Low-temperature synthesis of apatite-type La_(9.33)Ge_6O_(26) as electrolytes with high conductivity

In the present study,high-quality apatite-type La_(9.33)Ge_6O_(26) powders are successfully synthesized by a facile moltensalt synthesis method(MSSM) at low temperatures,using Li Cl,Li Cl/Na Cl mixture(mass ratio 1:1) as molten salt,respectively.Experimental results indicate that the optimal mass ratio between reactant and molten salt is 1:2,and Li Cl/Na Cl mixed molten-salt is more beneficial for forming high-quality La_(9.33)Ge_6O_(26) powders than Li Cl individual molten-salt.Comparing with the conventional solid-state reaction method(SSRM),the synthesis temperature of apatitetype La_(9.33)Ge_6O_(26) powders using the MSSM decreases more than 350?C,which can effectively avoid Ge loss in the preparation process of precursor powders.Furthermore,the powders obtained by the MSSM are homogeneous,nonagglomerated and well crystallized,which are very favorable for gaining dense pellets in the premise of avoiding Ge loss.On the basis of high-quality precursor powders,the dense and pure ceramic pellets of La_(9.33)Ge_6O_(26) are gained at a low temperature of 1100?C for 2 h,which exhibit higher conductivities(σ850?C(Li Cl)= 2.3 × 10~(-2) S·cm~(-1),σ850 ?C(Li Cl/Na Cl) = 4.9 × 10~(-2) S·cm~(-1)) and lower activation energies(Ea(Li Cl)= 1.02 e V,Ea(Li Cl/Na Cl)= 0.99 e V) than that synthesized by the SSRM.     

固态电解质锂镧锆氧(Li_7La_3Zr_2O_(12))制备及第一性原理研究

固态电解质(SSE)是锂离子电池(LIB)的关键材料.Li_7La_3Zr_2O_(12)(LLZO)固体电解质是全固态锂离子电池开发中的关键部分.采用高温固相法制备了不同烧结温度后的四方Li_7La_3Zr_2O_(12)(t-LLZO)和立方Li_7La_3Zr_2O_(12)(c-LLZO),分析了两种样品的结构性能.800℃下烧结12小时的t-LLZO呈四方相,晶格尺寸为a=b=13.13064?,c=12.66024?,离子电导率为3.42×10~(-8)S·cm~(-1);1000℃下烧结12小时的c-LLZO呈立方相,晶格尺寸为a=b=c=13.03544?,离子电导率为8.48×10~(-5)S·cm~(-1).另基于密度泛函理论(DFT)的第一性原理计算了四方相和立方相的LLZO固体电解质材料的能带结构、晶格参数、态密度和键布居.通过理论计算解释了四方相LLZO离子电导率低于立方相LLZO的原因.     

新型电极材料Sb掺杂BaSnO_3薄膜的外延生长及其在铁电薄膜电容器中的应用

本文利用脉冲激光沉积技术在SrTiO_3单晶衬底上生长了Sb掺杂BaSnO_3(BSSO)外延薄膜.结构和输运性质测量结果显示BSSO薄膜是一种具有立方钙钛矿结构导电性很好的薄膜材料,80K时呈现金属绝缘体转变,室温下薄膜的电阻率、载流子浓度和迁移率分别为ρ=2.43 mΩcm,n=1.65×1021 cm~(-3)和μ=1.75 cm~2/Vs.以BSSO薄膜为底电极制备了具有比较好电滞回线的Pb(Zr_(0.52)Ti_(0.48))O_3和Bi(Mn_(0.05)Fe_(0.95))O_3铁电电容器,表明BSSO薄膜是一种具有应用前景的新型电极材料.     

聚乙二醇辅助下的La-Co-O复合氧化物合成及其对苯的完全氧化性能研究（英文）

以聚乙二醇(PEG)作为分散剂,采用共沉淀法合成La-Co-O复合氧化物,考察添加不同分子量的PEG(0,2 000,6 000,20 000g·mol~(-1))对复合氧化物的物化性质及苯完全氧化性能的影响。采用N_2物理吸附、XRD、SEM、H_2-TPR、O_2-TPD和XPS进行催化剂表征。苯完全氧化反应结果显示催化剂活性顺序为LCO-PEG6000LCOLCO-PG20000LCO-PG2000,LCO-PEG6000催化剂在383℃时对苯的转化率达到99%,比LCO低126℃。N_2物理吸附实验表明所制备的样品的SBET均为9~10m·g~(-1)。XRD分析显示合成的催化剂均为LaCoO_3钙钛矿主相伴生少量La_2O_3和Co_3O_4杂相,但添加PEG有利于钙钛矿主相的形成。尤其是添加PEG6000有效地抑制了催化剂颗粒的团聚,合成的样品颗粒均匀且尺寸最小。H_2-TPR和O_2-TPD结果表明该催化剂具有更高的还原性能和晶格氧迁移能力,同时XPS分析显示表面活性Co~(3+)含量最高,这些性质使其具有最高的催化氧化活性。     

基于镍泡沫支撑的Co_3O_4纳米多孔结构的高性能超级电容器电极

在众多能量存储和转化器件中,超级电容器由于具有功率密度高、充放电迅速和优异的循环性能的优点而被广泛研究.然而,较低的比容量和能量密度,限制了超级电容作为大尺度能量存储和转化器件的广泛应用.为了提高超级电容器的比容量,需要增大电极材料和电解质的接触面积,进而促进电极材料俘获/释放电解质中的粒子(例如电子、离子或者小分子).在此,我们通过简单的水热法联合高温退火实验方案能够大规模制备出镍泡沫支撑的Co_3O_4多孔纳米结构.无需借助导电胶和粘合剂,在集流器镍泡沫上"生长"Co_3O_4多孔纳米结构直接作为超级电容的电极材料.这种多孔纳米结构和一体化设计思路不仅能够有效提高电极的导电性,而且能够有效缩短离子和电子的迁移路径.由于多孔的结构特征和优异的导电性能,Co_3O_4电极表现出超高比容量(在电流密度为2.5 m A·cm~(-2)和5.5 m A·cm~(-2)时,比容量分别为1.87 F·cm(-2)(936 F·g-1)和1.80 F·cm~(-2)(907 F·g-1))、较好的倍率性能(电流密度从2.5 m A·cm~(-2)增大到100 m A·cm~(-2)时,保留其48.37%的初始电容)和超高的循环稳定性(经历4000次电流密度为10 m A·cm~(-2)的循环充放电过程,保留其92.3%的比容量).这种多孔纳米结构和一体化设计思路对设计其他高性能储能器件具有重要的指导意义.     

新疆大中小城市夏季对流层NO_2垂直柱浓度变化特征

利用地基多轴差分光谱仪(Mini MAX—DOAS),选择新疆乌鲁木齐、库尔勒、博乐市具有代表性的大中小城市,于2014年6—8月对其市区、工业区、农田区的对流层NO_2浓度进行观测。结果表明:(1)大中小城市夏季大气对流层NO_2垂直柱浓度的日变化有波峰和波谷的波动,其峰值在大中小城市中有所差异,表现为乌鲁木齐(7.590×10~(15)molec·cm~(-2))库尔勒(7.559×10~(15)molec·cm~(-2))博乐(3.578×10~(15)molec·cm~(-2));(2)大中小城市夏季大气对流层NO_2垂直柱浓度大小与城市地表条件差异有关,尤其与观测区的车流量有密切关系,表现为市区(4.643×10~(15)molec·cm~(-2))工业区(4.469×10~(15)molec·cm~(-2))农田区(2.425×10~(15)molec·cm~(-2));(3)不同天气条件下大中小城市大气对流层NO_2的垂直柱浓度特征为雨天(3.082×10~(15)molec·cm~(-2))时浓度最小,说明降水对NO_2的浓度具有重要的影响。     

AlGaN/GaN高电子迁移率晶体管器件电离辐照损伤机理及偏置相关性研究

本文利用~(60)Coγ射线,针对AlGaN/GaN高电子迁移率晶体管(high-electron mobility transistors,HEMT)器件,开展了在不同偏置下器件电离辐照总剂量效应实验研究.采用1/f噪声结合直流电学特性参数对实验结果进行测量分析,分析结果表明,受到辐照诱生氧化物缺陷电荷与界面态的影响,当辐照总剂量达到1 Mrad(Si)时,零偏条件下AlGaN/GaN HEMT器件的电学参数退化得最大,其中,饱和漏电流减小36.28%,最高跨导降低52.94%;基于McWhorter模型提取了AlGaN/GaN HEMT器件辐照前后的缺陷密度,零偏条件下辐照前后缺陷密度变化最大,分别为4.080×10~(17)和6.621×10~(17)cm~(-3)·eV~(-1).其损伤机理是在氧化物层内诱生缺陷电荷和界面态,使AlGaN/GaN HEMT器件的平带电压噪声功率谱密度增加.     

Enhanced interface properties of diamond MOSFETs with Al_2O_3 gate dielectric deposited via ALD at a high temperature

The interface state of hydrogen-terminated(C–H) diamond metal–oxide–semiconductor field-effect transistor(MOSFET) is critical for device performance. In this paper, we investigate the fixed charges and interface trap states in C–H diamond MOSFETs by using different gate dielectric processes. The devices use Al_2O_3 as gate dielectrics that are deposited via atomic layer deposition(ALD) at 80℃ and 300℃, respectively, and their C–V and I–V characteristics are comparatively investigated. Mott–Schottky plots(1/C~2–VG) suggest that positive and negative fixed charges with low density of about 1011 cm~(-2) are located in the 80-℃-and 300-℃ deposition Al_2O_3 films, respectively. The analyses of direct current(DC)/pulsed I–V and frequency-dependent conductance show that the shallow interface traps(0.46 e V–0.52 e V and0.53 e V–0.56 e V above the valence band of diamond for the 80-℃ and 300-℃ deposition conditions, respectively) with distinct density(7.8 × 10~(13) e V~(-1)·cm~(-2)–8.5 × 10~(13) e V-1·cm~(-2) and 2.2 × 1013 e V~(-1)·cm~(-2)–5.1 × 10~(13) e V~(-1)·cm~(-2) for the80-℃-and 300-℃-deposition conditions, respectively) are present at the Al_2O_3/C–H diamond interface. Dynamic pulsed I–V and capacitance dispersion results indicate that the ALD Al_2O_3 technique with 300-℃ deposition temperature has higher stability for C–H diamond MOSFETs.     

Tb掺杂双层锰氧化物La_(4/3)Sr_(5/3)Mn_2O_7的磁熵变和电输运性质

研究了Tb掺杂对双层锰氧化物La_(4/3)Sr_(5/3)Mn_2O_7磁熵变和电输运性质的影响.样品采用传统固相反应法制备,两样品的名义组分可以表示为(La_(1-x)Tb_x)_(4/3)Sr_(5/3)Mn_2O_7(x=0,0.025),磁场为7 T时的最大磁熵变?S_M分别为-4.60 J/(kg·K)和-4.18 J/(kg·K).比较后发现,Tb元素的掺杂使得最大磁熵变值减小,但同时增大了相对制冷温区.电性测量结果表明,x=0.025的样品在高温区的导电机制可以用小极化子模型解释,与母体三维变程跳跃模型不同;当温度降低至三维长程铁磁有序温度(T_c~(3D))附近时,掺杂样品发生金属绝缘相变;掺杂后样品在T_c~(3D)附近,磁电阻取得极大值(约为56%),表明是本征磁电阻效应.     

High performance lateral Schottky diodes based on quasi-degenerated Ga_2O_3

Ni/β-Ga_2 O_3 lateral Schottky barrier diodes(SBDs) were fabricated on a Sn-doped quasi-degenerate n~+-Ga_2 O_3(201)bulk substrate. The resultant diodes with an area of 7.85 ×10~(-5) cm~2 exhibited excellent rectifying characteristics with an ideality factor of 1.21, a forward current density(J) of 127.4 A/cm2 at 1.4 V, a specific on-state resistance(R_(on,sp)) of1.54 mΩ·cm~2,and an ultra-high on/off ratio of 2.1 ×10~(11) at±1 V. Due to a small depletion region in the highly-doped substrate, a breakdown feature was observed at-23 V, which corresponded to a breakdown field of 2.1 MV/cm and a power figure-of-merit(VB2/R_(on)) of 3.4×10~5 W/cm~2. Forward current-voltage characteristics were described well by the thermionic emission theory while thermionic field emission and trap-assisted tunneling were the dominant transport mechanisms at low and high reverse biases, respectively, which was a result of the contribution of deep-level traps at the metal-semiconductor interface. The presence of interfacial traps also caused the difference in Schottky barrier heights of 1.31 eV and 1.64 eV respectively determined by current-voltage and capacitance-voltage characteristics. With reduced trapping effect and incorporation of drift layers, the β-Ga_2 O_3 SBDs could further provide promising materials for delivering both high current output and high breakdown voltage.     

铟锌氧化物薄膜晶体管局域态分布的提取方法

本文针对铟锌氧化物薄膜晶体管(IZO TFT)的低频噪声特性与变频电容-电压特性展开试验研究,基于上述特性对有源层内局域态密度及其在禁带中的分布进行参数提取.首先,基于IZO TFT的亚阈区I-V特性提取器件表面势随栅源电压的变化关系.基于载流子数随机涨落模型,在考虑有源层内缺陷态俘获/释放载流子效应基础上,通过γ因子提取深能态陷阱的特征温度;基于沟道电流噪声功率谱密度及平带电压噪声功率谱密度的测量,提取IZO TFT有源层内局域态密度及其分布.试验结果表明,带尾态缺陷在禁带内随能量呈e指数变化趋势,其导带底密度N1TA约为3.42×10~(20)cm~(-3)·eV-,特征温度TTA约为135 K.随后,将C-V特性与线性区I-V特性相结合,对栅端寄生电阻、漏端寄生电阻、源端寄生电阻进行提取与分离.在考虑有源层内局域态所俘获电荷与自由载流子的情况下,基于变频C-V特性对IZO TFT有源层内局域态分布进行参数提取.试验结果表明,深能态与带尾态在禁带内随能量均呈e指数变化趋势,深能态在导带底密度NDA约为5.4×10~(15)cm~(-3)·eV~(-1),特征温度TDA约为711 K,而带尾态在导带底密度NTA约为1.99×10~(20)cm~(-3)·eV~(-1),特征温度TTA约为183 K.最后,对以上两种局域态提取方法进行对比与分析.     

Oxygen ion conductivity of La_(0.8)Sr_(0.2)Ga_(0.83)Mg_(0.17-x)Co_xO_(3-δ) synthesized by laser rapid solidification

Materials La0.8Sr0.2Ga0.83Mg0.17-xCoxO3-δ with x = 0, 0.05, 0.085, 0.10, and 0.15 are synthesized by laser rapid solidification. It is shown that the samples prepared by laser rapid solidification give rise to unique spear-like or leaf-like microstructures which are orderly arranged and densely packed. Their electrical properties each show a general dependence of the Co content and the total conductivities of La 0.8 Sr 0.2 Ga 0.83 Mg 0.085 Co 0.085 O 3-δ prepared by laser rapid solidification are measured to be 0.067, 0.124, and 0.202 S·cm -1 at 600, 700, and 800℃, respectively, which are much higher than by conventional solid state reactions. Moreover, the electrical conductivities each as a function of the oxygen partial pressure are also measured. It is shown that the samples with the Co content values ≤ 8.5 mol% each exhibit basically ionic conduction while those for Co content values ≥ 10 mol % each show ionic mixed electronic conduction under oxygen partial pressures from 10 -16 atm (1 atm = 1.01325×10 5 Pa) to 0.98 atm. The improved ionic conductivity of La 0.8 Sr 0.2 Ga 0.83 Mg 0.085 Co 0.085 O 3-δ prepared by laser rapid solidification compared with by solid state reactions is attributed to the unique microstructure of the sample generated during laser rapid solidification.     

高Tb3+离子含量磁光玻璃的Faraday效应及发光性能

采用高温熔融法制备了高Tb³⁺离子含量的GeO₂-B₂O₃-SiO₂系统磁光玻璃,测试了其Verdet常数和发光性能,探究了玻璃的Faraday效应、发光性能及光学碱度。研究结果表明:Verdet常数和光学碱度均随着Tb₂O₃含量的增加而线性增大,当Tb₂O₃摩尔分数为70%时,Verdet常数达到-5 000 min·T^-1·cm^-1 (632.8 nm),所有磁光玻璃样品随Tb₂O₃含量变化均发出明亮的黄绿光。由于浓度猝灭效应,高Tb₂O₃含量缩短了Tb³⁺离子间距,增强了交叉弛豫效应,降低了发光强度和荧光寿命。     

Growth condition optimization and mobility enhancement through inserting AlAs monolayer in the InP-based In_xGa_(1-x)As/In_(0.52)Al_(0.48)As HEMT structures

The structure of In P-based In_xGa_(1-x) As/In0.52Al0.48 As pseudomorphic high electron mobility transistor(PHEMT)was optimized in detail.Effects of growth temperature,growth interruption time,Si δ-doping condition,channel thickness and In content,and inserted Al As monolayer(ML) on the two-dimensional electron gas(2DEG) performance were investigated carefully.It was found that the use of the inserted Al As monolayer has an enhancement effect on the mobility due to the reduction of interface roughness and the suppression of Si movement.With optimization of the growth parameters,the structures composed of a 10 nm thick In0.75Ga0.25 As channel layer and a 3 nm thick Al As/In0.52Al0.48 As superlattices spacer layer exhibited electron mobilities as high as 12500 cm~2·V-1·s~(-1)(300 K) and 53500 cm~2·V~(-1_·s~(-1)(77 K) and the corresponding sheet carrier concentrations(Ns) of 2.8×10~(12)cm~(-2)and 2.9×1012cm~(-2),respectively.To the best of the authors' knowledge,this is the highest reported room temperature mobility for In P-based HEMTs with a spacer of 3 nm to date.     

Effects of cation- or oxide ion-defect on conductivities of apatite-type La–Ge–O system ceramics

A series of apatite-type La–Ge–O ceramics were prepared and their cation-defect at the 4f+6h sites and oxide ion-defect at 2a site were investigated. In La_xGe₆O_12+1.5x ceramics of x=6–12, the higher conductivities were obtained in the region of apatite composition, La_x(GeO₄)₆O_1.5x−12 (x=8–9.33), and the highest conductivity was achieved for La₉(GeO₄)₆O_1.5 (x=9), where the number of cation (La³⁺) occupying the 4f+6h sites is 9 and the number of oxide ion occupying the 2a site is 1.5. The ceramics with cation- and oxide ion-defects were La_9−0.66xSr_x(GeO₄)₆O_1.5 (x=0–1), La_9−1.33xZr_x(GeO₄)₆O_1.5 (x=0–1), La_9−xSr_x(GeO₄)₆O_1.5−0.5x (x=0–3), La_9−xZr_x(GeO₄)₆O_1.5+0.5x (x=0–1), La_x(GeO₄)_3x−21(AsO₄)_27−3xO_1.5 (x=0–3), La_x(GeO₄)_33−3x(AlO₄)_3x−27O_1.5 (x=0–3), La₉(GeO₄)_6−x (AlO₄)_xO_1.5−0.5x (x=0–3), La₉(GeO₄)_6−x(AsO₄)_xO_1.5+0.5x (x=0–1), La_9.33−xSr_x(GeO₄)₆O_2−0.5x (x=0–1.2) and La_x(GeO₄)_4.5(AlO₄)_1.5O_1.5x−12.75 (x=8.8–9.83), which were prepared by the partial substitution of La³⁺and GeO₄⁴⁻of the basic apatite La₉(GeO₄)₆O_1.5 with Sr²⁺ or Zr⁴⁺ and AlO₄⁵⁻ or AsO₄³⁻. Such substitutions lowered the conductivity of La₉(GeO₄)₆O_1.5. These results were discussed by the electrostatic interaction between Sr²⁺, Zr⁴⁺, AlO₄⁵⁻ or AsO₄³⁻ and oxide ion as a conductive species.     

红色荧光粉La2Mo2O9:Eu3+,W6+的制备及发光性能

采用高温固相法合成出La₂Mo₂O₉:Eu³⁺,W⁶⁺系列红色荧光粉,其结构为立方晶系的β- La₂Mo₂O₉。在395 nm光激发下,样品La_1.40Mo₂O₉:0.60Eu³⁺发射出很强的红光,最强发射峰位于616 nm处。适量地掺杂W⁶⁺离子可以提高样品的激发和发射强度,在395 nm光激发下,La_1.40Mo_1.84O₉:0.60Eu³⁺,0.16W⁶⁺荧光粉的Eu³⁺的⁵D₀→⁷F₂跃迁发射强度最大,是样品La_1.40Mo₂O₉:0.60Eu³⁺的1.23倍。最后,将La_1.40Eu_0.60Mo_1.84O₉:0.16W⁶⁺荧光粉与~395 nm发射的InGaN芯片一起制作成红光发光二极管(LED),该LED发射出很强的红光。     

非晶锂离子导体B2O3-Li2O-LiCl一Al2O3中VO2+的电子自旋共振

两种非晶锂离子导体B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃-0.1V₂O₅(x=0.05和0.15)的电子自旋共振谱研究表明:(i)ESR线型是高斯型,证实V₂O₅添加量适当;(ii)超精细结构来源于VO²⁺络离子,具有四角对称性,属C_4v群。越精细耦合张量的平行分量平均值A_//=0.0175cm^-1,垂直分量A_⊥=0.0063cm^-1。由g_//(g_⊥)求出其基态²B_2g与第一激发态²E_g的能级间距△₁=2.46×10⁴ cm^-1,基态与第二激发态²B_1g的能级间距△₂=3.03×10⁴ cm^-1;(iii)变温实验证实:Al₂O₃组分较少(x=0.05)的非晶ESR强度比x=0.15的非晶高3倍至2倍,而Al₂O₃组分越多则ESR强度随温升下降越小。     

部分耗尽结构绝缘体上硅器件的低频噪声特性

针对部分耗尽结构绝缘体上硅(silicon-on-insulator, SOI)器件低频噪声特性展开实验与理论研究. 实验结果表明, 器件低频噪声主要来源于SiO₂-Si界面附近缺陷态对载流子的俘获与释放过程; 基于此理论可提取前栅和背栅氧化层界面附近缺陷态密度分别为8×10¹⁷ eV^-1·cm^-3和2.76×10¹⁷ eV^-1·cm^-3. 基于电荷隧穿机理, 在考虑隧穿削弱因子、隧穿距离与时间常数之间关系的基础上, 提取了前、背栅氧化层内缺陷态密度随空间的分布情况. 此外, SOI器件沟道电流归一化噪声功率谱密度随沟道长度的增加而线性减小, 这表明器件低频噪声主要来源于沟道的闪烁噪声. 最后, 基于电荷耦合效应, 分析了背栅电压对前栅阈值电压、沟道电流以及沟道电流噪声功率谱密度的影响.     

La3+存在形式对白云鄂博稀选尾矿微晶玻璃性能的影响

选取白云鄂博稀选尾矿和粉煤灰为主要原料, 采用熔铸法制备了0–4 wt%La₂O₃掺杂的CaO-MgO-Al₂O₃-SiO₂系微晶玻璃. 利用DTA, XRD, SEM, TEM+EDS和性能测试手段研究La³⁺在白云鄂博稀选尾矿微晶玻璃中的存在形式及其对该微晶玻璃显微结构、抗折强度和耐腐蚀性的影响. 结果表明, La³⁺以置换固溶方式进入辉石主晶相, 1 wt%的La₂O₃可促进辉石主晶相形成. 超过1 wt%的La₂O₃与基础玻璃组分反应生成Ca₃La₆(SiO₄)₆第二相, 并与辉石相争夺Ca²⁺和Si⁴⁺离子来阻碍辉石相形成. 添加1 wt% La₂O₃的微晶玻璃综合性能最优, 其抗折强度和密度分别为198 MPa和3.18 g/cm³.     

Quantum oscillations and nontrivial transport in(Bi_(0.92)In_(0.08))_2Se_3

Quantum phase transition in topological insulators has drawn heightened attention in condensed matter physics and future device applications.Here we report the magnetotransport properties of single crystalline(Bi_(0.92)In_(0.08))_2Se_3.The average mobility of～1000 cm~2·V~(-1)·s~(-1)is obtained from the Lorentz law at the low field(3 T)up to 50 K.The quantum oscillations rise at a field of～5 T,revealing a high mobility of～1.4×10~4cm~2·V~(-1)·s~(-1)at 2 K.The Dirac surface state is evident by the nontrivial Berry phase in the Landau–Fan diagram.The properties make the(Bi_(0.92)In_(0.08))_2Se_3a promising platform for the investigation of quantum phase transition in topological insulators.