Charge trapping and breakdown in thin SiO2 polysilicon-gate MOS capacitors

Charge trapping during high-field (Fowler-Nordheim) injection in thin SiO₂ films is investigated. Constant and pulsed current injection as well as C-V measurements are used to determine the evolution of trapped charge and interface state densities. The relation between these charges, which can be influenced by temperature and γ radiation, and dielectric breakdown is studied. We establish the dominant role of negative trapped charge.     

SiO2 passivation film effects on microwave characteristics of YBa2Cu3O7−x-based resonators

SiO₂ film coated as a passivation layer for YBa₂Cu₃O_7−x (YBCO)-based microwave devices is investigated by measuring the microwave characteristics of microstrip line resonators. The SiO₂ film is deposited with its 0.3 to 0.4 μm thickness by a sputtering method using Ar + 30%O₂ plasma. These deposition conditions do not degrade the microwave characteristics and the critical temperature (T_c). Next, the SiO₂ film coated resonators are compared with the uncoated ones for two kinds of degradation conditions: a 200°C annealing in air, and an exposure to air at 85°C and 85% RH (relative humidity). We find that the SiO₂ passivation film prevents the YBCO thin film from the surface degradation and reacting with water.     

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.     

High field phenomena in thin plasma nitrided SiO2 films

The effects of high field tunnel electron injection on the electrical properties of Al - thin plasma nitrided SiO₂ films - Si (p-type) structures are studied. Under high field injection, it has been observed that electron trapping, positive charge generation near the Si-SiO₂ interface (slow states) and fast state generation at the Si-SiO₂ interface have taken place. After high temperature N₂ annealing, the nitridation induced electron trap density is considerably decreased. Furthermore, under high field injection the generation rate of both the slow states and the interface states and consequently, the degradation rate of the nitrided oxide films have been also decreased after annealing.     

多面体共替代对Sr_2(Al_(1–x) Mg_x)(Al_(1–x) Si_(1+x))O_7:Eu~(2+)晶体结构和发光颜色的影响

采用高温固相法合成Sr_(1.98)(Al_(1–x) Mg_x)(Al_(1–x) Si_(1+x))O_7: 2%Eu~(2+)荧光粉完全固溶体,利用X射线衍射、光致发光光谱和光学显微镜进行晶体结构和发光性能的研究. Sr_2Al_2SiO_7和Sr_2MgSi_2O_7同构化合物中包含[MgO_4]、[SiO_4]和[AlO_4]四面体,较大体积的[MgO_4]和较小体积的[SiO_4],共同替代体积相似的[AlO_4],导致[(Si/Al)O_4]收缩和[(Mg/Al)O_4]膨胀,晶胞参数c减少, a和V增大,使Eu~(2+)周围的环境发生改变,晶体场劈裂程度减小,发射峰位从503 nm蓝移至467 nm,实现发光光谱从绿色(0.2384, 0.3919)到蓝色(0.1342,0.1673)的转变.当x为0时,发射峰的半高宽为120 nm, x从0.25增加到1时,半高宽由89 nm逐渐减小至50 nm,多面体的替代会改变荧光粉的发光性能.     

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.     

High temperature reaction and defect chemistry at the Si/SiO2 interface

The generation of structural and electrical defects in Si/SiO₂ structures upon high temperature annealing by the oxide decomposition reaction Si+SiO₂→2SiO ↑ has been studied using scanning electron microscopy (SEM) and ramped current-voltage measurements. The SiO decomposition is nucleated at crystalline defects in the substrate and results in the formation of voids in the oxide. The voids grow laterally with annealing time, independent of the nature of the defect. Prior to the formation of physical voids in the oxide, defects become electrically active, leading to low field dielectric breakdown. The breakdown degradation is prevented when the O₂ pressure in the annealing ambient is sufficient to reverse the decomposition reaction by reoxidizing the SiO product at the interface.     

Ce3+掺杂SiO2-Al2O3-Gd2O3玻璃的闪烁性能

通常, Ce离子掺杂的低密度玻璃有较高的发光效率, 而高密度的Ce离子掺杂玻璃其发光效率很低. 为了解释这一现象, 采用高温熔融法获得了SiO₂-Al₂O₃-Gd₂O₃三元系统的玻璃形成区, 并在还原气氛下制备了Ce³⁺掺杂SiO₂-Al₂O₃-Gd₂O₃以及SiO₂-Al₂O₃-Gd₂O₃-Ln₂O₃ (Ln=Y, La, Lu)闪烁玻璃, 研究了其光谱和闪烁性能. 测试结果显示: 随着Gd₂O₃含量增加, 玻璃紫外截止波长发生红移, 荧光强度降低, 衰减时间缩短; 加入Lu₂O₃, La₂O₃, Y₂O₃后, 紫外截止波长发生红移, 荧光强度降低, 衰减时间变短; 当Gd₂O₃超过10% mol时, X射线荧光积分光产额从相当于锗酸铋 晶体的61%降低到13%. 荧光强度降低、衰减时间缩短的原因是随着玻璃的紫外截止波长红移玻璃的能带宽度变窄, 使得Ce³⁺离子的d电子轨道开始接近玻璃的导带, Ce³⁺离子受辐射后跃迁到d电子轨道的电子会通过导带与玻璃中的空穴复合, 产生电荷迁移猝灭效应.     

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。     

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.     

γ射线作用下氧化铪基MOS结构总剂量效应研究

使用原子层淀积方法得到了7.8 nm厚度的HfO₂薄膜并通过直接溅射金属铝电极得到了Al/HfO₂/Si MOS电容结构,测量得到了HfO₂基MOS结构在60Co γ射线辐照前后的电容-电压特性,使用原子力显微镜得到了HfO₂薄膜在辐照前后的表面微观形貌,使用X射线光电子能谱方法测量得到了HfO₂薄膜在辐照前后的化学结构变化。研究发现,使用原子层淀积方法制备的HfO₂薄膜表面质量较高;γ射线辐照在HfO₂栅介质中产生了数量级为1012 cm-2的负的氧化层陷阱电荷;HfO₂薄膜符合化学计量比,介质内部主要的缺陷为氧空位且随着辐照剂量的增加而增加,说明辐照在介质中引入了陷阱从而导致MOS结构性能的退化。     

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.     

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：     

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.     

SiO2薄膜内部短程有序微结构研究

SiO₂薄膜是重要的低折射率材料之一, 针对离子束溅射(IBS)和电子束蒸发(EB)的SiO₂薄膜, 采用红外光谱反演技术获得在400–1500 cm^-1波数内的介电常数, 通过对介电能损函数的分析获得了两种薄膜在横向和纵向光学 振动模式下的振动频率和Si–O–Si键角.研究结果表明, 在EB SiO₂薄膜短程有序范围内, SiO₄的连接方式主要是类柯石英结构、3-平面折叠环和热液石英结构的SiO₄连接方式; 在IBS SiO₂薄膜短程有序范围内, SiO₄的连接方式复杂主要是类柯石英结构、3-平面折叠环、 4-平面折叠环结构和类热液石英结构. 关键词： 2薄膜')" href="#">SiO₂薄膜 离子束溅射 电子束蒸发 短程有序     

三联吡啶钌超分子包合物及其SiO2复合纳米粒的电化学发光信号放大

利用环糊精类物质能够形成超分子包合物的性质,研究了电中性的β-环糊精（β-CD）和负电性的羧甲基-β-环糊精（CM-β-CD）与电化学发光（ECL）活性物质三联吡啶钌（Ru（bpy）₃²⁺）形成超分子包合物的能力及其对ECL的增强作用。结果表明：形成的超分子包合物能够增强Ru（bpy）₃²⁺的ECL,其中CM-β-CD具有更强的增强作用。相对于Ru（bpy）₃²⁺,CM-β-CD增强了1.42倍,而β-CD仅为1.28倍。以制备的表面电荷为负的SiO₂纳米粒为载体,考察了其对Ru（bpy）₃²⁺超分子包合物的吸附能力。结果表明,与Ru（bpy）₃²⁺的CM-β-CD超分子包合物相比,SiO₂纳米粒载体对Ru（bpy）₃²⁺的β-CD 超分子包合物表现出了更强的吸附能力。制备了ECL信号放大能力最强的β-CD-Ru（bpy）₃²⁺超分子包合物的SiO₂复合纳米粒。     

红色荧光粉Na8.33 La1.67(SiO4)6 O2:Eu3+的制备及发光特性

采用高温固相法制备了Na_(8. 33)La_(1. 67)(SiO_4)_6O_2∶Eu~(3+)红色发光材料,利用X射线衍射仪测定其晶体结构,利用Hitachi F4600表征其发光光谱。在紫外光激发下,样品Na_(8. 33)La_(1. 67)(SiO_4)_6O_2∶Eu~(3+)呈多峰发射,分别对应于Eu~(3+)的~5D_0-~7F_j(j=0,1,2,3,4)能级跃迁,主峰是位于615 nm的~5D_0-~7F_2跃迁发射。研究了Eu~(3+)掺杂浓度对材料发光性质的影响,改变Eu~(3+)掺杂浓度,样品的发射强度随之改变,Na_(8. 33)La_(1. 67)(SiO_4)_6O_2∶Eu~(3+)材料的Eu~(3+)浓度为15%时,发光强度最大。讨论了浓度猝灭的机理,理论计算表明引起Eu~(3+)离子能量弥散的主要原因是离子间交换相互作用。     

Ba9Y2(SiO4)6: Ce3+,Mn2+荧光粉的发光特性及能量传递

利用高温固相法制备了Ba₉Y₂(SiO₄)₆:Ce³⁺,Mn²⁺(BYS:Ce³⁺,Mn²⁺)荧光粉,并通过X射线衍射(XRD)谱、激发和发射光谱及荧光寿命的测试对材料的结构、发光特性和能量传递进行了研究。在327 nm激发下,BYS:Ce³⁺,Mn²⁺发射光谱中包含2个发射峰,分别为位于407 nm的Ce³⁺的蓝紫光发射和位于597 nm的Mn²⁺的红光发射。在该体系中,发现了Ce³⁺向Mn²⁺的有效能量传递,使得Mn²⁺在597 nm处的红光发射显著提高,当x(Mn²⁺)=0.25时,BYS:Ce³⁺,xMn²⁺的能量传递效率可达39%。实验表明,该荧光粉可为紫外基白光LED提供良好的红光光源。     

Reversible H2 passivation of Si ≡ Si3 interface defects in (1 1 1)Si/SiO2

K-band electron spin resonance (ESR) at 4.3 K has revealed the dipole-dipole (DD) interaction effects between [1 1 1]P_b centers (^*Si ≡ Si₃ defects with unpaired sp³ hybrid [1 1 1]) at the 2 dimensional (1 1 1)Si/SiO₂ interface. This has been enabled by the perfectly reversible H₂ passivation of P_b, which affects the defect's spin state. Sequential hydrogenation at 253–353°C and degassing treatments in high vacuum at 743–835°C allowed to vary the P_b density in the range 5 × 10¹⁰ < [P_b] (1.14 ± 0.06) × 10¹³ cm^-2. With increasing [P_b] fine structure doublets are clearly resolved. It is found that (1 1 1)Si/SiO₂ interfaces, dry thermally grown at ≈920°C, naturally comprise a ^*Si ≡ Si₃ defect density — passivated or not — of 1.14 × 10¹³ cm^-2.     

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.