花状掺杂W-VO$lt;sub$gt;2$lt;/sub$gt;/ZnO热致变色纳米复合薄膜研究

为解决掺杂引起的二氧化钒薄膜的红外调制幅度下降以及二氧化钒复合薄膜相变温度需要进一步降低等问题, 采用纳米结构、掺杂改性和复合结构等多种机理协同作用的方案, 利用共溅射氧化法, 先在石英玻璃上制备高(002)取向的ZnO薄膜, 再在ZnO层上室温共溅射沉积钒钨金属薄膜, 最后经热氧化处理获得双层钨掺杂W-VO₂/ZnO纳米复合薄膜. 利用X射线衍射、X射线光电子能谱、扫描电镜和变温光谱分析等对薄膜的结构、组分、形貌和光学特性进行了分析. 结果显示, W-VO₂/ZnO 纳米复合薄膜呈花状结构, 取向性提高, 在保持掺杂薄膜相变温度(约39 ℃)和热滞回线宽度(约6 ℃)较低的情况下, 其相变前后的红外透过率差量增加近2倍, 热致变色性能得到协同增强. 关键词： 2')" href="#">VO₂ ZnO W掺杂 热致变色     

Interfacial properties of 2D WS2 on SiO2 substrate from X-ray photoelectron spectroscopy and first-principles calculations

Two-dimensional (2D) WS₂ films were deposited on SiO₂ wafers, and the related interfacial properties were investigated by high-resolution X-ray photoelectron spectroscopy (XPS) and first-principles calculations. Using the direct (indirect) method, the valence band offset (VBO) at monolayer WS₂/SiO₂ interface was found to be 3.97 eV (3.86 eV), and the conduction band offset (CBO) was 2.70 eV (2.81 eV). Furthermore, the VBO (CBO) at bulk WS₂/SiO₂ interface is found to be about 0.48 eV (0.33 eV) larger due to the interlayer orbital coupling and splitting of valence and conduction band edges. Therefore, the WS₂/SiO₂ heterostructure has a Type I energy-band alignment. The band offsets obtained experimentally and theoretically are consistent except the narrower theoretical bandgap of SiO₂. The theoretical calculations further reveal a binding energy of 75 meV per S atom and the totally separated partial density of states, indicating a weak interaction and negligible Fermi level pinning effect between WS₂ monolayer and SiO₂ surface. Our combined experimental and theoretical results provide proof of the sufficient VBOs and CBOs and weak interaction in 2D WS₂/SiO₂ heterostructures.     

Annealing effects on structure and laser-induced damage threshold of Ta2O5/SiO2 dielectric mirrors

The effects of annealing on structure and laser-induced damage threshold (LIDT) of Ta₂O₅/SiO₂ dielectric mirrors were investigated. Ta₂O₅/SiO₂ multilayer was prepared by ion beam sputtering (IBS), then annealed in air under the temperature from 100 to 400 °C. Microstructure of the samples was characterized by X-ray diffraction (XRD). Absorption of the multilayer was measured by surface thermal lensing (STL) technique. The laser-induced damage threshold was assessed using 1064 nm free pulsed laser at a pulse length of 220 μs.

It was found that the center wavelength shifted to long wavelength gradually as the annealing temperature increased, and kept its non-crystalline structure even after annealing. The absorbance of the reflectors decreased after annealing. A remarkable increase of the laser-induced damage threshold was found when the annealing temperature was above 250 °C.     

A quantum chemical study of ZrO2 atomic layer deposition growth reactions on the SiO2 surface

Zirconium oxide (ZrO₂) is one of the leading candidates to replace silicon oxide (SiO₂) as the gate dielectric for future generation metal-oxide-semiconductor (MOS) based nanoelectronic devices. Experimental studies have shown that a 1–3 monolayer SiO₂ film between the high permittivity metal oxide and the substrate silicon is needed to minimize electrical degradation. This study uses density functional theory (DFT) to investigate the initial growth reactions of ZrO₂ on hydroxylated SiO₂ by atomic layer deposition (ALD). The reactants investigated in this study are zirconium tetrachloride (ZrCl₄) and water (H₂O). Exchange reaction mechanisms for the two reaction half-cycles were investigated. For the first half-reaction, reaction of gaseous ZrCl₄ with the hydroxylated SiO₂ surface was studied. Upon adsorption, ZrCl₄ forms a stable intermediate complex with the surface SiO₂–OH^* site, followed by formation of SiO₂–O–Zr–Cl^* surface sites and HCl. For the second half-reaction, reaction of H₂O on SiO₂–O–Zr–Cl^* surface sites was investigated. The reaction pathway is analogous to that of the first half-reaction; water first forms a stable intermediate complex followed by evolution of HCl through combination of a Cl atom from the surface site and an H atom from H₂O. The results reveal that the stable intermediate complexes formed in both half-reactions can lead to a slow film growth rate unless process parameters are adjusted to lower the stability of the complex. The energetics of the two half-reactions are similar to those of ZrO₂ ALD on ZrO₂ and as well as the energetics of ZrO₂ ALD on hydroxylated silicon. The energetics of the growth reactions with two surface hydroxyl sites are also described.     

二氧化硅对稀土掺杂二氧化钛薄膜形貌与发光性能的影响

为提高稀土掺杂TiO₂薄膜的上转换效率,采用溶胶-凝胶法和旋涂镀膜工艺制备了Yb³⁺-Er³⁺共掺杂SiO₂/TiO₂上转换光致发光薄膜,研究了SiO₂对TiO₂薄膜形貌以及发光性能的影响。利用FE-SEM观察了薄膜的表面形貌,利用分光光度计测试了薄膜在近红外光区域的透射率的变化,并用荧光光谱仪测试了薄膜的上转换发光光谱。结果表明：SiO₂的掺杂导致TiO₂颗粒尺寸显著减小,TiO₂薄膜在近红外的透射率也有所下降。在980 nm红外光激发下,SiO₂/TiO₂薄膜在630~670 nm处获得了明显的上转换红光发射,在516~537 nm和537~570 nm处获得了较弱的上转换绿光发射。由上转换发光强度与激光泵浦功率的关系推知,绿色和红色上转换发光均为双光子吸收发射过程。     

超低密度SiO2气凝胶的制备研究

超低密度的SiO2气凝胶是一种经典的三维网状纳米多孔材料,已经广泛应用于如保温隔热、吸附等多种领域。以四甲氧基硅烷(TMOS)为硅源,采用酸碱两步法,利用乙醇超临界干燥技术制备了超低密度的SiO2气凝胶,分别利用SEM\TEM\BET等表征手段对该气凝胶进行了一系列的研究,发现当其密度为0.6 mg/cm3时,气凝胶拥有最佳的综合性能。该种气凝胶具有超低密度、高比表面积、加工成型性好、制备周期短等优点,有望在激光惯性约束聚变实验中作为冷冻靶发挥巨大的作用。     

High and low thermal nitridation of SiO2 thin films

Thin thermal SiO₂ films on crystalline silicon substrate were nitrided at low ammonia pressures (10^-6P_NH310^-1 mbar) for times varying from 1 to 10 h, by means of two techniques. (i) Surface nitridation has been achieved by thermal activation at high temperature (HT), in the range 800–1100°C. (ii) A new process at low temperature (LT), was employed at T ≈ 30°C, under electron-beam irradiation; the nitridation-reaction rate depends on the electron energy (reaching a maximum within the energy range 1 to 2 keV), and on the electron flux. Conduction and electron trapping on the nitrided oxide films depends on the chemical compositions and on the amount of nitrogen incorporated into the bulk of the films and/or at the SiO₂-Si interface.     

Thermal and mechanical properties and micro-mechanism of SiO2/epoxy nanodielectrics

In addition to electrical insulation properties, the thermal properties of nanodielectrics, such as glass transition temperature, thermal expansion coefficients, thermal conductivity, and mechanical properties, including Young's modulus, bulk modulus, and shear modulus, are also very important. This paper describes the molecular dynamics simulations of epoxy resin doped with SiO₂ nanoparticles and with SiO₂ nanoparticles that have been surface grafted with hexamethyldisilazane (HMDS) at 10% and 20% grafting rates. The results show that surface grafting can improve certain thermal and mechanical properties of the system. Our analysis indicates that the improved thermal performance occurs because the formation of thermal chains becomes easier after the surface grafting treatment. The improved mechanical properties originate from two causes. First, doping with SiO₂ nanoparticles inhibits the degree of movement of molecular chains in the system. Second, the surface grafting treatment weakens the molecular repulsion between SiO₂ and epoxy resin, and the van der Waals excluded region becomes thinner. Thus, the compatibility between SiO₂ nanoparticles and polymers is improved by the grafting treatment. The analysis method and conclusions in this paper provide guidance and reference for the future studies of the thermal and mechanical properties of nanodielectrics.     

Composite protonic solid electrolytes in the CsHSO4-SiO2 system

Transport, thermal and structural properties of the composite solid electrolytes (1 −x)CsHSO₄---xSiO₂ (where x = 0–0.8) were investigated. The composites were prepared by mechanical mixing of components followed by heating at temperatures near CsHSO₄ melting point (483 K). The dependence of low temperature phase conductivity on x has a maximum with a value 2.5 orders of magnitude higher than that of pure CsHSO₄ and conductivity is governed by protons. Heterogeneous doping is shown to change markedly the thermodynamic parameters of the ionic component. The phase transition temperature CsHSO₄ in the composites decreases from 414 to 350 K with the increase of the content of heterogeneous additive SiO₂ from 0 to 0.7. As x raises CsHSO₄ the amorphization takes place and the relative change of ionic conductivity at phase transition diminishes, the phase transition becomes diffusive and disappears for the 0.2CsHSO₄---0.8SiO₂ composite.     

Synthesis and characterization of monodispersed CdS nanoparticles in SiO2 fibers by sol–gel method

Cadmium sulfide (CdS) has been synthesized by a sol–gel route in order to obtain chemically protected, stable nanoparticles. The CdS nanoparticles in the SiO₂ gel matrix were dried to form monoliths of 1 in. diameter. The TEOS:H₂O:HCl:C₂H₅OH and TEOS/Cd mole ratios were varied to obtain narrow size distributed CdS nanoparticles. The UV absorption measurements indicated sharp absorption at 260 and 350 nm for different precursor compositions. SiO₂ gel containing the CdS nanoparticles was spin coated onto substrates in order to monitor the surface morphology of the samples. Scanning electron microscope measurements revealed formation of CdS nanoparticles within the branches of gel-network. Depending upon the mole ratio of additives and drying method, fibers or monolithic tablets of CdS nanoparticles could be produced.     

鞍山式铁矿SiO2含量的热红外光谱分析方法

SiO₂含量是铁矿石质量控制的主要技术指标,亦是衡量铁矿石品质好坏的关键指标之一,对选矿方法、配矿流程的确定具有重要意义。传统的SiO₂含量测定法虽然准确度高,但工作量大,操作繁琐,花费时间长,难以快速、高效确定铁矿石中SiO₂含量。采用红外光谱辐射计Turbo FT对辽宁省鞍钢集团鞍千矿业有限责任公司的“鞍山式”铁矿样品进行热红外光谱测试,分析了光谱特征,构建了比值指数(RI)、差值指数(DI)和归一化指数(NDI),并确定光谱指数与样品SiO₂含量相关性最显著的敏感波段及对应的相关系数值;优选出与样品SiO₂含量相关性最显著的归一化指数(NDI),构建样品SiO₂含量的定量反演模型,并进行了验证。结果表明,三种光谱指数与样品SiO₂含量的敏感波段均位于余辉带特征(RF)的左边界8.06与8.2 μm处,相关系数均达到0.9以上,其中NDI与样品SiO₂含量的相关性最高;基于NDI构建了实验样品SiO₂含量的二次函数反演模型,预测误差为3.57%。该方法相对于传统的研磨化验法,具有工作强度小、便捷、快速、高效、无污染的优点,对遥感找矿也具有一定指导意义。     

Eu2O3在η-Al2O3和SiO2上固体-固体表面相互作用的研究

用穆斯堡尔谱和X射线衍射技术研究了Eu₂O₃在η-Al₂O₃和硅胶上的固体表面吸附。 关键词：     

GaSb基PECVD法制备SiO2薄膜的应力研究

为了实现在GaSb衬底上获得低应力的SiO₂薄膜,研究了等离子体增强化学气相沉积法（PECVD）在晶格失配较大的GaSb衬底上沉积SiO₂薄膜的应力情况。通过改变薄膜沉积时的工艺条件,如反应温度、射频功率、反应压强、气体流量比,并基于曲率法模型,对镀膜前后的曲率半径进行了实验测量,利用Stoney公式计算相关应力值并绘制应力变化曲线。详细讨论了PECVD工艺条件的改变对SiO₂薄膜应力所产生的影响。同时通过在Si衬底上沉积SiO₂薄膜,对比分析了导致薄膜应力产生的因素及变化过程。实验结果表明,在沉积温度为300℃、射频功率为20 W、腔体压强为90 Pa、气体流量比SiH₄/N₂O为125/70 cm³·min^-1的工艺参数下,PECVD法在GaSb衬底上沉积的SiO₂薄膜应力相对较小。     

Ce3+和Mn2+掺杂的Ba9(Y2-xScx)(SiO4)6光谱特性和温度特性研究

采用高温固相法制备了Ba₉(Y_2-xSc_x)(SiO₄)₆:Ce³⁺,Mn²⁺(x=0,0.5,1.0,1.5,2.0)样品。在该体系中,当Sc³⁺含量从x=0逐渐增加至x=2时,Ce³⁺的蓝光发射强度提高了1.7倍;同时,Mn²⁺的红光发射强度提高了1.9倍,显示了优良的红光特性。样品的发射光谱和漫反射光谱表明,Ce³⁺、Mn²⁺发射强度的增加与Ce³⁺吸收能力和Ce³⁺向Mn²⁺能量传递的提升有直接关系。研究了样品Ba₉Sc₂(SiO₄)₆:Ce³⁺,Mn²⁺的热稳定性。随着温度的升高,Mn²⁺的红光发射呈现先升后降的态势。当温度从室温升至488 K时,Mn²⁺发射强度仅下降至室温时的84%,表现出优良的热稳定性。高亮的红光发射和优良的热稳定性表明该荧光材料可为紫外基白光LED提供良好的红色光源。     

紫外波段SiO2/Si3N4介质膜分布式布拉格反射镜的制备与研究

采用光学传递矩阵方法设计了紫外波段SiO₂/Si₃N₄介质膜分布式布拉格反射镜, 并利用等离子体增强化学气相沉积技术在蓝宝石(0001)衬底上制备了SiO₂/Si₃N₄介质膜分布式布拉格反射镜. 光反射测试表明, 样品反射谱的峰值波长仅与理论模拟谱线相差10 nm, 并随着反射镜周期数的增加而蓝移. 由于SiO₂与Si₃N₄具有相对较大的折射率比, 因而制备的周期数为13的样品反射谱的峰值反射率就已大于99%. 样品反射谱的中心波长为333 nm, 谱峰的半高宽为58 nm. 样品截面的扫描电子显微镜和表面的原子力显微镜测量结果表明, 样品反射谱的中心波长蓝移是由子层的层厚和界面粗糙度的变化引起的. X射线反射谱表明,子层界面过渡层对于反射率的影响较小, 并且SiO₂膜的质量比Si₃N₄差, 也是造成反射率低于理论值的原因之一.     

基于Ni电极和ZrO_2/SiO_2/ZrO_2介质的MIM电容的导电机理研究

研究了基于Ni电极和原子层淀积的ZrO_2/SiO_2/ZrO_2对称叠层介质金属-绝缘体-金属(MIM)电容的电学性能.当叠层介质的厚度固定在14nm时,随着SiO_2层厚度从0增加到2nm,所得电容密度从13.1 fF/μm~2逐渐减小到9.3fF/μm~2,耗散因子从0.025逐渐减小到0.02.比较MIM电容的电流-电压(I-V)曲线,发现在高压下电流密度随着SiO_2厚度的增加而减小,在低压下电流密度的变化不明显,还观察到电容在正、负偏压下表现出完全不同的导电特性,在正偏压下表现出不同的高、低场I-V特性,而在负偏压下则以单一的I-V特性为主导.进一步对该电容在高、低场下以及电子顶部和底部注入时的导电机理进行了研究.结果表明,当电子从底部注入时,在高场和低场下分别表现出普尔-法兰克(PF)发射和陷阱辅助隧穿(TAT)的导电机理;当电子从顶部注入时,在高、低场下均表现出TAT导电机理.主要原因在于底电极Ni与ZrO_2之间存在镍的氧化层(NiO_x),且ZrO_2介质层中含有深浅两种能级陷阱(分别为0.9和2.3 eV),当电子注入的模式和外电场不同时,不同能级的陷阱对电子的传导产生作用.     

Nitridation of thin SiO2 films in N2 and NH3 plasmas

A low-temperature (700°C) plasma-enhanced nitridation process which improves the dielectric breakdown of thin silicon dioxide (SiO₂) layers is presented. It uses a new, production compatible, parallel plate plasma reactor working at low RF frequencies. Nitrided oxides produce less charge trapping under high field stress, higher breakdown charge and a tighter distribution of breakdown fields than pure SiO₂. More nitrogen is incorporated in films treated in a NH₃ plasma than in a N₂ plasma. However, the latter present better electrical properties.     

组装条件对涂布法制备SiO2结构色涂层光谱性质影响研究

为了实现结构色涂层在纸张表面的快速制备，研究不同组装条件对SiO₂结构色涂层呈色效果的影响，采用快速涂布的方法，在纸张表面制备出了大面积且具有随角异色特性的结构色涂层。探讨SiO₂微球粒径、分散液浓度及涂布次数等因素对结构色涂层光学特性的影响，通过优化自组装条件和分析周期性结构构筑类型，阐明快速涂布法构建的SiO₂微球在激光打标纸上的自组装过程及结构色呈色机理。应用数码相机、3D激光共聚焦形貌测量显微镜等仪器对样品的颜色外观和微观结构进行测量，表征样品的呈色性能及表面结构。使用X-Rite MA68Ⅱ多角度分光光度仪及光纤光谱仪测量反射光谱，进而用CIEL*a*b*色度值对制备的结构色涂层的光学性能进行分析。结果表明，通过快速涂布自组装法制备所得的结构色涂层，SiO₂微球粒径尺度对样品色调影响显著，随着微球粒径的增加，反射光谱中心波长发生红移，且该涂层有角度依赖特性，当固定入射角度为45°时，随着探测方向与镜面反射方向夹角的增大，中心波长发生红移；微球溶液的浓度可以调控结构色涂层反射光谱曲线的半高宽及反射率峰值，进而影响样品的亮度和彩度，而对于光子带隙的位置无明显影响。微球浓度为4%时，样品表面呈现出基材本身的黑色，微球浓度为8%时，200，220和250 nm粒径的样品表面分别可以呈现彩度较低的蓝色、绿色、黄色，微球浓度增加到10%时，纸张表面的结构色涂层彩度提高，色调不变；随着涂布次数的增加，反射光谱曲线的半高宽变窄，且反射峰位发生蓝移，涂布次数达到3次时，反射峰位最接近于根据布拉格定律计算出的理论值，但涂布次数的增加也使得结构色涂层表面产生白色的不均匀现象。     

Electrical properties of pure and Li2O-doped CuO/Fe2O3 system precalcined at different temperatures

The electrical properties of pure and Li₂O-doped CuO/Fe₂O₃ solids were investigated. Pure and variously doped solids were subjected to thermal treatment at 1073–1273 K and the amount of dopant was varied between 0.84 to 3.36 mol%. The effect of precalcination temperature and amount of Li₂O added on the electrical conductivity σ, activation energy E_a and dielectric constant * were studied. The variation of ′ and ″ as a function of frequency for pure and variously doped solids precalcined at different temperatures was also investigated. The results obtained were discussed.     

LaON/SiO2和HfON/SiO2双隧穿层MONOS存储器存储特性的比较

本文对比研究了LaON/SiO₂和HfON/SiO₂双隧穿层MONOS存储器的存储特性. 实验结果表明,LaON/SiO₂双隧穿层MONOS存储器具有较大的存储窗口,快的编程/擦除速度及好的疲劳和保持特性. 其机理在于LaON较大的介电常数有效提高了编程/擦除过程中载流子的注入效率,较小的O 扩散系数减少了界面陷阱,从而减少了保持期间存储电荷通过陷阱辅助隧穿的泄漏. 而且N的结合在界面附近形成了强的La-N,Hf-N 和O-N键,可有效降低编程/擦除循环应力对界面的损伤,使器件具有好的疲劳特性. 此外,研究了退火温度对存储特性的影响,结果表明800 ℃退火样品的存储特性比700 ℃退火的好,这是因为800 ℃时NO退火可在LaON（HfON）中引入更多的N,且能更好释放应力,使介质中缺陷减少. 关键词： MONOS 双隧穿层 LaON HfON