渐变折射率Ta_2O_5/SiO_2薄膜多脉冲激光损伤特性

采用离子束溅射(IBS)的方式,制备了1064nm高反射Ta2O5/SiO2渐变折射率光学薄膜。对其光学性能和在基频多脉冲下抗损伤性能进行了分析。通过渐变折射率的设计方式,很好地抑制了边带波纹,增加了1064nm反射率。通过对损伤阈值的分析发现,随着脉冲个数的增加,损伤阈值下降明显;但是在20个脉冲数后,损伤阈值(维持在22J/cm2左右)几乎保持不变直到100个脉冲数。通过Leica显微镜对损伤形貌的观察,发现损伤诱因是薄膜表面的节瘤缺陷。通过扫描电镜(SEM)以及聚集离子束(FIB)对薄膜表面以及断面的观察,证实了薄膜的损伤起源于薄膜表面的节瘤缺陷。进一步研究得出,渐变折射率薄膜在基频光单脉冲下损伤主要是由初始节瘤缺陷引起的,在后续多脉冲激光辐照下初始节瘤缺陷引起烧蚀坑的面积扩大扫过薄膜上的其他节瘤缺陷,引起了其他节瘤缺陷的喷射使损伤加剧,造成损伤的"累积效应"。     

Influence of overcoat on laser-induced damage threshold of 532 and 800 nm TiO2/SiO2 high reflectors

TiO₂/SiO₂ high reflectors with and without a SiO₂ overcoat are deposited by electron-beam evaporation. The film properties are characterized by visible spectrometry measures, structure analysis, roughness and laser-induced damage threshold (LIDT) tests, surface defects and damage morphology observation. The effects of overcoats on LIDT at 532 nm, 8 ns and 800 nm, 220 ps laser pulses are investigated. The relations between film structure, roughness, surface defects, electric field and LIDT are discussed. It is found that overcoats can increase the LIDT at these two laser wavelengths. The reduction of peak temperature, the low defects density and roughness, the low intrinsic absorption of SiO₂ and its amorphous structure are the main reasons for LIDT improvement by overcoats.     

Effects of deposition rates on laser damage threshold of TiO2/SiO2 high reflectors

TiO₂ single layers and TiO₂/SiO₂ high reflectors (HR) are prepared by electron beam evaporation at different TiO₂ deposition rates. It is found that the changes of properties of TiO₂ films with the increase of rate, such as the increase of refractive index and extinction coefficient and the decrease of physical thickness, lead to the spectrum shift and reflectivity bandwidth broadening of HR together with the increase of absorption and decrease of laser-induced damage threshold. The damages are found of different morphologies: a shallow pit to a seriously delaminated and deep crater, and the different amorphous-to-anatase-to-rutile phase transition processes detected by Raman study. The frequency shift of Raman vibration mode correlates with the strain in film. Energy dispersive X-ray analysis reveals that impurities and non-stoichiometric defects are two absorption initiations resulting to the laser-induced transformation.     

Preparation of sol-gel ZrO2-SiO2 highly reflective multilayer films and laser-induced damage threshold characteristic

Sol-gel (ZrO₂/SiO₂)¹² ZrO₂ films were prepared by spin coating method. The reflectivity spectrum of the films was measured with a Lambda 900 spectrometer. In order to investigate laser-induced damage threshold (LIDT) characteristic of highly reflective films, one-layer ZrO₂ and SiO₂ films, two-layer ZrO₂/SiO₂ and SiO₂/ZrO₂ films were also prepared by spin coating method. LIDT of each film was measured. Damage morphology after laser irradiation was characterized by optical microscopy (Nikon E600K). The experimental results showed that the reflectivity of (ZrO₂/SiO₂)¹² ZrO₂ film at 1064 nm and 355 nm wavelength is 99.7%. The LIDT results decreases as the number of layer of films increases. All the films have similar damage morphology. The experimental results are explained by the different temperature profiles of the films.     

Study of modulation property to incident laser by surface micro-defects on KH2PO4 crystal

KH₂PO₄ crystal is a crucial optical component of inertial confinement fusion. Modulation of an incident laser by surface micro-defects will induce the growth of surface damage, which largely restricts the enhancement of the laser induced damage threshold. The modulation of an incident laser by using different kinds of surface defects are simulated by employing the three-dimensional finite-difference time-domain method. The results indicate that after the modulation of surface defects, the light intensity distribution inside the crystal is badly distorted, with the light intensity enhanced symmetrically. The relations between modulation properties and defect geometries (e.g., width, morphology, and depth of defects) are quite different for different defects. The modulation action is most obvious when the width of surface defects reaches 1.064 μ. For defects with smooth morphology, such as spherical pits, the degree of modulation is the smallest and the light intensity distribution seems relatively uniform. The degree of modulation increases rapidly with the increase of the depth of surface defects and becomes stable when the depth reaches a critical value. The critical depth is 1.064 μ for cuboid pits and radial cracks, while for ellipsoidal pits the value depends on both the width and the length of the defects.     

XPS investigation of diffusion of two-layer ZrO2/SiO2 and SiO2/ZrO2 sol–gel films

Two-layer ZrO₂/SiO₂ and SiO₂/ZrO₂ films were deposited on K9 glass substrates by sol–gel dip coating method. X-ray photoelectron spectroscopy (XPS) technique was used to investigate the diffusion of ZrO₂/SiO₂ and SiO₂/ZrO₂ films. To explain the difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films, porous ratio and surface morphology of monolayer SiO₂ and ZrO₂ films were analyzed by using ellipsometry and atomic force microscopy (AFM). We found that for the ZrO₂/SiO₂ films there was a diffusion layer with a certain thickness and the atomic concentrations of Si and Zr changed rapidly; for the SiO₂/ZrO₂ films, the atomic concentrations of Si and Zr changed relatively slowly, and the ZrO₂ layer had diffused through the entire SiO₂ layer. The difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films was influenced by the microstructure of SiO₂ and ZrO₂.     

Effect of O-vacancy defects on the Schottky barrier heights in Ni/SiO2 and Ni/HfO2 interfaces

We perform first-principles density functional calculations to study the electronic structure of Ni/HfO₂ and Ni/SiO₂ interfaces and the effect of O-vacancy (V_O) defects on the Schottky barrier height and the effective work function. We generate two interface models in which Ni is placed on O-terminated HfO₂ (1 0 0) and α-quartz (1 0 0) surfaces. As the concentration of V_O defects at the interface increases, the p-type Schottky barrier height tends to increase in the Ni/HfO₂ interface, due to the reduction of interface dipoles, whereas it is less affected in the Ni/SiO₂ interface.     

溶胶-凝胶ZrO2-TiO2高折射率光学膜层的抗激光损伤性能研究

采用溶胶-凝胶方法制备了ZrO₂-TiO₂(Ti含量为0—100mol%)高折射率光学薄膜. 借助激光动态光散射技术研究溶胶微结构. 采用傅里叶变换红外光谱、原子力显微镜、薄膜光学常数分析仪、漫反射吸收光谱及强激光辐照实验，对膜层的结构、光学性能及抗激光损伤性能进行了系统表征. 结果显示，溶胶-凝胶工艺可以在部分牺牲折射率的情况下，使膜层的抗激光损伤性能得到大幅度提升. 随Ti含量从0mol%增加至100mol%，膜层的平均损伤阈值呈下降趋势，当Ti含量从0mol%增加至60mol%时，平均损伤阈值从57.1J/cm²下降到21.1J/cm²(辐照激光波长为1053nm，脉冲宽度为10ns，“R/1”测试模式)，当Ti含量从60mol%增加至100mol%时，平均损伤阈值变化很小. 综合溶胶微结构、膜层光学性能和损伤实验结果可以推断，强激光诱导多光子吸收是引起膜层损伤的主要原因. 不同配比的复合膜之间光学带隙的显著差异导致相同辐照激光情况下多光子吸收的概率发生变化，从而导致损伤阈值的规律性变化. 关键词： 2-TiO₂薄膜')" href="#">ZrO₂-TiO₂薄膜 溶胶-凝胶 激光诱导损伤 光学带隙     

Influence of ZrO2 in HfO2 on reflectance of HfO2/SiO2 multilayer at 248 nm prepared by electron-beam evaporation

Influence of ZrO₂ in HfO₂ on the reflectance of HfO₂/SiO₂ multilayer at 248 nm was investigated. Two kinds of HfO₂ with different ZrO₂ content were chosen as high refractive index material and the same kind of SiO₂ as low refractive index material to prepare the mirrors by electron-beam evaporation. The impurities in two kinds of HfO₂ starting coating materials and in their corresponding single layer thin films were determined through glow discharge mass spectrum (GDMS) technology and secondary ion mass spectrometry (SIMS) equipment, respectively. It showed that between the two kinds of HfO₂, either the bulk materials or their corresponding films, the difference of ZrO₂ was much larger than that of the other impurities such as Ti and Fe. It is the Zr element that affects the property of thin films. Both in theoretical and in experimental, the mirror prepared with the HfO₂ starting material containing more Zr content has a lower reflectance. Because the extinction coefficient of zirconia is relatively high in UV region, it can be treated as one kind of absorbing defects to influence the optical property of the mirrors.     

Influence of SiO2 additional layers on the laser induced damage threshold of Ta2O5 films

A series of Ta₂O₅ films with different SiO₂ additional layers including overcoat, undercoat and interlayer was prepared by electron beam evaporation under the same deposition process. Absorption of samples was measured using the surface thermal lensing (STL) technique. The electric field distributions of the samples were theoretical predicted using thin film design software (TFCalc). The laser induced damage threshold (LIDT) was assessed using an Nd:YAG laser operating at 1064 nm with a pulse length of 12 ns. It was found that SiO₂ additional layers resulted in a slight increase of the absorption, whereas they exerted little influence on the microdefects. The electric field distribution among the samples was unchanged by adding an SiO₂ overcoat and undercoat, yet was changed by adding an interlayer. SiO₂ undercoat. The interlayer improved the LIDT greatly, whereas the SiO₂ overcoat had little effect on the LIDT.     

Substrate effects on the oxygen gas sensing properties of SnO2/TiO2 thin films

In this study, SnO₂/TiO₂ thin films are fabricated on SiO₂/Si and Corning glass 1737 substrates using a R.F. magnetron sputtering process. The gas sensing properties of these films under an oxygen atmosphere with and without UV irradiation are carefully examined. The surface structure, morphology, optical transmission characteristics, and chemical compositions of the films are analyzed by atomic force microscopy, scanning electron microscopy and PL spectrometry. It is found that the oxygen sensitivity of the films deposited on Corning glass 1737 substrates is significantly lower than that of the films grown on SiO₂/Si substrates. Therefore, the results suggest that SiO₂/Si is an appropriate substrate material for oxygen gas sensors fabricated using thin SnO₂/TiO₂ films.     

SiO2的赝晶化及AlN/SiO2纳米多层膜的超硬效应

采用反应磁控溅射法制备了一系列不同SiO₂层厚度的AlN/SiO₂纳米多层膜，利用X射线衍射仪、高分辨透射电子显微镜和微力学探针表征了多层膜的微结构和力学性能，研究了SiO₂层在多层膜中的晶化现象及其对多层膜生长方式及力学性能的影响. 结果表明，由于受AlN六方晶体结构的模板作用，溅射条件下以非晶态存在的SiO₂层在其厚度小于0.6 nm时被强制晶化为与AlN相同的六方结构赝晶体并与AlN形成共格外延生长. 由于不同模量的两调制层存在晶格错配度，多层膜中产生了拉、压交变的应力场，使得多层膜产生硬度升高的超硬效应. SiO₂随层厚的进一步增加又转变为以非晶态生长，多层膜的外延生长结构受到破坏，其硬度也随之降低. 关键词： 2纳米多层膜')" href="#">AlN/SiO₂纳米多层膜 赝晶化 应力场 超硬效应     

Metal carbide-induced negative flatband voltage shift in TaCx and HfCx/HfO2 gate stacks

We systematically investigated the role of the top interface for TaC_x and HfC_x/HfO₂ gate stacks on the effective work function (Φ_m,eff) shift by inserting a SiN layer at the gate/HfO₂ top interface or HfO₂/SiO₂ bottom interface. We found that Φ_m,eff of the TaN gate electrode on HfO₂ was larger than that on SiO₂ because of the HfO₂/SiO₂-bottom-interface dipole. On the other hand, we found that Φ_m,eff values of the TaC_x and HfC_x gate electrodes on HfO₂ agree with Φ_m,eff on SiO₂. This is because the potential offset of the opposite direction with respect to the bottom interface dipole appears at the metal carbide/HfO₂ interface. It is thus concluded that the top interface in the metal carbide/HfO₂ gate stacks causes the negative Φ_m,eff shift.     

单层SiO2物理膜与化学膜激光损伤机理的对比研究

采用离子束溅射沉积技术和溶胶-凝胶技术在K9基片上镀制了厚度相近的SiO₂单层介质膜，用表面热透镜技术对两类膜层分别进行了热吸收及实时动态热畸变实验测试，结合散射光阈值测试及实验前后膜层的显微观测，对相同基底、相同膜层材料而采用不同方法镀制的光学膜层，发现化学膜的强激光损伤阈值远高于相应物理膜；从热力学响应及膜层特性差异的角度揭示了化学膜层的强激光损伤阈值远高于相应物理膜层的微观机理，即物理膜具有高吸收下的致密膜层快传导的基底热冲击效应，而化学膜则有低吸收下的疏松空隙填充慢传导的延缓效应，大量的实验数据及现象都证实了这一结论. 关键词： 强激光辐照损伤 损伤形貌 热冲击 热吸收     

Low-temperature deposition of stoichiometric HfO2 on silicon: Analysis and quantification of the HfO2/Si interface from electrical and XPS measurements

An understanding of the exact structural makeup of dielectric interface is crucial for development of novel gate materials. In this paper a study of the HfO₂/Si interface created by the low-temperature deposition ultrathin stoichiometric HfO₂ on Si substrates by reactive sputtering is presented. Analysis, quantification and calculation of layer thickness of an HfO₂/Hf-Si-O_x/SiO₂ gate stack dielectrics have been performed, using X-ray photoelectron spectroscopy (XPS) depth profile method, angle resolved XPS and interface modeling by XPS data processing software. The results obtained were found to be in good agreement with the high frequency capacitance-voltage (C-V) measurements. The results suggest a development of a complex three layer dielectric stack, including hafnium dioxide layer, a narrow interface of hafnium silicate and broad region of oxygen diffusion into silicon wafer. The diffusion of oxygen was found particularly detrimental to the electrical properties of the stack, as this oxygen concentration gradient leads to the formation of suboxides of silicon with a lower permittivity, κ.     

Effect of SiO2 protective layer on the femtosecond laser-induced damage of HfO2/SiO2 multilayer high-reflective coatings

Two kinds of HfO₂/SiO₂ 800 nm high-reflective (HR) coatings, with and without SiO₂ protective layer were deposited by electron beam evaporation. Laser-induced damage thresholds (LIDT) were measured for all samples with femtosecond laser pulses. The surface morphologies and the depth information of all samples were observed by Leica optical microscopy and WYKO surface profiler, respectively. It is found that SiO₂ protective layer had no positive effect on improving the LIDT of HR coating. A simple model including the conduction band electron production via multiphoton ionization and impact ionization is used to explain this phenomenon. Theoretical calculations show that the damage occurs first in the SiO₂ protective layer for HfO₂/SiO₂ HR coating with SiO₂ protective layer. The relation of LIDT for two kinds of HfO₂/SiO₂ HR coatings in calculation agrees with the experiment result.     

Au/SiO2纳米多层薄膜的制备及其性质表征

利用多靶磁控溅射技术制备了Au/SiO₂纳米颗粒分散氧化物多层复合薄膜.研究了在保持Au单层颗粒膜沉积时间一定时薄膜厚度一定、变化SiO₂的沉积时间及SiO₂的沉积时间一定而改变薄膜厚度时，多层薄膜在薄膜厚度方向的微观结构对吸收光谱的影响.研究结果表明：具有纳米层状结构的Au/SiO₂多层薄膜在560 nm波长附近有明显的表面等离子共振吸收峰，吸收峰的强度随Au颗粒的浓度增加而增强，在Au颗粒浓度相同的情况下，复合薄膜 关键词： 2纳米复合薄膜')" href="#">Au/SiO₂纳米复合薄膜 多靶磁控溅射 吸收光谱 有效介质理论     

Influence of different oxidants on band alignment of HfO2 films deposited by atomic layer deposition

Based on X-ray photoelectron spectroscopy (XPS), influences of different oxidants on band alignment of HfO₂ films deposited by atomic layer deposition (ALD) are investigated in this paper. The measured valence band offset (VBO) value for H₂O-based HfO₂ increases from 3.17 eV to 3.32 eV after annealing, whereas the VBO value for O₃-based HfO₂ decreases from 3.57 eV to 3.46 eV. The research results indicate that the silicate layer changes in different ways for H₂O-based and O₃-based HfO₂ films after annealing process, which plays a key role in generating the internal electric field formed by the dipoles. The variations of the dipoles at the interface between the HfO₂ and SiO₂ after annealing may lead the VBO values of H₂O-based and O₃-based HfO₂ to vary in different ways, which is in agreement with the varition of flat band (V_FB) voltage.     

Evidence of GeO volatilization and its effect on the characteristics of HfO2 grown on Ge substrate

HfO₂ films are deposited by atomic layer deposition (ALD) using tetrakis ethylmethylamino hafnium (TEMAH) as the hafnium precursor, while O₃ or H₂O is used as the oxygen precursor. After annealing at 500℃ in nitrogen, the thickness of Ge oxide's interfacial layer decreases, and the presence of GeO is observed at the H₂O-based HfO₂ interface due to GeO volatilization, while it is not observed for the O₃-based HfO₂. The difference is attributed to the residue hydroxyl groups or H₂O molecules in H₂O-based HfO₂ hydrolyzing GeO₂ and forming GeO, whereas GeO is only formed by the typical reaction mechanism between GeO₂ and the Ge substrate for O₃-based HfO₂ after annealing. The volatilization of GeO deteriorates the characteristics of the high-κ films after annealing, which has effects on the variation of valence band offset and the C–V characteristics of HfO₂/Ge after annealing. The results are confirmed by X-ray photoelectron spectroscopy (XPS) and electrical measurements.     

Influences of CO2 laser annealing on mechanical and laser-induced damage properties of ZrO2 thin films

Zirconium dioxide (ZrO₂) thin films were deposited on BK7 glass substrates by the electron beam evaporation method. A continuous wave CO₂ laser was used to anneal the ZrO₂ thin films to investigate whether beneficial changes could be produced. After annealing at different laser scanning speeds by CO₂ laser, weak absorption of the coatings was measured by the surface thermal lensing (STL) technique, and then laser-induced damage threshold (LIDT) was also determined. It was found that the weak absorption decreased first, while the laser scanning speed is below some value, then increased. The LIDT of the ZrO₂ coatings decreased greatly when the laser scanning speeds were below some value. A Nomarski microscope was employed to map the damage morphology, and it was found that the damage behavior was defect-initiated both for annealed and as-deposited samples. The influences of post-deposition CO₂ laser annealing on the structural and mechanical properties of the films have also been investigated by X-ray diffraction and ZYGO interferometer. It was found that the microstructure of the ZrO₂ films did not change. The residual stress in ZrO₂ films showed a tendency from tensile to compressive after CO₂ laser annealing, and the variation quantity of the residual stress increased with decreasing laser scanning speed. The residual stress may be mitigated to some extent at proper treatment parameters.