单层膜体吸收与界面吸收研究

采用热透镜测量方法进行了SiO₂和HfO₂单层膜的体吸收与界面吸收分离研究.首先推导了光从薄膜侧及基底侧入射时单层膜内的驻波场分布,给出了单一厚度薄膜分离体吸收和界面吸收的计算方程式以及求解薄膜消光系数的方法.利用电子束蒸发工艺制备了半波长光学厚度(λ=1064 nm)的SiO₂和HfO₂单层膜,通过热透镜的测量数据实际分离了两种薄膜的体吸收和界面总吸收.计算结果表明,对于吸收小至10^{-6关键词： 驻波场理论 光热技术 薄膜吸收 消光系数}     

脉冲激光辐照光学薄膜的缺陷损伤模型

建立了缺陷吸收升温致薄膜激光损伤模型,该模型从热传导方程出发,考虑了缺陷内部的温度分布以及向薄膜的传导过程,通过引入散射系数简化了Mie散射理论得出的吸收截面.对电子束蒸发沉积的ZrO₂:Y₂O₃单层膜进行了激光破坏实验,薄膜样品的损伤是缺陷引起的,通过辉光放电质谱法对薄膜制备材料的纯度分析发现材料中的主要杂质元素为铂,其含量为0.9％.利用缺陷损伤模型对损伤过程进行了模拟,理论模型和实验结果取得了较好的一致性.     

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。     

激光诱导多层光学薄膜损伤分析与仿真

提出一种全面分析光学薄膜损伤特性的方法,根据热传导理论与电子增殖理论建立激光辐照下多层介质膜的损伤理论模型。以HfO₂/SiO₂多层高反膜为例,计算红外纳秒脉冲激光作用下膜系内部的温度场、应力场以及自由电子数密度分布,对其热学特性与电子增殖特性进行综合评估后,得到不同输入条件下膜系的损伤阈值。结果表明,薄膜材料的损伤特性会受到驻波场的影响,在1064 nm波长的激光辐照下HfO₂/SiO₂ 多层介质薄膜的热致应力损伤效应先于热熔融效应先于场效应发生,且薄膜中SiO₂层发生热损伤,而薄膜并未发生场损伤,此外薄膜的损伤阈值随着激光脉宽的增大而增大。     

沉积速率和氧分压对HfO2薄膜残余应力的影响

采用ZYGO MarkIII-GPI数字波面干涉仪对以K9玻璃为基底的电子束蒸发方法制备的HfO₂薄膜中的残余应力进行了研究,讨论了沉积速率、氧分压这两种工艺参量对HfO₂薄膜残余应力的影响.实验结果表明：在所有的工艺条件下,薄膜的残余应力均为张应力;随着沉积速率的升高,氧分压的减小,薄膜的堆积密度逐渐增大,而残余应力呈减小趋势.同时用X射线衍射技术测量分析了不同工艺条件下HfO₂薄膜的晶体结构,探讨了HfO₂薄膜晶体 关键词： 残余应力 2薄膜')" href="#">HfO₂薄膜 沉积速率 氧分压     

缺陷对HfO2薄膜的激光弱吸收与损伤阈值的影响

激光弱吸收是导致光学薄膜损伤的重要原因。在(5~43)mPa的氧分压下制备并测试了一组HfO2薄膜。实验发现,当氧分压小于20mPa时,薄膜弱吸收越大,损伤阈值越低;当氧分压大于20mPa时,薄膜的损伤阈值与弱吸收并不一一对应,具有较高弱吸收的薄膜可能同时具有较高的损伤阈值。建立了缺陷模型,采用有限元法模拟了缺陷对弱吸收测量和损伤阈值测量的影响,分析了缺陷尺寸、密度、吸收系数对弱吸收和损伤阈值的影响。研究结果显示,吸收系数高于薄膜1 000倍的缺陷可以降低薄膜的损伤阈值1 000倍,却并不影响薄膜的弱吸收。缺陷对HfO2薄膜的激光弱吸收与损伤阈值测试有完全不同的影响,是导致某些薄膜弱吸收与损伤阈值背离的原因。     

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     

HfO2基铁电薄膜的结构、性能调控及典型器件应用

大数据、物联网和人工智能的快速发展对存储芯片、逻辑芯片和其他电子元器件的性能提出了越来越高的要求.本文介绍了HfO₂基铁电薄膜的铁电性起源,通过掺杂元素改变晶体结构的对称性或引入适量的氧空位来降低相转变的能垒可以增强HfO₂基薄膜的铁电性,在衬底和电极之间引入应力、减小薄膜厚度、构建纳米层结构和降低退火温度等方法也可以稳定铁电相.与钙钛矿氧化物铁电薄膜相比, HfO₂基铁电薄膜具有与现有半导体工艺兼容性更强和在纳米级厚度下铁电性强等优点.铁电存储器件理论上可以达到闪存的存储密度,读写次数超过10¹⁰次,同时具有读写速度快、低操作电压和低功耗等优点.此外,还总结了HfO₂基薄膜在负电容晶体管、铁电隧道结、神经形态计算和反铁电储能等方面的主要研究成果.最后,讨论了HfO₂基铁电薄膜器件当前面临的挑战和未来的机遇.     

Al掺杂对HfO2俘获层可靠性影响第一性原理研究

采用基于MS(Materials Studio)软件和密度泛函理论的第一性原理方法, 研究了HfO₂ 俘获层的电荷俘获式存储器(Charge Trapping Memory, CTM)中电荷的保持特性以及耐擦写性. 在对单斜晶HfO₂中四配位氧空位(V_O4) 缺陷和V_O4 与Al替位Hf掺杂的共存缺陷体(Al+V_O4)两种超晶胞模型进行优化之后, 分别计算了其相互作用能、形成能、Bader电荷、态密度以及缺陷俘获能. 相互作用能和形成能的计算结果表明共存缺陷体中当两种缺陷之间的距离为2.216 Å时, 结构最稳定、缺陷最容易形成; 俘获能计算结果表明, 共存缺陷体为双性俘获, 且与V_O4缺陷相比, 俘获能显著增大; Bader电荷分析表明共存缺陷体更有利于电荷保持; 态密度的结果说明共存缺陷体对空穴的局域能影响较强; 计算两种模型擦写电子前后的能量变化表明共存缺陷体的耐擦写性明显得到了改善. 因此在HfO₂俘获层中可以通过加入Al杂质来改善存储器的保持特性和耐擦写性. 本文的研究可为改善CTM数据保持特性和耐擦写性提供一定的理论指导.     

薄膜体内缺陷对损伤概率的影响

由实验中得到的激光损伤概率与表面杂质密度的关系出发，结合XRD测试和激光损伤测试的结果，得到体缺陷或杂质破坏起主导作用的损伤机理.将激光作用时杂质吸收的热学和力学过程与杂质分布的统计规律结合起来，得到了深埋于薄膜内部的杂质诱导薄膜损伤概率与杂质密度、激光功率密度以及薄膜厚度的关系.该模型认为能诱导薄膜破坏的杂质尺寸范围与杂质填埋深度有关，所以不同深度处能诱导薄膜损伤的杂质密度不一样，理论结果与实验结果符合得很好.该理论模型还可以很好地解释损伤形貌.     

Influence of negative ion element impurities on laser induced damage threshold of HfO2 thin film

Negative ion element impurities breakdown model in HfO₂ thin film was reported in this paper. The content of negative ion elements were detected by glow discharge mass spectrum analysis (GDMS); HfO₂ thin films were deposited by the electron-beam evaporation method. The weak absorption and laser induced damage threshold (LIDT) of HfO₂ thin films were measured to testify the negative ion element impurity breakdown model. It was found that the LIDT would decrease and the absorption would increase with increasing the content of negative ion element. These results indicated that negative ion elements were harmful impurities and would speed up the damage of thin film.     

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.     

Optical and structural properties of thin films deposited from laser fused Zirconia,Hafnia, and Yttria

The optical and structural properties of films deposited from laser sintered Zirconia (ZrO₂), Hafnia (HfO₂), and Yttria (Y₂O₃) and from the commercially available (unprocessed material) Zirconia, Hafnia and Yttria, were studied and compared. All the films had low absorption. Films deposited from the laser sintered material had very low optical inhomogeneity. ZrO₂ films showed negative inhomogeneity for films deposited from the unprocessed material. The refractive index increased for ZrO₂ films deposited from the laser sintered material. HfO₂ and Y₂O₃ films showed positive inhomogeneity when deposited from the unprocessed material. The refractive index of the films of these materials decreased when deposited from the laser sintered material. The thin films of ZrO₂ and Y₂O₃ prepared from laser sintered material had stable monoclinic and cubic structures respectively while HfO₂ films were found to be amorphous.     

Influence of substoichiometer on the laser-induced damage characters of HfO2 thin films

HfO₂ is one of the most important high refractive index materials for depositing high power optical mirrors. In this research, HfO₂ thin films were prepared by dual-ion beam reactive sputtering method, and the laser-induced damage thresholds (LIDT) of the sample were measured in 1-on-1 mode for laser with 1064 nm wavelength. The results indicate that the LIDT of the as-grown sample is only 3.96 J/cm², but it is increased to 8.98 J/cm² after annealing under temperature of 200 °C in atmosphere. By measuring the laser weak absorption and SIMS of the samples, we deduced that substoichiometer is the main reason for the low LIDT of the as-grown sample, and the experiment results were well explained with the theory of electronic-avalanche ionization.     

Structural and optical properties of nitrogen-incorporated HfO2 gate dielectrics deposited by reactive sputtering

High-k HfO_xN_y thin films with different nitrogen-incorporation content have been fabricated on Si (1 0 0) substrate by means of radio-frequency reactive sputtering method. Analyses from X-ray diffraction (XRD) and atomic force microscopic have indicated that the increase of the crystallization temperature of HfO₂ thin films and the decrease of the roughness root-mean-square value of HfO₂ thin films due to the incorporation of nitrogen. Based on a parameterized Tauc-Lorentz (TL) dispersion model, the optical properties of the HfO_xN_y thin films related to different nitrogen-incorporation content are systematically investigated by spectroscopic ellipsometer. Increase in the refractive index and the extinction coefficient and reduction in band gap with increase of nitrogen-incorporation content are discussed in detail.     

Characterization of the interface between the Hf-based high-k thin film and the Si using spatially resolved electron energy-loss spectroscopy

The interfacial structures of HfO₂ and HfAlO thin films on Si have been investigated using spatially resolved electron energy-loss spectroscopy. We have found that interfaces are not atomically sharp, and variation in the symmetry of the local atomic coordination lasts for a couple of monolayers for both the as-deposited HfO₂ and the HfAlO samples. Annealing of the HfO₂ film in the oxygen environment leads to the formation of a thick SiO₂/SiO_x stack layer in-between the original HfO₂ and the Si substrate. As a comparison, the interfacial stability is significantly improved by Al incorporation into the HfO₂ film (forming HfAlO), which effectively reduced/eliminated the interfacial silicon oxide formation during the oxygen annealing process. The mechanism of the high-k film/substrate stabilization by Al incorporation is discussed based on the experimental results.     

Mechanism for defect dependence of damage morphology in HfO2/SiO2 high reflectivity coating under nanosecond ultraviolet laser irradiation

High reflectivity coating is designed and fabricated with HfO₂/SiO₂ stacks. The laser-induced damage experiment is prepared by a third-order harmonic generation of Nd:YAG laser (355 nm, 8 ns). Typical damage micrographs are obtained using atomic force microscope (AFM) and scanning electron microscope (SEM). A theoretical model based on the thermal transfer is tried to describe the defect dependence of damage morphology. Three situations are considered in this model: single defect, couple defects and high absorption film. The calculated results show that the second situation agrees well with the experiment.     

Profile of the refractive index distribution over the depth of (HfO2)x(Al2O3)1 ? x films

Capabilities of the method of laser null ellipsometry for the study of optical parameters of thin films of multicomponent alloys are demonstrated. Films of alloys (HfO₂) _x (Al₂O₃)_{1 − x} on single-crystal silicon are obtained by the chemical vapor deposition with the use of the following volatile compounds: hafnium dipivaloylmethanate (IV) and aluminum acetylacetonate (III). The selection of initial sets for their optical parameters is justified. The selected model is shown to correspond to experimental data. In films deposited from the mixture of precursors, the refractive index increases from a substrate to a film surface. Due to the separation of sources, films described by a single-layer model were deposited. This fact is indicative of the homogeneous distribution of components over the film thickness.     

Phase transformations in films deposited by laser ablation of Hf in an oxygen Atmosphere

The structure of the hafnium dioxide films grown during pulsed laser sputtering of an Hf target in an oxygen atmosphere is examined, and the phase transformations that occur in them at annealing are studied by transmission electron microscopy and electron diffraction. Amorphous, tetragonal, orthorhombic, and monoclinic HfO₂ phases are detected in the films. The tetragonal modification of HfO₂ exhibits an epitaxy effect on a KCl(001) substrate. When the amorphous film is annealed in vacuum or air, it crystallizes to form the monoclinic modification of HfO₂. The action of an electron beam on the amorphous film in vacuum leads to the formation of the orthorhombic and monoclinic modifications of HfO₂. The transformation from the orthorhombic to the monoclinic modification of HfO₂ is accompanied by a phase size effect. At the final stage of crystallization, the monoclinic modification represented by HfO₂ dendrite crystals is the predominant structural constituent.     

Atomic layer deposition of nanolaminate oxide films on Si

Among the methods for depositing thin films, atomic layer deposition is unique for its capability of growing conformal thin films of compounds with a control of composition and thickness at the atomic level. The conformal growth of thin films can be of particular interest for covering nanostructures since it assures the homogeneous growth of the ALD film in all directions, independent of the position of the sample with respect to the incoming precursor flow. Here we describe the technique for growing the HfO₂/Al₂O₃ bilayer on Si substrate and our in situ approach for its investigation by means of synchrotron radiation photoemission. In particular, we study the interface interactions between the two oxides for various thickness compositions ranging from 0.4 to 2.7 nm. We find that the ALD of HfO₂ on Si induces the increase of the interfacial SiO₂ layer, and a change in the band bending of Si. On the contrary, the ALD of Al₂O₃ on HfO₂ shows negligible interaction between layers as the binding energies of Hf4f, Si2p, and O1s core level peaks and the valence band maximum of HfO₂ do not change and the interfacial SiO₂ does not increase.