C、N、F掺杂对VO2电子结构影响的研究

二氧化钒(VO₂)是一种热至变色材料,在临界温度340 K有金属-半导体相变.第一性原理计算结果发现:C、N、F元素以1.56;、3.13;、4.69;的原子浓度掺杂M1相VO₂的带隙Eg1降低到0.349～0.612 eV,其中氮元素以4.69;的浓度掺杂VO₂的带隙Eg1最小(0.349 eV).在C、N、F掺杂M1相VO₂体系中,3.13;的N掺杂可以有效降低相变温度,并且对可见光透过率影响不大,所以3.13;的N原子掺杂VO₂可以在实际中应用.     

NaCa2Mg2(VO4)3∶Eu3+颜色可调荧光粉的熔盐法合成及其发光性能研究

以廉价的NaCl为熔盐，采用熔盐法合成了NaCa_2-xMg₂(VO₄)₃∶xEu³⁺(0≤x≤0.10)系列颜色可调荧光粉，系统研究了合成条件、Eu³⁺掺杂对样品结构及发光性能的影响。结果表明，反应温度为800℃、反应时间为0.5 h、原料与熔盐的质量比为1∶3是合成NaCa₂Mg₂(VO₄)₃的适宜反应条件，所得样品为NaCa₂Mg₂(VO₄)₃纯相，且结晶度高。样品微观形貌随着反应温度的升高由珊瑚状演变为表面光滑的不规则多面体。Eu³⁺掺杂对NaCa₂Mg₂(VO₄)₃的晶体结构影响较小，但对其发光性能影响较大。随着Eu³⁺浓度(x)的增加，VO     

稀土掺杂萤石结构卤化物晶体团簇结构研究

稀土掺杂萤石卤化物在国民经济、国防建设等领域发挥着不可替代的作用。萤石卤化物特殊的晶体结构导致稀土离子团聚，目前针对稀土离子团聚的系统研究还比较少。本文以稀土掺杂萤石卤化物为研究对象，采用第一性原理计算系统研究了从稀土离子单体到高阶团簇的结构特征、演变规律、联系及其影响因素。研究发现，稀土离子单体中心1|0|0|1₁(C_4v)和1|0|0|1₂(C_3v)稳定性随离子半径变化而改变，且不同晶体的变化趋势不同，与晶格畸变分析结果一致。晶格畸变与库仑作用相互耦合决定了电荷补偿间隙卤离子的占位倾向性，即C_4v和C_3v中心的相对稳定性。此外，共价效应使得PbF₂和SrCl₂晶体单体中心结构及其稳定性与CaF₂、SrF₂和BaF₂不同。研究还揭示了晶体离子性和晶胞尺寸对单体中心能量差斜率的影响。文中还研究了稀土离子高阶团簇的结构，其稳定性演变规律与单体中心相对...     

(111)取向0.7PMN-0.3PT薄膜机电耦合性能

铁电薄膜由于其优异物理性能,而被广泛应用于微电子、光电子、微机电领域。在铁电薄膜理论研究方面,热力学理论可以有效地预测铁电薄膜的相结构、极化特性和机电性能等,且已在(001)取向铁电薄膜的研究中取得了较好的应用,而对于(111)取向铁电薄膜的研究报道非常少。因此,本文通过对序参量坐标转换的方法,构建了(111)取向薄膜的热力学势能函数及其机电性能计算方法。基于此,研究了(111)取向0.7PMN-0.3PT铁电薄膜的相结构及其机电性能。研究结果表明,(111)取向0.7PMN-0.3PT铁电薄膜的相结构主要存在沿晶轴方向三个极化可互换的对称相:顺电相PE、菱方相R和单斜相M_A(或M_B)。在应变和外电场的调控下,(111)取向0.7PMN-0.3PT薄膜展现出优良的机电性能,在R和M_A相变点处,介电常数ε11、ε22、ε33和面外压电系数d33取得了极大值。在外电场E₃分别为0、50 kV/cm、100 kV/cm和200 kV/cm时,面外介电常数ε33的峰值分别为4 382、2 646、2 102和1 600,面外压电系数d33的峰值分别为303.8 pm/V、241.9 pm/V、219.7 pm/V和195.1 pm/V。应变和外电场能够较好地调控薄膜的机电耦合性能,可为优异机电耦合性能的器件制备提供参考。     

溅射羽辉与基底夹角对掺氧二硫化钼薄膜光学性质的影响

二硫化钼(MoS₂)在环境中的热稳定性和化学稳定性好,迁移率相对较高,已应用于气体传感器、光电探测器和场效应管等器件的研制。采用氧气辅助技术生长的氧掺杂MoS₂(MoS_2-xO_x)不仅可以调控MoS₂单晶尺寸,还能提高MoS₂单晶光致发光强度。本文采用射频反应磁控溅射技术、自然环境中氧化和热退火工艺,改变溅射羽辉与玻璃基底夹角来制备MoS_2-xO_x薄膜并研究其光学性质。采用X射线光电子能谱分析了样品的元素和价态;扫描电子显微镜观测的结果表明,溅射羽辉与基底成45°(θ=45°)时表面形貌为最优;紫外-可见分光光度计的测试结果表明,随着厚度和氧含量的增加,MoS_2-xO_x薄膜的光学带隙减小;采用COMSOL Multiphysics软件模拟了MoS_2-xO_x薄膜光学透过率,理论和实验结果相吻合。本文的研究结果将为MoS_2-xO_x薄膜在光学领域的应用提供科学参考。     

高居里温度铁电单晶PIN-PT的机电性能

弛豫铁电单晶Pb(In_1/2Nb_1/2)O₃-PbTiO₃(PIN-PT)相较于常用的Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃(PMN-PT)具有更高的居里温度,在高稳定性、高性能的传感器、换能器方面具有应用前景。本工作采用谐振法研究了[001]方向极化的0.66PIN-0.34PT铁电单晶的全矩阵机电性能参数。0.66PIN-0.34PT 单晶的三方-四方相变温度(T_RT)约为160 ℃,居里温度(T_C)约为260 ℃,室温压电系数d₃₃、d₃₁、d₁₅分别为1 340 pC/N、-780 pC/N、321 pC/N,介电常数ε^T₃₃、ε^S₃₃、ε^T₁₁、ε^S₁₁分别为2 700、905、2 210、1 927,机电耦合系数 k₃₃、k₃₁、k₁₅、k_t分别为 87%、58%、38%、61%。其纵向压电常数(d₃₃)和纵向机电耦合系数(k₃₃)小于 PMN-PT 单晶,但是横向压电性能(d₃₁)和剪切压电性能(d₁₅)都略高于PMN-PT单晶。另外,研究了机电耦合性能随温度的变化趋势,发现0.66PIN-0.34PT单晶在150 ℃以下有较好的温度稳定性。     

适温离子交换掺铒铌酸锂薄膜的制备研究

本文通过制备KNO₃和Er(NO₃)₃熔融混合物,将其与铌酸锂薄膜在高温管式炉中混合进行适温热扩散,并结合退火工艺,发明了一种直接在铌酸锂薄膜上掺杂Er³⁺的方法。通过不断变换热扩散温度、掺杂试剂浓度比例和晶体切向等参数,用控制变量法探究了不同参数对适温离子交换法掺杂Er³⁺效果的影响,在热扩散和退火温度360℃及KNO₃和Er(NO₃)₃质量比25∶1的参数设置下获得了表面形貌较佳的Z切掺铒铌酸锂薄膜。通过飞行时间二次离子质谱仪并利用已知掺杂浓度的薄膜进行定标,检测了所获得的掺铒铌酸锂薄膜中的Er³⁺浓度情况,对所采用适温离子交换法的有效性进行了验证。这一方法大幅简化了铌酸锂薄膜掺杂的工艺,同时节约了成本,有助于后续在铌酸锂薄膜平台上实现分区掺杂的工作,为未来定制化铌酸锂光子集成平台的搭建提供参考。     

NiCoSe4薄膜制备及其在染料敏化太阳能电池中的应用

作为染料敏化太阳能电池的关键构成部分,对电极一直是研究的重点,尤其是硒化物对电极。本文采用恒电位沉积-溶剂热-硒化过程制备出钴镍基硒化物薄膜,并直接作为染料敏化太阳能电池的对电极。物相、形貌以及表面元素价态等分析表明,在氟掺杂氧化锡(FTO)玻璃上可直接获得NiCoSe₄薄膜,该薄膜是一种由纳米颗粒构成的片状多孔结构。电化学测试结果表明,NiCoSe₄薄膜在基于I^-/I^-₃氧化还原电对的电解液中具有良好的电催化活性,由其构成的电池器件也展现出了良好的光伏性能,且光电转换效率达到了7.84%,高于铂基电池器件效率的6.95%。     

Ti3(ZnxAl1-x)C2固溶体热学、电学和力学性质的理论研究

采用第一性原理的密度泛函理论平面波赝势法, 通过投影缀加波(PAW)和广义梯度近似(GGA)系统地研究了Ti₃(Zn_xAl_1-x)C₂的结构、能量、声子性质、电子性质和弹性性质。对MAX相Ti₃AlC₂晶体中A位置的Al元素用Zn元素进行替换掺杂,构建出Ti₃(Zn_xAl_1-x)C₂(x=0,0.25,0.5,0.75,1)固溶体结构模型。计算分析表明:在所研究的掺杂浓度范围内Ti₃(Zn_xAl_1-x)C₂均是热力学、动力学和力学稳定的脆性材料;此外,Ti₃(Zn_xAl_1-x)C₂(x=0,0.25,0.5,0.75,1)均呈现金属性,在费米能级处的电子态密度主要贡献来自Ti-3d态,同时具有离子键、共价键和金属键的综合性质。随着Zn原子掺杂浓度的增加,在一定程度上其导电性和塑性均增强。     

射频磁控溅射氧气流量对制备的Ga2O3∶Cr薄膜光致发光性能的影响

在不同氧气流量下,采用双靶射频磁控共溅射的方法在蓝宝石(α-Al₂O₃)基底上制备得到系列掺Cr的Ga₂O₃(Ga₂O₃∶Cr)薄膜,详细研究了薄膜在900 ℃退火前后的结构和光学性能。结果表明,未退火的Ga₂O₃∶Cr薄膜为非晶结构,其发光主要位于蓝绿波段。经900 ℃退火后,薄膜的结构由非晶变为多晶,且在近红外波段观测到了来源于Cr³⁺掺杂的发光。退火后的薄膜结晶质量和近红外发光均与氧气流量密切相关,而其光学带隙不受氧气流量的影响。在所研究的氧气流量范围,4 mL/min氧气流量下薄膜的近红外发光强度最强,这与此条件下薄膜结晶质量较好以及Cr³⁺替代Ga³⁺的数量较多有关。以上研究成果可为制备高质量Ga₂O₃∶Cr薄膜提供参考。     

Preparation and physical properties of amorphous V2O5 containing TiO2, Na2O or Li2O

V₂O₅ gels containing up to 18 mol% of TiO₂ were obtained through the simultaneous hydrolysis of alkoxides in ethanol solution. V₂O₅ gels containing Na₂O or Li₂O were obtained through the ion exchange method. The crystallization temperature, T_cr, of the gels increased and the H₂O content of the gels decreased by the addition of TiO₂ or Na₂O. These additives seem to stabilize the amorphous state of the gels. On the other hand, T_cr and the H₂O-content slightly varied with the addition of Li₂O. No ionic polarization was observed in coating films of the gels dried at temperatures below T_cr. The dc conductivity of the films was anisotropic, and increased with the addition of Li₂O or Na₂O. However, it decreased with increasing TiO₂ content. The fiber-like structure of gels was observed by TEM. The gels obtained from alkoxides were thin and short in comparison with the gels obtained through the ion exchange method.     

Structure and thermal stability of MOCVD ZrO2 films on Si (1 0 0)

The structure and thermal stability of ZrO₂ films grown on Si (1 0 0) substrates by metalorganic chemical vapor deposition have been studied by high-resolution transmission electron microscopy, selected area electron diffraction and X-ray energy dispersive spectroscopy. As-deposited films consist of tetragonal ZrO₂ nanocrystallites and an amorphous Zr silicate interfacial layer. After annealing at 850°C, some monoclinic phase is formed, and the grain size is increased. Annealing a 6 nm thick film at 850°C in O₂ revealed that the growth of the interfacial layer is at the expense of the ZrO₂ layer. In a 3.0 nm thick Zr silicate interfacial layer, there is a 0.9 nm Zr-free SiO₂ region right above the Si substrate. These observations suggest that oxygen reacted with the Si substrate to grow SiO₂, and SiO₂ reacted with ZrO₂ to form a Zr silicate interfacial layer during the deposition and annealing. Oxygen diffusion through the tetragonal ZrO₂ phase was found to be relatively easier than through the monoclinic phase.     

Coordination of aluminum in amorphous sodium aluminosilicate films

Amorphous sodium aluminosilicate thin films containing large amounts of Al₂O₃ were deposited on fused silica substrates by rf-sputtering, and their aluminum K-band X-ray emission spectra were measured by using an electron probe X-ray microanalyser in order to determine the coordination number of aluminum ions in the amorphous thin films.

The chemical shifts for the amorphous films with Al₂O₃/Na₂O<1 were almost identical with those of tetrahedrally coordinated aluminum ions in microline. On the other hand, for the amorphous films with Al₂O₃/Na₂O>1, the chemical shifts increased with increasing Al₂O₃/NA₂OF ratio, approaching that of amorphous alumina. From the comparison with the chemical shifts of -Al₂O₃ and mullite, the coordination state of aluminum ions in amorphous alumina was found to be about 5, and its structure was found similar to be that in crystalline Al₂O₃ with spinel-type structure. These results indicate that in amorphous sodium aluminosilicate thin films aluminum ions exist in the tetrahedrally coordinated state when the Al₂O₃/Na₂O ratio is nearly equal to or less than unity. However, when the Al₂O₃/Na₂O ratio exceeds unity, some of the aluminum ions begin to assume the octahedrally coordinated state and increase in number with increasing Al₂O₃/Na₂O ratio.     

The structural relaxation and glass transition of La---Al---Ni and Zr---Al---Cu amorphous alloys with a significant supercooled liquid region

An amorphous phase with a wide supercooled liquid region, > 50 K, was found to form over wide composition ranges in the La---Al---Ni and Zr---Al---Cu systems. The largest values for the temperature span between the crystallization temperature, T_x, and the glass transition temperature, T_g, ΔT_x(-T_x−T_g), are 69 K for La₅₅ Al₂₅Ni₂₀ and 88 K for Zr₆₅Al_7.5Cu_27.5. The structural relaxation behavior on annealing was examined for the two amorphous alloys with the largest ΔT_x values. The magnitude of the structural relaxation increases gradually with increasing annealing temperature, T_a, and then rapidly in the T_a range slightly below T_g and decreases significantly on annealing T_g. The rapid increase in the magnitude of the structural relaxation on annealing near T_g is due to the glass transition. The single-stage structural relaxation indicates that there is no distinct difference in relaxation times (atomic bonding forces) between the constituent atoms in the two metal-metal-type amorphous alloys. The existence of an optimum bonding state is thought to cause the wide supercooled liquid region for the two amorphous alloys.     

SIMS study of the concentration of dopants in LPCVD silicon thin films

Measurements of solid phase dopant concentration (S) of LPCVD Si thin films as a function of substrate temperature (T_s = 500−640 ° C) and gas phase doping ratio (R = 1 × 10⁻⁵ −4 × 10⁻²) by SIMS indicate different behaviors of P and B in the films. A linear relation S = b(T)R is observed for B-doped film with b(T) varying from 4 to 50 depending on T_s. Boron-doped microcrystalline film has a higher doping efficiency than that of P-doped ones.     

Vapor phase epitaxy of pure VO2 and V1−xCrxO2

The vapor phase epitaxy of thin epilayers of VO₂ and V_1−xCrxO₂ on TiO₂ transparent substrates is described. Chemical vapor deposition occurs by reacting a (VOCL₃/CrO₂Cl₂/H₂O/H₂) mixture at about 800°C using argon as a carrier gas. The preparation of pure VO₂ requires special care to make it homogeneously stoichiometric and to obtain steep concentration profiles at the TiO₂/VO₂ interface. Layers were obtained which had electrical and optical properties comparable to the best bulk crystals grown by other techniques. Homogeneous solid solutions of V_1−xCr_xO₂ epilayers were also grown for the first time in the range o < x < 0.17. Chromium concentration and homogeneity were determined by electron microprobe analysis. The separation coefficient k was also found to vary with x. It is close to unity below x = 0.001 and above this value Cr is incorporated more easily. High quality heteroepitaxial layers (1 cm² area, 1 to 30 μm thickness) of V_1−xCr_xO₂ have for the first time allowed the measurement of the optical absorption coefficient.     

Microstructure and growth rate of chemical vapour deposited TiN films in a vertical cold wall reactor

TiN films were grown on SUS304 substrates heated by an induction furnace in a vertical cold wall reactor. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction were used to characterize the microstructures of films obtained at different deposition conditions (temperature, gas flow rate and gas composition). Film structures obtained in the present vertical reactor had the following features compared with those in the tubular reactor: (1) Abnormally grown “star-shaped” crystals were observed on the surfaces of films deposited in the following ranges of total gas flow rate (Q_T), temperature (T) and partial pressures (P): 9.0×10⁻⁶ ≤ Q_T ≤ 1.6×10⁻⁵ m³ s⁻¹, 1223 ≤ T ≤ 1273 K, 0.92 ≤ P_TiCl4 ≤ 6.18 kPa, P_H2 = P_N2. The matrix grains were responsible for (211) preferred orientation. (2) Surface morphologies did not vary so much with P_TiCl4. On the other hand, a drastic change was brought about by adding HCl to the source gas, i.e., plate-shaped crystals dominated and the large “star-shaped” crystals were no longer present. (3) The apparent activation energy for deposition reaction was 230 kJ/mol (1173 ≤ T ≤ 1273 K) and 76.5 kJ/mol (1273 ≤ T ≤ 1373 K) at P_TiCl4 = 2.43 kPa and P_H2 = P_N2 = 49.45 kPa.     

Thermal stability and crystallization kinetics of new As–Ge–Se–Sb glasses

Thermal stability and crystallization kinetics of As₁₄Ge₁₄Se_72−xSb_x (where x = 3, 6, 9, 12 and 15 at.%) glasses are studied by the differential scanning calorimetry. The values of the glass transition temperature (T_g) and the peak temperature of crystallization (T_p) are found to be dependent on heating rate and antimony content. From the heating rate dependence of T_g and T_p the values of the activation energy for glass transition (E_t) and the activation energy for crystallization (E_c) are evaluated and their composition dependence discussed. Crystallization studies have been made under non-isothermal conditions with the samples heated at several uniform rates. Using a recent analysis developed for non-isothermal crystallization studies, information on some aspects of the crystallization process has been obtained. The stability calculations emphasized that the thermal stability decreases with increasing the Sb content.     

Cation site occupation by Ag/Na ion-exchange in R2O–Al2O3–SiO2 glasses

Ag⁺/Na⁺ ion-exchanged R₂O–Al₂O₃–SiO₂ glasses with uniform concentration profile of Ag⁺ and Na⁺ were prepared by heat treatment in molten silver salt followed by holding at the same temperature in an ambient atmosphere. Their glass transition temperature (T_g) and thermal expansion coefficient (TEC) were measured and structures were investigated using ²⁹Si-MAS NMR, ²⁷Al-MAS NMR, IR and Raman spectroscopies. Both T_g and TEC decreased with increase of the exchange ratio, but T_g was still above the ion-exchange temperature of 400°C even for the fully exchanged sample. The ²⁹Si- and ²⁷Al-MAS NMR spectra were mostly unchanged and no sign of the structural alteration of the glass network was observed. On the other hand, the vibrational spectra showed remarkable peak shifts depending on the exchange ratio. From these structural results, it was found that when the exchange ratio was low, the introduced Ag⁺ ions were stabilized at the non-bridging oxygen (NBO) site, and then Na⁺ ions in AlØ₄ site were exchanged by Ag⁺ ions after full replacement of NBO sites, where Ø represents the bridging oxygen.     

Water and the glass transition temperature of silicate melts

Literature data on the effect of water on the glass transition in silicate melts are gathered for a broad range of total water content c_w from 3 × 10⁻⁴ to 27 wt%. In terms of a reduced glass transition temperature T_g^*=T_g/T_g^GN, where T_g^GN is T_g of the melt containing c_w≈0.02 wt% total water, a uniform dependence of T_g^* on total water content (c_w) is evident for silicate melts. T_g^* decreases steadily with increasing water content, most strongly at the lowest water content where H₂O is dominantly dissolved as OH. For water-rich melts, the variation of T_g^* is less pronounced, but it does not vanish even at the largest water contents reported (≈27 wt%). T_g^* vs. c_w is fitted by a three-component model. This approach accounts for different transition temperatures of the dry glass, hydroxyl and molecular water predicting T_g^* as a weighted linear combination of these temperatures. The required but mostly unknown water speciation in the glasses was estimated using IR-spectroscopy data for hydrous sodium trisilicate and rhyolite.