8a͑Li1/3,Ti5/3͒16d O4+e−+Li+→͑Li2͒16c͑Li1/3,Ti5/3͒16d O4 Based on this equation,during the insertion process,lithium ions are in the tetrahedral͑8a͒sites and the guest lithium ions move to the octahedral͑16c͒sites,thus the total insertion capacity is determined by the number of free octahedral sites.The merits of adopting spinel Li4Ti5O12include itsflat electrical potential,nearly zero volume change,and excellent reversibility during the insertion/extraction process of Li ions.Li4Ti5O12thinfilm prepared by the sol-gel process for lithium battery electrodes has been reported in the past.8-10The sol-gel growth method is known to be difficult to incorporate into the con-ventional semiconductor process.This article reports the successful growth of spinel Li4Ti5O12thinfilms using a radio frequency͑RF͒magnetron sputtering technique.Through a series of examinations of the crystallinity,surface morphology,and electrochemical properties of the high quality Li4Ti5O12thinfilm,this paper demonstrates the great potential of Li4Ti5O12used as the material of the electrodes of solid-state thin-film batteries.ExperimentalLi4Ti5O12thinfilms were deposited by rf magnetron sputtering from a2in.diameter target onto Au͑100nm͒/ Ti͑10nm͒/SiO2/Si substrate maintained at various temperatures in the range of500-700°C.The substrate was adhered to the surface of the heater by a silver paste,and the temperature was determined bythe thermocouple in the heater.All substrates were cleaned in anorganic solvent͑acetone,methanol,isopropanol͒using a ultrasoniccleaner.The background pressure of the chamber before the heating of the substrate was less than10−5Torr.Aufilm functions as acurrent collector,while the Ti layer is the buffer layer that improves the adhesion between Au and SiO2.These two metal layers were deposited by standard dc magnetron sputtering.The Li4Ti5O12target was prepared by the solid-state reaction of TiO2and Li2CO3pow-ders.The mixed powder was calcined at800°C.Then it was re-ground,cold pelletized,and sintered at950°C in the ambient air.The X-ray diffraction͑XRD͒patterns showed a pure spinel phase with the space group Fd3¯m.Before the deposition,the target was presputtered for about20min.Thefilms were deposited at the pres-sure of30mTorr with the mixed Ar/O2͑3:2͒gas,and the power density was estimated to beϳ4W/cm2.Allfilms have a thickness around230nm.The crystal structure was examined by an X-ray diffractometer͑MAC Science͒employing Cu K␣line.The surface morphologies of Li4Ti5O12films deposited at various temperatureswere observed with a JEOL6500F scanning electron microscope ͑SEM͒.The electrochemical properties of the oxidefilms were measuredin a two-electrode cell at room temperature.The cell uses an oxidefilm as the working electrode combined with a lithium metal foil asthe counter electrode.In the cell,the electrolyte was prepared by adopting1M LiPF6dissolved in a solution of ethylene carbonate ͑EC͒and ethylmethyl carbonate͑EMC͒with the volume ratio of 1:1.All cells were assembled inside the argon-filled glove box.For galvanostatic cycling testing,cells were discharged and charged at the constant current density of10␮A/cm2between1.0and2.0V. Cyclic voltammetry͑CV͒was performed at a sweep rate of 0.5mV/s for the characterization of thefilm electrode.ResultsTexture and crystallinity of the as-deposited thinfilms.—Figure 1shows the X-ray diffraction͑XRD͒patterns of the Li4Ti5O12thin films grown on the Au/Ti/SiO2/Si substrate at different deposition temperatures.The well-crystallized thinfilm can be obtained at the deposition temperatures above500°C,and it exhibits a texture growth in the͑111͒plane.The texture growth along certain direc-tions is beneficial to the performance of the thin-film electrode.11 These thinfilms are colorless insulators,as expected.As the sub-strate temperature is increased,the crystallinity of thefilms is sub-z E-mail:ycliao@.tw Journal of The Electrochemical Society,152͑4͒A653-A657͑2005͒0013-4651/2005/152͑4͒/A653/5/$7.00©The Electrochemical Society,Inc.A653stantially improved,and it shows a highly preferred orientation along the ͓111͔,which is the major diffusion channel of Li ion.As mentioned earlier,the Au layer functions as the current col-lector for the electrode.Surprisingly,we find that this Au layer en-hances the crystallinity of the as-grown thin films,thus gold acts as a buffer layer between the substrate and the Li 4Ti 5O 12film as well.As shown in Fig.1,the Au layer also exhibits the preferred ͑111͒orientation at the deposition temperature.The preferred orientation of the Au buffer layer provides a better template to grow ͑111͒-oriented Li 4Ti 5O 12films.This statement is proved by comparing the XRD patterns between the Li 4Ti 5O 12films deposited on the sub-strates Au/Ti/SiO 2/Si and SiO 2/Si ͑Fig.2͒.The ͑111͒peak of Li 4Ti 5O 12film grown at 700°C is enhanced by using the Au/Ti/SiO 2/Si substrate,while the amorphous SiO 2layer did not act as a good template to deposit Li 4Ti 5O 12film.The preferred orientation along ͓111͔in the Au layer also plays an important role here.Our experimental results indicate that there is no preferred orientation in the Li 4Ti 5O 12film deposited on a gold foil without a specific texture.This gives further support to the above statement.The lattice constant of Li 4Ti 5O 12film deposited on Au/Ti/SiO 2/Si,calculated from the XRD data,does not show any specific trend with the deposition temperature.The average of cubic lattice constants of the four samples is 8.291Åwith a standard deviationof 0.006Å.This value is only 0.81%less than the bulk value ͑8.358Å͒of Li 4Ti 5O 12.Perhaps it is the strain of gold ͑2a 0=8.158Å,a 0is the cubic lattice constant of gold ͒that leads to this result.To conclude the discussion on the XRD data,the gold layer on the substrate can promote the texture growth of Li 4Ti 5O 12along ͓111͔.The evolvement of surface morphology of Li 4Ti 5O 12film with the deposition temperature is shown in Fig.3.There exists a transi-tion of surface morphology around the growth temperature of 650°C.At the deposition temperature of 600°C,the Li 4Ti 5O 12film is smooth and shows densely packed grains ͑Figs.3a and 4a ͒.Above 650°C,more dispersed island-like grains emerge in the film,as shown in the cross-sectional SEM image of the sample deposited at 700°C ͑Fig.4b ͒,and the film exhibits a rougher surface.The length scale of this porous structure is around 0.1-0.2␮m.This kind of structure does not exist in the Li 4Ti 5O 12film grown on the SiO 2/Si substrate at the same growth temperature,which is demonstrated in Fig.4c.The formation of these grain structures should be attributed to the presence of islands on the Au layer.These islands,which form preferentially along the ͓111͔plane,serve as the nucleation sites for the depositing Li 4Ti 5O 12materials.Consequently,the preferred ori-ented Li 4Ti 5O 12grains with good crystallinity and the island-like structure appear only on the Au-buffered substrate.This is consistent with our XRD results.Electrochemical measurement of the as-deposited thin films .—Figure 5shows the CVs obtained from the Li 4Ti 5O 12films grown at various substrate temperatures.All cyclic voltammogram measurements were operated in the potential range between 1.0and 2.0V at a scan rate of 0.5mV/s.The measurement results indicate that the primary insertion and extraction potential of Li ion are in a range between 1.5and 1.6V,which have been suggested resulting from the coexistence of the spinel phase and the rock-salt phase during the extraction and insertion processes of Li +ions.12The CV diagrams clearly show that the shape and peak current density of redox peaks depend on the growth temperature.As increasing the deposition temperature,the difference in the peak potential and the width of the redox peak reduce gradually.This reveals the better crystallinity of the film grown at a higher temperature.The value of the potential,which is 1.54and 1.59V in Li insertion and extraction of the film deposited at 700°C respectively,agrees with the typical value of Li 4Ti 5O 12.13This result indicates that the insertion and extraction of lithium ions are easier to accomplish in the film syn-thesized under higher deposition temperature.The observation is consistent with the previous data that the films grown at higher temperature exhibits better crystallinity and preferred orientation.These films provide more reversible channels for Li ions to diffuse in the three-dimensional framework of Li 4Ti 5O 12.14Figure 6shows the discharge behaviors between 1.0and 2.0V of the films deposited at various temperatures at the constant current density of 10␮A/cm 2.All these as-grown films show the potential plateau around 1.55V,which is the typical redox value of spinel-phase Li 4Ti 5O 12.The discharge capacity for the films deposited at 700°C is about 53␮Ah/cm 2␮m,and it is much greater than the films deposited at 600°C.These observations are consistent with the results of cyclic voltammograms,where the peak current density relating to the capacity is enhanced significantly from the deposition temperature of 600to 650°C.The capacity of the deposited thin film increases substantially as the deposition temperature over 650°C.However,the crystallinity does not change drastically above 650°C.This suggests that the crystallinity of the as-grown film is not the sole reason responsible for the large energy capacity.The plot of both ⌬2␪of ͑111͒diffraction peak and the discharge capacity confirms this suggestion further.In the left axis of Fig.7,it shows that the crystallinity of Li 4Ti 5O 12film improves gradually with rais-ing the growth temperature while there is a significant enhancement of discharge capacity above 650°C,as shown in the right axis.The transitions of electrochemical properties coincide with the transition of surface morphology ͑Fig.3and 4͒.It is apparent that thesurfaceFigure 1.XRD patterns of the Li 4Ti 5O 12films deposited on Au/Ti/SiO 2/Si at various deposition temperatures.It shows that both Li 4Ti 5O 12film and the gold layer have the preferred orientation ͑111͒.Figure 2.XRD patterns of the Li 4Ti 5O 12films on the two substrates Au/Ti/SiO 2/Si and SiO 2/Si grown at 700°C.The film on Au/Ti/SiO 2/Si has a much better crystallinity than the film on SiO 2/Si.A654Journal of The Electrochemical Society ,152͑4͒A653-A657͑2005͒morphology of the film also plays an important role on the capacity.Owing to the finite diffusion length of Li ions in Li 4Ti 5O 12,Li ions cannot fully penetrate into the grains.Those island-like grains that exist in the films deposited at higher temperatures provide much more effective area for the insertion of Li ions.This statement is inagreement with the previous study on the relationship between the charge capability and the particle size of Li 4Ti 5O 12.15In that paper,Kavan et al.showed that the charge capacity is proportional to the surface area of Li 4Ti 5O 12powder before the particle size reaches to few tens of nanometers.Therefore,the high capacity of Li 4Ti 5O 12film deposited on Au/Ti/SiO 2/Si at 700°C results from both the rougher island-like grains and the good crystallinity,and conse-quently,it has sharp redox peaks and a large capacity.ConclusionsSpinel-phase Li 4Ti 5O 12thin films are successfully grown by rf magnetron sputtering on Au/Ti/SiO 2/Si substrate.Thedeposi-Figure 3.SEM images of the surface morphology of Li 4Ti 5O 12thin films deposited on Au/Ti/SiO 2/Si at ͑a ͒600,͑b ͒650,and ͑c ͒700°C.The surface morphology transits to a rougher one at the deposition temperature above650°C.Figure 4.SEM image of the cross-sectional structure of Li 4Ti 5O 12thin films deposited at ͑a ͒600and ͑b ͒700on Au/Ti/SiO 2/Si and ͑c ͒700°C on SiO 2/Si.The film on Au/Ti/SiO 2/Si grown at 700°C has a disperse-like grain structure while the same one deposited at 600°C shows the close-packed grains.This is attributed to the effect of the gold layer because the film grown on SiO 2/Si at 700°C did not have a columnar structure.A655Journal of The Electrochemical Society ,152͑4͒A653-A657͑2005͒tion temperature influences the physical and electrochemical characteristics of the films profoundly.Li 4Ti 5O 12films grown on Au/Ti/SiO 2/Si can possess good crystallinity and proper surface morphology for the application in an electrode of a thin film ing the optimized Li 4Ti 5O 12thin film,the test cell of Li/Li 4Ti 5O 12exhibits sharp redox peaks and a large capacity.The capacity of this film estimated by the discharge curve is 53␮Ah/cm 2␮m,and this value is comparable to those elec-trodes prepared by other methods.Both CV diagrams and dis-charge curves show that thin film Li 4Ti 5O 12/Au/Ti/SiO 2/Si depos-ited by sputtering can be used as an excellent negative electrode in a lithium thin-film battery.The results of this study demonstrate the potential for the realization of lithium-based solid-state thin-film batteries.AcknowledgmentsThe authors thank Chen-En Wu for help taking the SEM images.We also thank Phillip Wu for help editing the English writing.This work is supported by the Taiwan National Science Council grant no.NSC91-2112-M-007-056.Figure 5.Cyclic voltammograms of Li 4Ti 5O 12thin films deposited on Au/Ti/SiO 2/Si at various deposition temperatures ͑a ͒600,͑b ͒650,and ͑c ͒700°C in 1M in LiPF 6/EC +EMC at 0.5mV/s.The peak current density is significantly enhanced above 650°C.The potentials of reduction peak ͑Li +insertion ͒and oxidization peak ͑Li +extraction ͒agree with otherstudies.Figure 6.Initial discharge curves of Li 4Ti 5O 12thin films deposited on Au/Ti/SiO 2/Si at various temperatures.The substantial increase of charge capacity indicates that there should be some transition around the deposition temperature of 650°C.The capacity of the film grown at 700°C reaches to nearly 90%of the theoretical value ͑60␮Ah/cm 2␮m ͒.Figure 7.The plot of both ⌬2␪of ͑111͒diffraction peak ͑left axis ͒and the discharge capacity ͑right axis ͒.It indicates that the enhancement of capacity of Li 4Ti 5O 12thin film does not totally result from the improvement of crys-tallinity.Because the discharge curve of the film deposited at 500°C did not have any observable plateau,the discharge capacity of this film is nominally zero in our measurement.A656Journal of The Electrochemical Society ,152͑4͒A653-A657͑2005͒National Tsing Hua University assisted in meeting the publication costs of this article.References1. C.N.Polo da Fonseca,J.Davalos,M.Kleinke,M.C.A.Fantini,and A.Gorenstein,J.Power Sources,81-82,575͑1999͒.2.M.Yoshimura,K.S.Han,and S.Tsurimoto,Solid State Ionics,106,39͑1998͒.3. F.K.Shokoohi,J.M.Tarascon,B.J.Wolkens,D.Guyomard,and C.C.Chang,J.Electrochem.Soc.,137,1845͑1992͒.4. E.Ferg,R.J.Gummow,A.de Kock,and M.M.Thackeray,J.Electrochem.Soc.,141,L147͑1994͒.5.N.Koshiba,K.Takada,M.Nakanishi,K.Chikayama,and Z.Takehara,DenkiKagaku oyobi Kogyo Butsuri Kagaku,62,970͑1994͒.6.G.X.Wang,D.H.Bradhurst,S.X.Dou,and H.K.Liu,J.Power Sources,83,156͑1999͒.7.T.Ohzuku,A.Ueda,and N.Yamamoto,J.Electrochem.Soc.,142,1431͑1995͒.8.Y.H.Rho,K.Kanamura,M.Fujisaki,J.Hamagami,S.Suda,and T.Umegaki,SolidState Ionics,151,151͑2002͒.9.L.Kavan and M.Grätzel,Electrochem.Solid-State Lett.,5,A39͑2002͒.10.Y.H.Rho,K.Kanamura,and T.Umegaki,Chem.Lett.,2001,1322.11.K.-F.Chiu,F.C.Hsu,G.S.Chen,and M.K.Wu,J.Electrochem.Soc.,150,503͑2003͒.12.S.Scharner,W.Weppner,and P.Schmid-Beurmann,J.Electrochem.Soc.,146,857͑1999͒.13. D.Peramunage and K.M.Abraham,J.Electrochem.Soc.,145,2609͑1998͒.14. C.-M.Shen,X.-G.Zhang,Y.-K.Zhou,and H.-L.Li,Mater.Chem.Phys.,78,437͑2002͒.15.L.Kavan,G.Procházka,T.M.Spitler,M.Kalbáč,M.Zakalová,T.Drezen,and M.Grätzel,J.Electrochem.Soc.,150,1000͑2003͒.A657Journal of The Electrochemical Society,152͑4͒A653-A657͑2005͒。

姜泰勒效应锰酸锂摘要：一、引言1.介绍姜泰勒效应2.姜泰勒效应在锰酸锂中的应用二、姜泰勒效应的原理1.姜泰勒效应的定义2.姜泰勒效应的发生条件3.姜泰勒效应的影响因素三、锰酸锂的性质1.锰酸锂的基本性质2.锰酸锂的晶体结构3.锰酸锂的电化学性能四、姜泰勒效应在锰酸锂中的应用1.提高锰酸锂的电化学性能2.改善锰酸锂的循环稳定性3.提高锰酸锂的安全性能五、总结1.姜泰勒效应对锰酸锂的重要性2.未来发展方向正文：一、引言姜泰勒效应，是指在某些离子化合物中，当温度变化时，其晶格会发生畸变，从而导致离子间距和晶格常数发生变化的现象。

锰酸锂作为一种重要的锂离子电池正极材料，其性能受到姜泰勒效应的影响较大。

本文将详细介绍姜泰勒效应在锰酸锂中的应用及其重要性。

二、姜泰勒效应的原理1.姜泰勒效应的定义姜泰勒效应是由英国物理学家威廉·泰勒（William Taylor）和约翰·姜（John J.）于1951年首次发现的。

他们发现，在某些离子晶体中，当温度变化时，晶格会发生畸变，从而导致离子间距和晶格常数发生变化。

这种现象被称为姜泰勒效应。

2.姜泰勒效应的发生条件姜泰勒效应的发生需要满足以下条件：（1）晶体具有较高的离子性；（2）晶格中存在较弱的离子间相互作用力；（3）温度变化较大。

3.姜泰勒效应的影响因素姜泰勒效应的程度受到以下因素的影响：（1）离子化合物的类型；（2）晶格结构；（3）离子间距离；（4）温度变化。

三、锰酸锂的性质1.锰酸锂的基本性质锰酸锂（LiMn2O4）是一种具有尖晶石结构的锂离子电池正极材料，具有较高的理论容量和较优的电化学性能。

2.锰酸锂的晶体结构锰酸锂的晶体结构为尖晶石结构，由锂离子（Li+）、锰离子（Mn2+）和氧离子（O2-）组成。

3.锰酸锂的电化学性能锰酸锂具有较高的理论容量（约为148 mAh/g），较好的循环稳定性和倍率性能。

但在实际应用中，锰酸锂的性能受到其晶体结构、离子间相互作用力等因素的影响，导致其性能受限。

第５０卷增刊化工新型材料Ｖｏｌ．５０Ｓｕｐｐｌ．

２０２２年１０月ＮＥＷ　ＣＨＥＭＩＣＡＬ　ＭＡＴＥＲＩＡＬＳ

全氟聚醚硅氮烷的制备及其疏水涂层的性能研究苏厚鑫　樊　荣　唐旭东＊

（天津科技大学化工与材料学院，天津３００４５７）

摘　要　以Ｋ型全氟聚醚羧酸（数均分子量Ｍｎ＝３３００和６０００）和双［３－（三甲氧基甲硅烷基）丙基］胺为原料，

通

过硅氢加成合成３种全氟聚醚硅氮烷用红外光谱（ＦＴ－ＩＲ）、核磁氢谱（１　ＨＮＭＲ）、Ｘ射线光电子能谱（ＸＰＳ）对Ｋ型全

氟聚醚硅氮烷的结构进行表征，并利用接触角和耐摩擦实验对全氟聚醚硅氮烷的耐摩擦性能进行测试。探究了相对

分子量大小、分子结构对涂层耐磨性能影响，以及涂层的耐化学稳定性和透光性能的优劣。结果表明：全氟聚醚硅氮

烷（Ｍ

ｎ＝３３００和６０００）均具有优异的疏水性能。二氯一甲基硅烷合成的全氟聚醚硅氮烷（Ｋ６０００－ＰＦＰＥ　Ｓｉｌａｚａｎｅ　Ｓｉ－Ｎ

（４））的耐摩擦性能最好，在负载质量为

１０００ｇ

的外力作用下钢丝绒往返循环摩擦２０００次后水接触角仍能保持在

９７．７°。化学稳定性和透光性能测试结果表明涂层具有良好的耐酸性、耐盐性和透光性能。关键词

全氟聚醚，硅氮烷，接触角，耐摩擦性能

中图分类号　ＴＱ３１７　文献标识码　Ａ　文章编号：１００６－３５３６（２０２２）Ｓ－０２７３－０５

ＤＯＩ：１０．１９８１７／ｊ．ｃｎｋｉ．ｉｓｓｎ１００６－３５３６．２０２２．Ｓ．０５２　

Ｓｔｕｄｙ　ｏｎ　ｔｈｅ　ｐｒｅｐａｒａｔｉｏｎ　ｏｆ　ｐｅｒｆｌｕｏｒｏｐｏｌｙｅｔｈｅｒ　ｓｉｌａｚａｎｅ　ａｎｄｔｈｅ　ｐｅｒｆｏｒｍａｎｃｅ　ｏｆ　ｉｔｓ　ｈｙｄｒｏｐｈｏｂｉｃ　ｃｏａｔｉｎ

ｇ

Ｓｕ　Ｈｏｕｘｉｎ　Ｆａｎ　Ｒｏｎｇ　Ｔａｎｇ　Ｘｕｄｏｎｇ

（Ｓｃｈｏｏｌ　ｏｆ　Ｃｈｅｍｉｃａｌ　Ｅｎｇｉｎｅｅｒｉｎｇ　ａｎｄ　Ｍａｔｅｒｉａｌ　Ｓｃｉｅｎｃｅ，Ｔｉａｎｊｉｎ　Ｕｎｉｖｅｒｓｉｔｙ　ｏｆ　Ｓｃｉｅｎｃｅ　ａｎｄ

第４０卷㊀第７期２０１９年７月发㊀光㊀学㊀报ＣＨＩＮＥＳＥＪＯＵＲＮＡＬＯＦＬＵＭＩＮＥＳＣＥＮＣＥＶｏｌ ４０Ｎｏ ７Ｊｕｌｙꎬ２０１９文章编号:１０００￣７０３２(２０１９)０７￣０９１５￣０７界面处理对ＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴｓ器件动态特性的影响韩㊀军１ꎬ赵佳豪１ꎬ赵㊀杰１ꎬ２ꎬ邢艳辉１∗ꎬ曹㊀旭１ꎬ付㊀凯２ꎬ宋㊀亮２ꎬ邓旭光２ꎬ张宝顺２(１.北京工业大学信息学部光电子技术省部共建教育部重点实验室ꎬ北京㊀１００１２４ꎻ２.中国科学院苏州纳米技术与纳米仿生研究所纳米器件与应用重点实验室ꎬ江苏苏州㊀２１５１２３)摘要:研究不同界面处理对ＡｌＧａＮ/ＧａＮ金属￣绝缘层￣半导体(ＭＩＳ)结构的高电子迁移率晶体管(ＨＥＭＴ)器件性能的影响ꎮ采用Ｎ２和ＮＨ３等离子体对器件界面预处理ꎬ实验结果表明ꎬＮ２等离子体预处理能够减小器件的电流崩塌ꎬ通过对Ｎ２等离子体预处理的时间优化ꎬ发现预处理时间１０ｍｉｎ能够较好地提高器件的动态特性ꎬ３０ｍｉｎ时动态性能下降ꎮ进一步引入ＡｌＮ作为栅介质插入层并经过高温热退火后能够有效提高器件的动态性能ꎬ将器件的阈值回滞从４１１ｍＶ减小至１１１ｍＶꎬ动态测试表明ꎬ在９００Ｖ关态应力下ꎬ器件的电流崩塌因子从４２.０４减小至４.７６ꎮ关㊀键㊀词:电流崩塌ꎻＡｌＮ栅介质插入层ꎻ界面处理ꎻＡｌＧａＮ/ＧａＮ高电子迁移率晶体管中图分类号:ＴＮ３８６.２㊀㊀㊀文献标识码:Ａ㊀㊀㊀ＤＯＩ:１０.３７８８/ｆｇｘｂ２０１９４００７.０９１５ＩｍｐａｃｔｏｆＩｎｔｅｒｆａｃｅＴｒｅａｔｍｅｎｔｏｎＤｙｎａｍｉｃＣｈａｒａｃｔｅｒｉｓｔｉｃｏｆＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴｓＨＡＮＪｕｎ１ꎬＺＨＡＯＪｉａ￣ｈａｏ１ꎬＺＨＡＯＪｉｅ１ꎬ２ꎬＸＩＮＧＹａｎ￣ｈｕｉ１∗ꎬＣＡＯＸｕ１ꎬＦＵＫａｉ２ꎬＳＯＮＧＬｉａｎｇ２ꎬＤＥＮＧＸｕ￣ｇｕａｎｇ２ꎬＺＨＡＮＧＢａｏ￣ｓｈｕｎ２(１.ＫｅｙＬａｂｏｒａｔｏｒｙｏｆＯｐｔｏ￣ｅｌｅｃｔｒｏｎｉｃｓＴｅｃｈｎｏｌｏｇｙꎬＭｉｎｉｓｔｒｙｏｆＥｄｕｃａｔｉｏｎꎬＢｅｉｊｉｎｇＵｎｉｖｅｒｓｉｔｙｏｆＴｅｃｈｎｏｌｏｇｙꎬＢｅｉｊｉｎｇ１００１２４ꎬＣｈｉｎａꎻ２.ＫｅｙＬａｂｏｒａｔｏｒｙｏｆＮａｎｏＤｅｖｉｃｅｓａｎｄＡｐｐｌｉｃａｔｉｏｎｓꎬＳｕｚｈｏｕＩｎｓｔｉｔｕｔｅｏｆＮａｎｏ￣ｔｅｃｈａｎｄＮａｎｏ￣ｂｉｏｎｉｃｓꎬＣｈｉｎｅｓｅＡｃａｄｅｍｙｏｆＳｃｉｅｎｃｅｓꎬＳｕｚｈｏｕ２１５１２３ꎬＣｈｉｎａ)∗ＣｏｒｒｅｓｐｏｎｄｉｎｇＡｕｔｈｏｒꎬＥ￣ｍａｉｌ:ｘｉｎｇｙａｎｈｕｉ＠ｂｊｕｔ.ｅｄｕ.ｃｎＡｂｓｔｒａｃｔ:ＴｈｅｅｆｆｅｃｔｓｏｆｄｉｆｆｅｒｅｎｔｋｉｎｄｓｏｆｉｎｔｅｒｆａｃｅｔｒｅａｔｍｅｎｔｏｎｔｈｅｃｈａｒａｃｔｅｒｉｓｔｉｃｏｆＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴｓｗｅｒｅｓｔｕｄｉｅｄｉｎｔｈｉｓｐａｐｅｒ.Ｎ２ａｎｄＮＨ３ｐｌａｓｍａｐｒｅｔｒｅａｔｍｅｎｔｗｅｒｅｕｓｅｄｔｏｉｍｐｒｏｖｅｔｈｅｉｎｔｅｒｆａｃｅｑｕａｌｉｔｙ.ＴｈｅｒｅｓｕｌｔｓｓｈｏｗｔｈａｔＮ２ｐｌａｓｍａｐｒｅｔｒｅａｔｍｅｎｔｃｏｕｌｄｒｅｄｕｃｅｔｈｅｃｕｒｒｅｎｔｃｏｌｌａｐｓｅｏｆｄｅｖｉｃｅｓ.ＢｙｏｐｔｉｍｉｚｉｎｇｔｈｅｔｉｍｅｏｆＮ２ｐｌａｓｍａｐｒｅｔｒｅａｔｍｅｎｔꎬｉｔｗａｓｆｏｕｎｄｔｈａｔｔｈｅｄｙｎａｍｉｃｃｈａｒａｃｔｅｒｉｓｔｉｃｏｆｄｅｖｉｃｅｓｗｉｔｈ１０ｍｉｎｔｈｅｐｒｅｔｒｅａｔｍｅｎｔｗａｓｉｍｐｒｏｖｅｄꎬｗｈｉｌｅｔｈａｔｏｆ３０ｍｉｎｗａｓｄｅｇｒａｄｅｄ.Ａｓａｇａｔｅｄｉｅｌｅｃｔｒｉｃｉｎ￣ｔｅｒｃａｌａｔｉｏｎｌａｙｅｒꎬｔｈｅａｎｎｅａｌｅｄＡｌＮｉｎｔｅｒｌａｙｅｒｃａｎｅｆｆｅｃｔｉｖｅｌｙｉｍｐｒｏｖｅｔｈｅｄｙｎａｍｉｃｃｈａｒａｃｔｅｒｉｓｔｉｃｏｆｔｈｅｄｅｖｉｃｅ.ＴｈｅＶｔｈｈｙｓｔｅｒｅｓｉｓｗａｓｄｅｃｒｅａｓｅｄｆｒｏｍ４１１ｍＶｔｏ１１１ｍＶꎬａｎｄｔｈｅｄｅｖｉｃｅｃｕｒｒｅｎｔｃｏｌｌａｐｓｅｆａｃｔｏｒｗａｓｒｅｄｕｃｅｄｆｒｏｍ４２.０４ｔｏ４.７６ａｆｔｅｒｕｎｄｅｒＯＦＦ￣ｓｔａｔｅＶＤｓｔｒｅｓｓｏｆ９００.Ｋｅｙｗｏｒｄｓ:ｃｕｒｒｅｎｔｃｏｌｌａｐｓｅꎻＡｌＮｇａｔｅｄｉｅｌｅｃｔｒｉｃｉｎｓｅｒｔｉｏｎｌａｙｅｒꎻｉｎｔｅｒｆａｃｅｔｒｅａｔｍｅｎｔꎻＡｌＧａＮ/ＧａＮｈｉｇｈｅｌｅｃｔｒｏｎｍｏｂｉｌｉｔｙｔｒａｎｓｉｓｔｏｒｓ㊀㊀收稿日期:２０１８￣０８￣２０ꎻ修订日期:２０１８￣１０￣１７㊀㊀基金项目:国家自然科学基金(６１２０４０１１ꎬ１１２０４００９ꎬ６１５７４０１１)ꎻ北京市自然科学基金(４１４２００５ꎬ４１８２０１４)ꎻ北京市教委科学研究基金(ＰＸＭ２０１８＿０１４２０４＿５０００２０)资助项目ＳｕｐｐｏｒｔｅｄｂｙＮａｔｉｏｎａｌＮａｔｕｒａｌＳｃｉｅｎｃｅＦｏｕｎｄａｔｉｏｎｏｆＣｈｉｎａ(６１２０４０１１ꎬ１１２０４００９ꎬ６１５７４０１１)ꎻＢｅｉｊｉｎｇＮａｔｕｒａｌＳｃｉｅｎｃｅＦｏｕｎｄａ￣ｔｉｏｎ(４１４２００５ꎬ４１８２０１４)ꎻＢｅｉｊｉｎｇＭｕｎｉｃｉｐａｌＥｄｕｃａｔｉｏｎＣｏｍｍｉｓｓｉｏｎＳｃｉｅｎｔｉｆｉｃＲｅｓｅａｒｃｈＦｕｎｄ(ＰＸＭ２０１８＿０１４２０４＿５０００２０)９１６㊀发㊀㊀光㊀㊀学㊀㊀报第４０卷１㊀引㊀㊀言ＧａＮ作为第三代半导体的代表ꎬ具有高禁带宽度㊁高击穿电场㊁高电子迁移率㊁以及耐酸碱等特点ꎮ以ＡｌＧａＮ和ＧａＮ异质结结构制备的高电子迁移率晶体管ꎬ由于极化效应产生的天然的高浓度㊁高迁移率的二维电子气ꎬ在功率开关器件的大功率及高频性能方面有很好的应用前景[１￣４]ꎮＭＩＳ￣ＨＥＭＴ器件可以有效地减小器件的栅极漏电ꎬ提高耐压ꎬ提高栅驱动能力ꎮ但是由于栅介质的引入ꎬ产生新的界面ꎬ界面质量给器件的应用带来新的问题ꎬ影响器件的可靠性和阈值回滞等ꎮＥｌｌｅｒ等[５]详细报道了对于ＧａＮ表面的处理过程ꎬ包括湿法化学处理[６]㊁真空退火处理[７]㊁气体氛围下退火处理[８]及离子束㊁等离子体处理[９￣１０]等ꎮＧａＮ材料表面存在含Ｏ的化合物和Ｎ空位[２ꎬ１１]ꎬ这两种缺陷态成为影响界面质量的主要因素ꎬ目前的报道中ꎬ集中于使用含Ｎ等离子体来处理器件表面[１２￣１４]ꎬ主要作用机理为去除Ｏ杂质和补充Ｎ空位ꎮＨａｓｈｉｚｕｍｅ[１５]在器件钝化作用前使用Ｎ２作为等离子体处理样品表面ꎬ得到了很高质量的钝化结果ꎬ而且界面态浓度下降ꎮＲｏｍｅｒｏ[１６]通过原位含氮气等离子体预处理ꎬ器件的电流崩塌㊁输出功率㊁增益等特性取得了非常好的效果ꎮ在本文研究中ꎬ我们对ＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴ器件工艺过程中的界面处理进行优化比较ꎬ实验利用等离子体预处理研究不同气体(Ｎ２和ＮＨ３)及不同预处理时间对器件直流性能和动态特性的影响ꎬ并在该研究基础上ꎬ继续引入ＡｌＮ栅介质插入层进行界面处理ꎬ研究采用ＡｌＮ栅介质插入层进行界面处理对器件动静态特性的影响ꎮ２㊀实㊀㊀验ＡｌＧａＮ/ＧａＮＨＥＭＴ外延材料是通过金属有机物化学气相沉积技术在Ｓｉ(１１１)衬底上生长的ꎬ外延结构依次为成核层㊁ＧａＮ缓冲层和ＡｌＧａＮ势垒层ꎮ器件的制备工艺过程为:(１)界面处理过程ꎻ(２)栅介质钝化层制备ꎬ采用ＬＰＣＶＤ沉积ＳｉＮｘ作为栅介质ꎬ主要考虑其具有良好的稳定性和漏电[７]ꎬ利用ＳｉＨ２Ｃｌ２和ＮＨ３作为Ｓｉ源和Ｎ源ꎬ温度７８０ħꎻ(３)注入隔离ꎬ采用Ｆ离子进行注入隔离ꎻ(４)欧姆接触制备ꎬ利用磁中性环路放电刻蚀ＳｉＮｘ形成窗口ꎬ电子束蒸发沉积Ｔｉ/Ａｌ/Ｎｉ/Ａｕ为２０/１３０/５０/５０ｎｍꎬＮ２氛围下８５０ħ退火３０ｓ形成欧姆接触ꎻ(５)栅电极制备ꎬ利用金属热蒸发沉积Ｎｉ/Ａｕ为５０/１０ｎｍ制备栅电极ꎮ图１(ａ)显示的是ＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴ器件基本结构示意图ꎬ器件栅介质层厚度为２０ｎｍꎬ器件栅长为２μｍꎬ栅宽为１００μｍꎬ栅漏距离为１６μｍꎬ栅源距离为４μｍꎮ其中对于界面处理工艺过程ꎬ设计了实验Ⅰ:采用不同预处理气体Ｎ２和ＮＨ３对ＡｌＧａＮ/ＧａＮＨＥＭＴ表面预处理ꎬ预处理时间均为５ｍｉｎꎬ实验分别设置为样品Ａ和样品Ｂꎮ在实验Ｉ基础上设计实验方案Ⅱ:选取Ｎ２作为预处理气体ꎬ研究不同预处理时间对ＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴ器件的影响ꎬ设置样品Ｃ㊁Ｄ㊁Ｅ分别预处理的时间为０ꎬ１０ꎬ３０ｍｉｎꎮ上述等离子体预处理温度为３５０ħꎬ压强为２６６Ｐａ(２０００ｍｔｏｒｒ)ꎬＲＦ功率为６０ＷꎬＬＦ功率为５０ＷꎮSiN x2DEGAlGaNSiBufferSGAlN2DEGAlGaNSiN xSiBufferSGDD（a）（b）图１㊀(ａ)实验器件基本结构示意图ꎻ(ｂ)引入插入层后的器件结构示意图ꎮＦｉｇ.１㊀(ａ)Ｓｃｈｅｍａｔｉｃｏｆｄｅｖｉｃｅｓｆｏｒｄｉｆｆｅｒｅｎｔｐｒｅ￣ｔｒｅａｔｍｅｎｔ.(ｂ)Ｓｃｈｅｍａｔｉｃｏｆｄｅｖｉｃｅｓｔｒｕｃｔｕｒｅｆｏｒｓａｍｐｌｅｗｉｔｈｉｎ￣ｓｅｒｔｉｏｎｌａｙｅｒ.为进一步改善ＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴ器件性能ꎬ在上述实验的基础上ꎬ设计实验Ⅲ:采取ＰＥＡＬＤ生长的ＡｌＮ作为栅介质插入层ꎬ设置样品Ｆ㊁Ｇ㊁Ｈꎬ引入ＡｌＮ插入层的器件结构示意图为图１(ｂ)ꎮ样品Ｆ作为空白对照组未引入插入层界面处理过程ꎬ样品Ｇ和样品Ｈ利用ＰＥＡＬＤ生长３ｎｍＡｌＮꎬＴＭＡｌ为Ａｌ源ꎬＮ２为Ｎ源ꎬ生长温度３００ħꎮ样品Ｈ在栅介质沉积后于Ｎ２氛围下１０００ħ退火２ｍｉｎꎮ样品栅介质ＬＰＣＶＤ￣ＳｉＮｘ１２ｎｍꎮ器件尺寸分别为:栅长２μｍꎬ栅宽１００μｍꎬ栅漏距离３０μｍꎬ栅源距离３μｍꎮ每组实验均采用安捷伦Ｂ１５０５Ａ进行测试表征ꎮ㊀第７期韩㊀军ꎬ等:界面处理对ＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴｓ器件动态特性的影响９１７㊀３㊀结果与讨论３.１㊀界面预处理气体的影响图２是Ｎ２和ＮＨ３预处理器件的转移输出曲线ꎬ从图２中可以看出不同的预处理气体对器件的直流特性具有明显的影响ꎮＮ２和ＮＨ３等离子体预处理之后器件的峰值跨导分别是６４.６ｍＳ/ｍｍ和７０.７ｍＳ/ｍｍꎬ饱和电流分别为５７９.３ｍＡ/ｍｍ和５５０ｍＡ/ｍｍꎮＮ２等离子体预处理的器件跨导峰值较ＮＨ３等离子体预处理器件低ꎬ但是饱和电流有所增加ꎮ在图２中还看到ꎬ相比于Ｎ２等离子体预处理ꎬＮＨ３等离子体预处理的实验结果中存在饱和电流下降的现象ꎬ这与Ｋｉｍ[１２]报道的一致ꎬ究其原因是在ＮＨ３在较低功率下产生等离子体的同时会产生一个Ｈ＋的钝化效果ꎮ类似的钝化对于器件的ＲＦ性能会有所提升ꎬ但对器件的ＤＣ特性有退化ꎬＨａｓｈｉｚｕｍｅ[１７]和Ｒｏｍｅｒｏ[１６]的研究已经证明了这一点ꎮ为了进一步对比采用Ｎ２和ＮＨ３不同预处理气体对表面态引起的器件性能退化作用ꎬ实验对样品Ａ和样品Ｂ进行了电流崩塌的表征ꎮ图３分别显示了关态下漏极电压600500-20V GS /VI D /(m A ·m m -1)4003002001000N 2plasmaNH 3plasma（a ）-15-10-55406080200G m /(m S ·m m -1)6005002V d /VI D /(m A ·m m -1)4003002001000N 2plasma NH 3plasma（b ）461012143V -3V -5V -7V -9V80V GS -15~3V 图２㊀Ｎ２和ＮＨ３等离子体预处输出曲线理器件转移输出曲线对比ꎮ(ａ)转移曲线ꎻ(ｂ)输出曲线ꎮＦｉｇ.２㊀ＴｔｒａｎｓｆｅｒａｎｄｏｕｔｐｕｔｃｕｒｖｅｓｆｏｒｓａｍｐｌｅＡｗｉｔｈＮ２ｐｌａｓｍａａｎｄｓａｍｐｌｅＢｗｉｔｈＮＨ３ｐｌａｓｍａ.(ａ)Ｔｒａｎｓ￣ｆｅｒｃｕｒｖｅｓ.(ｂ)Ｏｕｔｐｕｔｃｕｒｖｅｓ.10080300V d /VR D y n a m i c /R O N20010100506040200N 2plasma NH 3plasmaOFF 鄄state:V GS =-15VOFF 鄄ON swtiching time:t =200滋s ON 鄄state:V GS =0V V D =1V图３㊀Ｎ２和ＮＨ３等离子体预处理器件电流崩塌对比Ｆｉｇ.３㊀ＣｕｒｒｅｎｔｃｏｌｌａｐｓｅｆｏｒｓａｍｐｌｅＡｗｉｔｈＮ２ｐｌａｓｍａａｎｄｓａｍｐｌｅＢｗｉｔｈＮＨ３ｐｌａｓｍａ１０ꎬ５０ꎬ１００ꎬ２００ꎬ３００Ｖ下的电流崩塌ꎮ从图３中可以看到在不同的漏极偏压下ꎬＮ２等离子体预处理器件的电流崩塌因子明显较ＮＨ３等离子体预处理的小ꎬＮ２等离子体预处理器件在偏压１００Ｖ时崩塌因子最大值为３５.６ꎬＮＨ３等离子体预处理器件为５７.５ꎻ在偏压３００Ｖ时ꎬＮＨ３等离子体预处理器件的崩塌因子最大值为８５.３ꎬＮ２等离子体预处理器件为１９.１ꎮ对比器件的动静态性能ꎬ采用Ｎ２等离子体预处理能够有效地提高器件的动态性能ꎮ３.２㊀界面预处理时间的影响图４给出了不同预处理时间下ꎬ器件转移输出特性对比ꎮ结果显示不同预处理时间对样品的基本电学性能影响不明显ꎬ预处理后器件的静态性能没有大的提高ꎮ采用ｐｕｌｓｅ￣ＤＣ表征器件的动态性能ꎮ器件测试脉冲是(５ｍｓꎬ３ｍｓ)ꎬ即关态偏压施加的时间是３ｍｓꎬ测试周期是５ｍｓꎬ器件关态偏压为(ＶＤ:５０ＶꎬＶＧＳ:－２０Ｖ)ꎮ图５中展示了不同时间预处理器件的直流/脉冲输出电流曲线对比ꎮ相比于静态输出电流ꎬＣ㊁Ｄ㊁Ｅ样品的脉冲输出电流都发生了明显下降ꎬ其中未经过Ｎ２等离子体预处理的样品Ｃ下降最为严重ꎬ预处理时间１０ｍｉｎ的样品Ｄ结果最好ꎬ样品Ｃ㊁Ｄ及样品Ｅ的饱和电流下降幅度分别为３０６.１ꎬ９９.１ꎬ１８４.５ｍＡ/ｍｍꎮ该结果表明利用Ｎ２等离子体预处理能够明显地减小器件界面导致的性能退化ꎮ对比预处理１０ｍｉｎ的样品Ｄ和处理３０ｍｉｎ的样品Ｅ的结果ꎬ发现长时间的预处理对器件的性能有一定的损害ꎬ主要原因是长时间的预处理导致表面有正电荷或者新的施主态的积累ꎬ使得器件动态性能下降[１８]ꎮ９１８㊀发㊀㊀光㊀㊀学㊀㊀报第４０卷V GS /V600500-15I D /（m A ·m m -1）400300200CD E 1000-20-10-505V d :10V20406080G m /（m S ·m m -1）（a ）V D /V6005004I D /（m A ·m m -1）400300200C D E100001081214V GS （b ）-14~2V 622V -2V-6V-10V 图４㊀不同预处理时间下器件转移输出特性曲线ꎮ(ａ)转移曲线ꎻ(ｂ)输出曲线ꎮＦｉｇ.４㊀Ｔｒａｎｓｆｅｒａｎｄｏｕｔｐｕｔｃｕｒｖｅｓｆｏｒｔｈｒｅｅｓａｍｐｌｅｓ.(ａ)Ｔｒａｎｓｆｅｒｃｕｒｖｅｓ.(ｂ)Ｏｕｔｐｕｔｃｕｒｖｅｓ.6005002V D /VI D /（m A ·m m -1）（a ）Pulse:(5ms,3ms)Based:(V d ,V gs )(50V,-20V)DC:V g :-14~2V step:4V V d :0~10VDCPulse40030020010000468101214166005002V D /VI D /（m A ·m m -1）（b ）Pulse:(5ms,3ms)Based:(V d ,V gs )(50V,-20V)DC:V gs :-14~2V step:4V V d :0~10VDC Pulse40030020010000468101214166005002V D /VI D /（m A ·m m -1）（c ）Pulse:(5ms,3ms)Based:(V d ,V gs )(50V,-20V)DC:V gs :-14~2V step:4V V d :0~10VDC Pulse 4003002001000046810121416600500CV D /VI D /（m A ·m m -1）（d ）400300D E200DCPulse100图５㊀直流㊁脉冲输出曲线对比ꎮ(ａ)样品Ｃꎻ(ｂ)样品Ｄꎻ(ｃ)样品Ｅꎻ(ｄ)实验样品直流/脉冲下饱和电流对比ꎮＦｉｇ.５㊀ＣｏｍｐａｒｉｓｉｏｎｏｆｐｕｌｓｅｄＩ￣Ｖｃｈａｒａｃｔｅｒｉｓｔｉｃｓ.(ａ)ＳａｍｐｌｅＣ.(ｂ)ＳａｍｐｌｅＤ.(ｃ)ＳａｍｐｌｅＥ.(ｄ)ＣｏｍｐａｒｉｓｏｎｏｆｓａｔｕｒａｔｉｏｎｏｕｔｐｕｔｃｕｒｒｅｎｔｄｅｎｓｉｔｙｂｅｔｗｅｅｎｐｕｌｓｅｄａｎｄＤＣ.３.３㊀界面栅介质插入层的影响图６展示了器件的转移输出特性对比ꎮ为了更明显地显示ꎬ将样品Ｆ㊁Ｇ的对比结果显示于图６(ａ)㊁(ｂ)ꎬ将样品Ｇ㊁Ｈ的对比结果显示于图６(ｃ)㊁(ｄ)ꎮ样品Ｆ㊁Ｇ和Ｈ阈值电压分别为－６.４６ꎬ－７.６２ꎬ－７.０４Ｖꎬ由此看出采用ＡｌＮ栅介质插入层导致了器件的阈值向负漂移ꎬ是因为引入ＡｌＮ插入层会在表面形成极化正电荷ꎬ影响阈值电压ꎮ图６中给出了样品Ｆ㊁Ｇ和Ｈ导通电阻分别为１３.８ꎬ１５.７ꎬ２０.６Ω ｍｍꎮ和样品Ｆ比较ꎬ样品Ｇ和Ｈ导通电阻增加的原因可能是引入ＡｌＮ介质插入层会造成导通电阻在一定范围内退化ꎬ从而使饱和电流下降[１９￣２０]ꎮ观察图６(ｃ)ꎬ发现样品Ｈ中ꎬ从－１５Ｖ扫到５Ｖ的正向及从５Ｖ回扫到－１５Ｖ的转移曲线回滞明显消除ꎬ而没有高温退火的样品Ｇ中回滞现象明显ꎮ图７给出了实验样品的正向阈值与负向阈值的对比ꎬ器件的阈值在回扫过程中会出现正向漂移ꎬＦ㊁Ｇ和Ｈ器件的阈值回滞ΔＶｔｈ(Ｖｔｈ负向－Ｖｔｈ正向)分别为４１１ꎬ５０６ꎬ１１１ｍＶꎮ和样品Ｆ相比ꎬ样品Ｈ的ΔＶｔｈ降低７２.９９％ꎬ可以看出采用退火后ＡｌＮ栅介质插入层界面处理的器件阈值回滞明显消除ꎬ说明由界面引起的器件性能退化得到控制ꎮ另外ꎬ未经过退火的ＡｌＮ介质插入层的界面处理的器件Ｇ㊀第７期韩㊀军ꎬ等:界面处理对ＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴｓ器件动态特性的影响９１９㊀阈值回滞反而增大ꎬ这可能是ＡｌＮ材料中存在缺陷导致的ꎮ经过１０００ħ的退火过程的样品ＨꎬＡｌＮ材料存在重结晶过程ꎬ提高了ＡｌＮ材料质量ꎬ改善了界面质量ꎮ400-15V GS /VI D /（m A ·m m -1）（a ）30020010006Reference(F)AlN interlaye(G)V GS :-15~5VV D :15~-15V V D :10V-12-9-6-303２00４0６0８0Ｇm /（m S ·m m -1）400V D /VI D /（m A ·m m -1）（b ）3002001000Reference(F)AlN interlaye(G)２４６８１０R ON (F)=13.8赘·mm R ON (G)=15.7赘·mm400-15V GS /VI D /（m A ·m m -1）（c ）30020010006Anneal(H)AlN interlaye(G)V GS :15~5V V GS :15~-15V V D :10V-12-9-6-303２00４0６0８0Ｇm /（m S ·m m -1）400V D /VI D /（m A ·m m -1）（d ）3002001000AlN interlayer anneal(H)AlN interlaye(G)２４６８１０R ON (G)=15.7赘·mm R ON (G)=20.6赘·mmAlN interlayer(G)图６㊀样品转移㊁输出特性曲线对比ꎮ(ａ㊁ｂ)样品Ｆ㊁Ｇ对比ꎻ(ｃ㊁ｄ)样品Ｇ㊁Ｈ对比ꎮＦｉｇ.６㊀Ｃｏｍｐａｒｉｓｏｎｏｆｔｒａｎｓｆｅｒａｎｄｏｕｔｐｕｔｃｕｒｖｅｓｆｏｒｓａｍｐｌｅｓ.(ａꎬｂ)ＳａｍｐｌｅＦａｎｄｓａｍｐｌｅＧ.(ｃꎬｄ)ＳａｍｐｌｅＧａｎｄｓａｍｐｌｅＨ.-6.2FV t h /VGH506mV111mVV GS :-15~5V V GS :5~-15V411mV -6.0-6.4-6.6-6.8-7.0-7.2-7.4-7.6图７㊀样品Ｆ㊁Ｇ㊁Ｈ正回扫阈值回滞对比ꎮＦｉｇ.７㊀ＶｔｈｈｙｓｔｅｒｅｓｉｓｆｏｒｓａｍｐｌｅＦꎬｓａｍｐｌｅＧａｎｄｓａｍｐｌｅＨ.图８给出了样品Ｆ㊁Ｇ㊁Ｈ电流崩塌对比ꎮ对比样品Ｆ和Ｇ数据ꎬ可以看出未经过退火处理的ＡｌＮ插入层对器件的电流崩塌的改善不明显ꎬ这一结论同图７中器件阈值回滞变化相一致ꎮ对比样品Ｇ与Ｈ可以看出ꎬ器件的电流崩塌得到了很好的提高ꎬ９００Ｖ下电流崩塌因子由样品Ｇ中的４２.０４下降到样品Ｈ的４.７６ꎬ抑制效果明显ꎮ因此利用退火ＡｌＮ作为栅介质插入层进行界面处理ꎬ能够有效改善Ａｌ￣ＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴ器件界面ꎬ提高界面质量ꎬ抑制电流崩塌ꎬ提高器件可靠性ꎮQuiesent drain bias/V80R D y n a m i c /R O N40080010060402002006001000AlN interlayer anneal(H)AlN interlayer(G)Reference(F)图８㊀样品Ｆ㊁Ｇ㊁Ｈ电流崩塌对比ꎮＦｉｇ.８㊀ＣｕｒｒｅｎｔｃｏｌｌａｐｓｅｆｏｒｓａｍｐｌｅＦꎬｓａｍｐｌｅＧａｎｄｓａｍｐｌｅＨ.４㊀结㊀㊀论本文研究了ＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴ器件制备过程中不同界面处理对其性能的影响ꎮ研究发现ꎬ经过Ｎ２等离子体预处理较ＮＨ３等离子体预处理能够降低器件的电流崩塌因子ꎬ提高器件的可靠性ꎬ在该研究基础上优化了Ｎ２等离子体预处理时间ꎬ实验结果显示１０ｍｉｎ等离子体预处理能９２０㊀发㊀㊀光㊀㊀学㊀㊀报第４０卷够有效地提高器件脉冲下电流ꎮ进一步引入ＡｌＮ栅介质插入层ꎬ实验发现利用ＡｌＮ插入层及退火工艺能够有效地改善ＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴ器件界面质量ꎬ抑制电流崩塌ꎬ提高器件可靠性ꎬ器件的阈值回滞从４１１ｍＶ减小至１１１ｍＶꎬ实现在关态应力９００Ｖ下将器件的电流崩塌因子由４２.０４下降到４.７６ꎮ参㊀考㊀文㊀献:[１]ＺＨＡＮＧＺＬꎬＹＵＧＨꎬＺＨＡＮＧＸＤꎬｅｔａｌ..Ｓｔｕｄｉｅｓｏｎｈｉｇｈ￣ｖｏｌｔａｇｅＧａＮ￣ｏｎ￣ＳｉＭＩＳ￣ＨＥＭＴｓｕｓｉｎｇＬＰＣＶＤＳｉ３Ｎ４ａｓｇａｔｅｄｉｅｌｅｃｔｒｉｃａｎｄｐａｓｓｉｖａｔｉｏｎｌａｙｅｒ[Ｊ].ＩＥＥＥＴｒａｎｓ.ＥｌｅｃｔｒｏｎＤｅｖ.ꎬ２０１６ꎬ６３(２):７３１￣７３８.[２]ＬＩＵＳＣꎬＣＨＥＮＢＹꎬＬＩＮＹＣꎬｅｔａｌ..ＧａＮＭＩＳ￣ＨＥＭＴｓｗｉｔｈｎｉｔｒｏｇｅｎｐａｓｓｉｖａｔｉｏｎｆｏｒｐｏｗｅｒｄｅｖｉｃｅａｐｐｌｉｃａｔｉｏｎｓ[Ｊ].ＩＥＥＥＥｌｅｃｔｒｏｎＤｅｖ.Ｌｅｔｔ.ꎬ２０１４ꎬ３５(１０):１００１￣１００３.[３]ＫＥＬＥＫÇＩÖꎬＴＡŞＬＩＰＴꎬＹＵＨＢꎬｅｔａｌ..ＥｌｅｃｔｒｏｎｔｒａｎｓｐｏｒｔｐｒｏｐｅｒｔｉｅｓｉｎＡｌ０.２５Ｇａ０.７５Ｎ/ＡｌＮ/ＧａＮｈｅｔｅｒｏｓｔｒｕｃｔｕｒｅｓｗｉｔｈｄｉｆｆｅｒｅｎｔＩｎＧａＮｂａｃｋｂａｒｒｉｅｒｌａｙｅｒｓａｎｄＧａＮｃｈａｎｎｅｌｔｈｉｃｋｎｅｓｓｅｓｇｒｏｗｎｂｙＭＯＣＶＤ[Ｊ].Ｐｈｙｓ.ＳｔａｔｕｓＳｏｌｉｄｉꎬ２０１２ꎬ２０９(３):４３４￣４３８.[４]王凯ꎬ邢艳辉ꎬ韩军ꎬ等.掺Ｆｅ高阻ＧａＮ缓冲层特性及其对ＡｌＧａＮ/ＧａＮ高电子迁移率晶体管器件的影响研究[Ｊ].物理学报ꎬ２０１６ꎬ６５(１):０１６８０２￣１￣６.ＷＡＮＧＫꎬＸＩＮＧＹＨꎬＨＡＮＪꎬｅｔａｌ..ＧｒｏｗｔｈｓｏｆＦｅ￣ｄｏｐｅｄＧａＮｈｉｇｈ￣ｒｅｓｉｓｔｉｖｉｔｙｂｕｆｆｅｒｌａｙｅｒｓｆｏｒＡｌＧａＮ/ＧａＮｈｉｇｈｅｌｅｃｔｒｏｎｍｏｂｉｌｉｔｙｔｒａｎｓｉｓｔｏｒｄｅｖｉｃｅｓ[Ｊ].ＡｃｔａＰｈｙｓ.Ｓｉｎｉｃａꎬ２０１６ꎬ６５(１):０１６８０２￣１￣６.(ｉｎＣｈｉｎｅｓｅ)[５]ＥＬＬＥＲＢＳꎬＹＡＮＧＪＬꎬＮＥＭＡＮＩＣＨＲＪ.ＥｌｅｃｔｒｏｎｉｃｓｕｒｆａｃｅａｎｄｄｉｅｌｅｃｔｒｉｃｉｎｔｅｒｆａｃｅｓｔａｔｅｓｏｎＧａＮａｎｄＡｌＧａＮ[Ｊ].Ｊ.Ｖａｃ.Ｓｃｉ.Ｔｅｃｈｎｏｌ.Ａꎬ２０１３ꎬ３１(５):０５０８０７￣１￣２９.[６]ＸＩＯＮＧＣꎬＬＩＵＳＨꎬＬＩＹＨꎬｅｔａｌ..Ｈｏｔｃａｒｒｉｅｒｅｆｆｅｃｔｏｎｔｈｅｂｉｐｏｌａｒｔｒａｎｓｉｓｔｏｒｓ ｒｅｓｐｏｎｓｅｔｏｅｌｅｃｔｒｏｍａｇｎｅｔｉｃｉｎｔｅｒｆｅｒｅｎｃｅ[Ｊ].Ｍｉｃｒｏｅｌｅｃｔｒ.Ｒｅｌｉａｂｉｌ.ꎬ２０１５ꎬ５５(３￣４):５１４￣５１９.[７]ＺＨＡＮＧＺＬꎬＦＵＫꎬＤＥＮＧＸＧꎬｅｔａｌ..ＮｏｒｍａｌｌｙｏｆｆＡｌＧａＮ/ＧａＮＭＩＳ￣ｈｉｇｈ￣ｅｌｅｃｔｒｏｎｍｏｂｉｌｉｔｙｔｒａｎｓｉｓｔｏｒｓｆａｂｒｉｃａｔｅｄｂｙｕｓｉｎｇｌｏｗｐｒｅｓｓｕｒｅｃｈｅｍｉｃａｌｖａｐｏｒｄｅｐｏｓｉｔｉｏｎＳｉ３Ｎ４ｇａｔｅｄｉｅｌｅｃｔｒｉｃａｎｄｓｔａｎｄａｒｄｆｌｕｏｒｉｎｅｉｏｎｉｍｐｌａｎｔａｔｉｏｎ[Ｊ].ＩＥＥＥＥｌｅｃｔｒｏｎＤｅｖ.Ｌｅｔｔ.ꎬ２０１５ꎬ３６(１１):１１２８￣１１３１.[８]ＰＥＮＧＭＺꎬＺＨＥＮＧＹＫꎬＷＥＩＫꎬｅｔａｌ..Ｐｏｓｔ￣ｐｒｏｃｅｓｓｔｈｅｒｍａｌｔｒｅａｔｍｅｎｔｆｏｒｍｉｃｒｏｗａｖｅｐｏｗｅｒｉｍｐｒｏｖｅｍｅｎｔｏｆＡｌＧａＮ/ＧａＮＨＥＭＴｓ[Ｊ].Ｍｉｃｒｏｅｌｅｃｔｒ.Ｅｎｇ.ꎬ２０１０ꎬ８７(１２):２６３８￣２６４１.[９]ＶＡＮＫＯＧꎬＬＡＬＩＮＳＫＹ'ＴꎬＨＡŠＣ㊅ÍＫＳꎬｅｔａｌ..ＩｍｐａｃｔｏｆＳＦ６ｐｌａｓｍａｔｒｅａｔｍｅｎｔｏｎｐｅｒｆｏｒｍａｎｃｅｏｆＡｌＧａＮ/ＧａＮＨＥＭＴ[Ｊ].Ｖａｃｕｕｍꎬ２００９ꎬ８４(１):２３５￣２３７.[１０]ＭＥＹＥＲＤＪꎬＦＬＥＭＩＳＨＪＲꎬＲＥＤＷＩＮＧＪＭ.ＳＦ６/Ｏ２ｐｌａｓｍａｅｆｆｅｃｔｓｏｎｓｉｌｉｃｏｎｎｉｔｒｉｄｅｐａｓｓｉｖａｔｉｏｎｏｆＡｌＧａＮ/ＧａＮｈｉｇｈｅｌｅｃｔｒｏｎｍｏｂｉｌｉｔｙｔｒａｎｓｉｓｔｏｒｓ[Ｊ].Ａｐｐｌ.Ｐｈｙｓ.Ｌｅｔｔ.ꎬ２００６ꎬ８９(２２):２２３５２３￣１￣３.[１１]ＷＡＴＡＮＡＢＥＴꎬＴＥＲＡＭＯＴＯＡꎬＮＡＫＡＯＹꎬｅｔａｌ..Ｌｏｗ￣ｉｎｔｅｒｆａｃｅ￣ｔｒａｐ￣ｄｅｎｓｉｔｙａｎｄｈｉｇｈ￣ｂｒｅａｋｄｏｗｎ￣ｅｌｅｃｔｒｉｃ￣ｆｉｅｌｄＳｉＮＦｉｌｍｓｏｎＧａＮｆｏｒｍｅｄｂｙｐｌａｓｍａｐｒｅｔｒｅａｔｍｅｎｔｕｓｉｎｇｍｉｃｒｏｗａｖｅ￣ｅｘｃｉｔｅｄｐｌａｓｍａ￣ｅｎｈａｎｃｅｄｃｈｅｍｉｃａｌｖａｐｏｒｄｅｐｏｓｉｔｉｏｎ[Ｊ].ＩＥＥＥＴｒａｎｓ.ＥｌｅｃｔｒｏｎＤｅｖ.ꎬ２０１３ꎬ６０(６):１９１６￣１９２２.[１２]ＫＩＭＪＨꎬＣＨＯＩＨＧꎬＨＡＭＷꎬｅｔａｌ..Ｅｆｆｅｃｔｓｏｆｎｉｔｒｉｄｅ￣ｂａｓｅｄｐｌａｓｍａｐｒｅｔｒｅａｔｍｅｎｔｐｒｉｏｒｔｏＳｉＮｘＰａｓｓｉｖａｔｉｏｎｉｎＡｌＧａＮ/ＧａＮｈｉｇｈ￣ｅｌｅｃｔｒｏｎ￣ｍｏｂｉｌｉｔｙｔｒａｎｓｉｓｔｏｒｓｏｎｓｉｌｉｃｏｎｓｕｂｓｔｒａｔｅｓ[Ｊ].Ｊｐｎ.Ｊ.Ａｐｐｌ.Ｐｈｙｓ.ꎬ２０１０ꎬ４９(４Ｓ):０４ＤＦ０５. [１３]ＨＵＡＮＧＳꎬＪＩＡＮＧＱＭꎬＹＡＮＧＳꎬｅｔａｌ..ＥｆｆｅｃｔｉｖｅｐａｓｓｉｖａｔｉｏｎｏｆＡｌＧａＮ/ＧａＮＨＥＭＴｓｂｙＡＬＤ￣ｇｒｏｗｎＡｌＮｔｈｉｎｆｉｌｍ[Ｊ].ＩＥＥＥＥｌｅｃｔｒｏｎＤｅｖ.Ｌｅｔｔ.ꎬ２０１２ꎬ３３(４):５１６￣５１８.[１４]ＥＤＷＡＲＤＳＡＰꎬＭＩＴＴＥＲＥＤＥＲＪＡꎬＢＩＮＡＲＩＳＣꎬｅｔａｌ..ＩｍｐｒｏｖｅｄｒｅｌｉａｂｉｌｉｔｙｏｆＡｌＧａＮ￣ＧａＮＨＥＭＴｓｕｓｉｎｇａｎＮＨ３/ｐｌａｓ￣ｍａｔｒｅａｔｍｅｎｔｐｒｉｏｒｔｏＳｉＮｐａｓｓｉｖａｔｉｏｎ[Ｊ].ＩＥＥＥＥｌｅｃｔｒｏｎＤｅｖ.Ｌｅｔｔ.ꎬ２００５ꎬ２６(４):２２５￣２２７.[１５]ＨＡＳＨＩＺＵＭＥＴꎬＯＯＴＯＭＯＳꎬＯＹＡＭＡＳꎬｅｔａｌ..ＣｈｅｍｉｓｔｒｙａｎｄｅｌｅｃｔｒｉｃａｌｐｒｏｐｅｒｔｉｅｓｏｆｓｕｒｆａｃｅｓｏｆＧａＮａｎｄＧａＮ/ＡｌＧａＮｈｅｔｅｒｏｓｔｒｕｃｔｕｒｅｓ[Ｊ].Ｊ.Ｖａｃ.Ｓｃｉ.Ｔｅｃｈｎｏｌ.ꎬ２００１ꎬ１９(４):１６７５￣１６８１.[１６]ＲＯＭＥＲＯＭＦꎬＪＩＭÉＮＥＺＪＩＭＥＮＥＺＡꎬＭＩＧＵＥＬ￣ＳÁＮＣＨＥＺＭＩＧＵＥＬ￣ＳＡＮＣＨＥＺＪꎬｅｔａｌ..ＥｆｆｅｃｔｓｏｆＮ２ｐｌａｓｍａｐｒｅｔｒｅａｔ￣ｍｅｎｔｏｎｔｈｅＳｉＮｐａｓｓｉｖａｔｉｏｎｏｆＡｌＧａＮ/ＧａＮＨＥＭＴ[Ｊ].ＩＥＥＥＥｌｅｃｔｒｏｎＤｅｖ.Ｌｅｔｔ.ꎬ２００８ꎬ２９(３):２０９￣２１１.[１７]ＨＡＳＨＩＺＵＭＥＴꎬＯＯＴＯＭＯＳꎬＩＮＡＧＡＫＩＴꎬｅｔａｌ..ＳｕｒｆａｃｅｐａｓｓｉｖａｔｉｏｎｏｆＧａＮａｎｄＧａＮ/ＡｌＧａＮｈｅｔｅｒｏｓｔｒｕｃｔｕｒｅｓｂｙｄｉｅｌｅｃ￣ｔｒｉｃｆｉｌｍｓａｎｄｉｔｓａｐｐｌｉｃａｔｉｏｎｔｏｉｎｓｕｌａｔｅｄ￣ｇａｔｅｈｅｔｅｒｏｓｔｒｕｃｔｕｒｅｔｒａｎｓｉｓｔｏｒｓ[Ｊ].Ｊ.Ｖａｃ.Ｓｃｉ.Ｔｅｃｈｎｏｌ.Ｂꎬ２００３ꎬ２１(４):１８２８￣１８３８.㊀第７期韩㊀军ꎬ等:界面处理对ＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴｓ器件动态特性的影响９２１㊀[１８]ＲＥＩＮＥＲＭꎬＬＡＧＧＥＲＰꎬＰＲＥＣＨＴＬＧꎬｅｔａｌ..Ｍｏｄｉｆｉｃａｔｉｏｎｏｆ ｎａｔｉｖｅ ｓｕｒｆａｃｅｄｏｎｏｒｓｔａｔｅｓｉｎＡｌＧａＮ/ＧａＮＭＩＳ￣ＨＥＭＴｓｂｙｆｌｕｏｒｉｎａｔｉｏｎ:ｐｅｒｓｐｅｃｔｉｖｅｆｏｒｄｅｆｅｃｔｅｎｇｉｎｅｅｒｉｎｇ[Ｃ].ＰｒｏｃｅｅｄｉｎｇｓｏｆＩＥＥＥＩｎｔｅｒｎａｔｉｏｎａｌＥｌｅｃｔｒｏｎＤｅｖｉｃｅｓＭｅｅｔｉｎｇꎬＷａｓｈ￣ｉｎｇｔｏｎꎬＤＣꎬＵＳＡꎬ２０１５:３５.５.１￣３５.５.４.[１９]ＡＣＵＲＩＯＥꎬＣＲＵＰＩＦꎬＭＡＧＮＯＮＥＰꎬｅｔａｌ..ＩｍｐａｃｔｏｆＡｌＮｌａｙｅｒｓａｎｄｗｉｃｈｅｄｂｅｔｗｅｅｎｔｈｅＧａＮａｎｄｔｈｅＡｌ２Ｏ３ｌａｙｅｒｓｏｎｔｈｅｐｅｒｆｏｒｍａｎｃｅａｎｄｒｅｌｉａｂｉｌｉｔｙｏｆｒｅｃｅｓｓｅｄＡｌＧａＮ/ＧａＮＭＯＳ￣ＨＥＭＴｓ[Ｊ].Ｍｉｃｒｏｅｌｅｃｔｒ.Ｅｎｇ.ꎬ２０１７ꎬ１７８:４２￣４７.[２０]ＨＵＡＮＧＳꎬＪＩＡＮＧＱＭꎬＹＡＮＧＳꎬｅｔａｌ..ＭｅｃｈａｎｉｓｍｏｆＰＥＡＬＤ￣ｇｒｏｗｎＡｌＮｐａｓｓｉｖａｔｉｏｎｆｏｒＡｌＧａＮ/ＧａＮＨＥＭＴｓ:ｃｏｍｐｅｎ￣ｓａｔｉｏｎｏｆｉｎｔｅｒｆａｃｅｔｒａｐｓｂｙｐｏｌａｒｉｚａｔｉｏｎｃｈａｒｇｅｓ[Ｊ].ＩＥＥＥＥｌｅｃｔｒｏｎＤｅｖ.Ｌｅｔｔ.ꎬ２０１３ꎬ３４(２):１９３￣１９５.韩军(１９６４－)ꎬ男ꎬ北京人ꎬ博士ꎬ副教授ꎬ２００８年于北京工业大学获得博士学位ꎬ主要从事半导体材料与器件方面的研究ꎮＥ￣ｍａｉｌ:ｈａｎｊｕｎ＠ｂｊｕｔ.ｅｄｕ.ｃｎ邢艳辉(１９７４－)ꎬ女ꎬ吉林德惠人ꎬ博士ꎬ副教授ꎬ２００８年于北京工业大学获得博士学位ꎬ主要从事氮化镓半导体材料的生长㊁测试分析及器件等方面的研究ꎮＥ￣ｍａｉｌ:ｘｉｎｇｙａｎｈｕｉ＠ｂｊｕｔ.ｅｄｕ.ｃｎ。

掺杂元素对LLZO的制备及与金属锂界面性能的影响刘彦博;陈挺;郑鸿鹏;徐比翼;段华南;刘河洲;王可;吴勇民【摘要】Solid state lithium-ion battery represents an important trend of battery technology.For the researching for the interface's performance of solid state electrolyte,in this work,LLZO with different dopants (Ta,Nb, Sb and Te)was synthesized and the conductivity and interfacial resistance with lithium metal were compared. The ionic conductivity and interfacial properties under different temperatures were also investigated.The results show that the LLZO doped with Ta maintained the ionic conductivity of5×10-4 S/cm and had the best per-formance in terms of the interfacial resistance.The EIS results showed that the interfacial resistance was decrea-sing with the increasing temperature,so that the LLZO would be one of the most promising solid state electro-lyte.%针对固态电解质的界面性能的研究和改进,制备了掺杂不同元素(Ta、Nb、Sb和Te)的含锂石榴石LLZO,对比了它们的传导率和界面电阻,探究了不同温度下的LLZO的离子传导性能及界面性能.发现当掺杂了Ta元素的情况下保持原有的传导率,传导率为5×10-4 S/cm,并且能够获得最好界面性能,并且随着温度的升高,对Li的界面电阻在不断下降,是具有应用前景的固态电解质.【期刊名称】《功能材料》【年(卷),期】2017(048)012【总页数】5页(P12001-12004,12010)【关键词】LLZO;掺杂;界面电阻;交流阻抗【作者】刘彦博;陈挺;郑鸿鹏;徐比翼;段华南;刘河洲;王可;吴勇民【作者单位】上海交通大学材料科学与工程学院,金属基复合材料国家重点实验室,上海 200240;上海交通大学材料科学与工程学院,金属基复合材料国家重点实验室,上海 200240;上海交通大学材料科学与工程学院,金属基复合材料国家重点实验室,上海 200240;上海交通大学材料科学与工程学院,金属基复合材料国家重点实验室,上海 200240;上海交通大学材料科学与工程学院,金属基复合材料国家重点实验室,上海 200240;上海交通大学材料科学与工程学院,金属基复合材料国家重点实验室,上海 200240;上海空间电源研究所,空间电源技术国家重点实验室,上海 200245;上海空间电源研究所,空间电源技术国家重点实验室,上海 200245【正文语种】中文【中图分类】TM912当今市场上快速发展的电动汽车行业、太阳能风能等的能源行业、航空航天储能产业等，都对现阶段的电池提出了更高的要求，由于锂离子电池具有着重量轻，比能量高，寿命长，无记忆效应等优点[1-2]，得到了越来越多的应用，在一定程度上逐渐取代了镍氢电池和镍镉电池。

不同处理条件下铜离子溶液的电沉积行为铜离子的电沉积，是目前广泛应用于电子、汽车、航空、建筑等众多领域的一种重要技术。

而不同的处理条件，则会影响着铜离子电沉积的行为。

本文将从电沉积条件、溶液浓度、电流密度和PH值等几个方面来探讨不同处理条件下铜离子溶液的电沉积行为。

1.电沉积条件的影响电沉积条件是指在进行铜离子电沉积时所设置的参数，如电压、电流密度、时间等。

其中，电压会影响电沉积速率和密度，而电流密度则会影响电沉积品质和晶体形态。

时间则是电沉积完成的标志。

因此，我们在进行铜离子电沉积时，需要根据需要调整电压、电流密度和时间等参数。

2.溶液浓度的影响溶液浓度是指铜离子的浓度，它直接决定着电沉积所得的铜层质量。

通常情况下，在相同的电流密度下，铜离子的浓度越高，得到的铜层厚度也会越大。

但是过高的铜离子浓度也会导致表面粗糙和孔隙问题。

因此，我们在进行铜离子电沉积时，应该控制好浓度，以得到高质量的铜层。

3.电流密度的影响电流密度是指单位面积上电流通过的量，它会直接影响电沉积的速率和品质。

当电流密度较低时，铜层生长速率较慢，而且颗粒细小；而当电流密度较高时，则生长速率快，颗粒较粗大。

因此，合适的电流密度可以提高电沉积速率和铜层品质。

4.PH值的影响PH值是指溶液的酸碱度，它会对电沉积的结果产生影响。

当PH值过高时，会导致铜层中出现气泡和孔隙，严重影响铜层的品质；而当PH值过低时，则会导致电沉积速率下降，且铜层会出现暗色和较不均匀的现象。

因此，我们在进行铜离子电沉积时，需要控制好PH值，以得到高品质的铜层。

总之，在进行铜离子电沉积时，不同的处理条件会对结果产生影响。

因此，我们应该根据具体情况，对各个参数进行合理的调整和控制，以得到高品质的铜层。

电化学偏压
电化学偏压是指在电化学反应中，通过外加直流电压的方式来影响电极上的反应过程。

电化学偏压可以通过向电极施加阳极或阴极电位，从而引发氧化或还原反应。

在电化学阻抗谱测量中，直流偏压可以起到控制电极表面反应的作用。

是否需要施加偏压，取决于实验设计和目标。

例如，在腐蚀研究中，通常在开路电位下测量阻抗，不施加任何直流电位。

而在催化剂或锂电等研究中，通常需要在充电或放电状态下，或在不同电位下观察电极的性能和反应特性，此时需要施加直流偏压。

在使用电化学偏压时，需要根据实验条件和目标选择合适的偏压大小和施加方式，并进行相应的测试和数据分析，以获得可靠的实验结果。

第33卷第1期2021年1月化学研究与应用Chemical Research and ApplicationVol.33,No.1Jan.,2021文章编号:1004-1656(2021)01-0090-07热处理气氛对a-Fe203光阳极光电化学性能影响研究李龙珠*，吴浩宇，陈玉伟，杨蓉,唐惠东(常州工程职业技术学院化工与制药工程学院，江苏常州213164)摘要:分别在空气和氮气中对水热制备的薄膜进行热处理获得了纳米棒状a-Fe2()3光阳极。

对样品分别进行T X射线衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)、紫外-可见吸收光谱和光电化学性能测试。

与空气热处理获得的a-Fe2O3Air光阳极相比，氮气气氛热处理获得的a-Fe2O3N2光阳极正面光照电流密度显著提升达到0.42mA-cm'%正面光照下,a-Fe2O3N2光阳极的体内电荷分离效率弘强和表面电荷注入效率Nwfaee都有较大增加，说明％热处理明显增加了«-Fe203膜的载流子浓度，增强了体内载流子的传输和表面载流子注入效率。

关键词:光电化学电池;水分解；a-Fe203;水热法中图分类号:TK91文献标志码:AEffects of annealing atmosphere on the photoelectrochemicalperformance of a-Fe2O3photoanodesLI Long-zhu*,WU Hao-yu,CHEN Yu-wei,YANG Rong,TANG Hui-dong(School of Chemical and Pharmaceutical Engineering,Changzhou Vocational Institute of Engineering,Changzhou213164,China)Abstract:The hydrothermal prepared films were converted into nanorods-like a-Fe203photoanodes by annealing treatment in air and nitrogen,respectively・The samples were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM) ,X-ray photoelectron spectroscopy(XPS),UV-vis absorption spectroscopy and photoelectrochemical properties.Under front illumination,the photocurrent density of the a-Fe2O3photoanode annealed in nitrogen atmosphere increased significantly to0.42mA•cm'2compared with that of hematite photoanode annealed in air.The a-Fe203photoanode annealed in nitrogen atmosphere had gready increased ^buik i7surface under front illumination,which indicated that nitrogen heat treatment significantly increased the carrier concentration of the hematite film and enhanced the carrier transport in the bulk and surface carrier injection efficiency.Key words:photoelectrochemical；water splitting；a-Fe203；hydrothermal method收稿日期=2020-06-09；修回日期：2020-10-12基金项目：江苏省高等学校自然科学研究面上项目(19KJB510001)资助;江苏省青蓝工程项目资助；国家自然科学基金项目(51874050)资助联系人简介:李龙珠(1981-)，女,副教授，主要从事新能源材料制备研究。