红外高折射率材料碲锗铅的生长、性能及应用研究
发布时间：2018-07-16 14:54
【摘要】：为了满足数值天气预报的需要,用于大气的温度、湿度及成分遥感探测的大气垂直探测仪采用红外窄带滤光片将红外光谱通道精确分开,以准确提取各光谱通道的光学信息。由于红外窄带滤光片的设计制造是建立在合适的选取膜层材料的基础上,并且采用高折射率薄膜材料将能有效减少膜层的数量、降低产品设计和制造难度、提高产品在恶劣环境中的可靠性,对于红外高折射率材料的研究具有十分重要的意义。碲化铅(PbTe)是目前可供实际使用的折射率最高的红外材料。虽然多年来我们独特的碲化铅材料已应用于红外带通滤光片的设计和制造中,并在空间遥感任务中发挥了重要作用,然而由于其内禀性质造成机械强度较低,使由其构成的滤光片划片和切割过程中出现“崩边”。本项研究的主要目的和内容之一是研究碲化铅与另一种IV-VI族窄禁带半导体材料碲化锗所形成的赝二元合金固溶体——碲锗铅薄膜的力学性能,希望通过“固溶强化”来提高红外带通滤光片高折射率镀膜材料的机械强度。碲锗铅作为红外高折射率材料应用于红外带通滤光片的基础是生长出性能优异的材料。由于碲锗铅材料是一种具有铁电相变特性的赝二元合金固溶体,其中锗组分x值的决定着材料的物理性能。因此,如何控制由于溶质分凝问题而产生的组分分布不均匀性也是本项研究的主要内容之一。目前,红外带通滤光片的制造都是采用热蒸发技术。因此,将碲锗铅材料应用于红外带通滤光片的生产实际中,首先要研究蒸发碲锗铅体材料后沉积在基片上的薄膜组分与源材料组分之间的差异,薄膜组分的变化规律,以及薄膜晶体结构的特点,这也是本项研究主要内容之一。碲锗铅薄膜的基本吸收边随碲化锗含量的增加而移向短波。利用这种基本吸收边可调性和碲锗铅特有的高折射优势,将可以部分取代目前所使用的中波红外高折射率锗材料,以减少带通滤光片的膜层数量。探讨碲锗铅薄膜在中波红外的性能,以及作为高折射率材料取代锗的可能性,也是本项研究主要内容之一。在本项研究中取得了如下成果:1.通过对Bridgman法晶体生长过程中成分分凝与偏析及其控制原理的研究,对碲锗铅材料的生长过程进行了数值模拟分析,优化设计了材料生长工艺参数,实现了控制材料组分分布均匀性的目标。在此基础上生长出两种能够满足红外带通滤光片生产需要的碲锗铅材料。其中长波红外碲锗铅材料利用其优于碲化铅的力学性能,以解决工程应用中滤光片产品“崩边”的问题;中波红外碲锗铅材料利用其高于锗的折射率值,以及碲化铅薄膜基本吸收边的可调性,以期部分取代目前所使用的中波红外高折射率锗材料,减少所需的膜层数和入射角变化对滤光片产品光谱性能的影响。2.研究发现相比碲化铅薄膜,碲锗铅薄膜的硬度可提高5倍之多,杨氏模量可提高2倍之多,薄膜与锗基片的附着力可提高3倍之多,并且碲锗铅薄膜硬度与晶粒尺寸之间的关系遵循Hall-Petch方程。此外,从固溶强化的原理、碲锗铅材料铁电相变的基本原理、以及强局域化弹性应变场与位错迁移率之间的关系解释了室温下碲锗铅薄膜硬度和杨氏模量、薄膜与锗基片的附着力随源材料中锗浓度的变化机理。3.碲化铅和碲化锗的蒸汽压差值造成了热蒸发沉积的碲锗铅薄膜与源材料之间的组分不一致性。研究发现这种不一致性也与基片温度有关,在合适的基片温度,采用电子束蒸发碲锗铅材料沉积的薄膜与源材料之间的组分接近一致。这种一致性可以解释为碲化铅基半导体材料的低热导率特性引起电子束蒸发的“烧蚀”特性。研究还发现,随着锗浓度的增大,薄膜中碲浓度呈现出逐渐减少的趋势,薄膜的富碲特征转变为缺碲特征。这种组分相关性可以归因于锗离子半径小于铅离子半径,Ge-Te的键能弱于Pb-Te的键能,以及替代铅离子的锗离子偏离晶胞中心造成其与邻近碲离子的距离不同。此外,研究也发现在室温下具有菱形结构铁电相的碲锗铅薄膜中出现了碲化锗和碲的高压相,呈现出高压多相性。其可以通过诱发碲锗铅铁电相变的锗替代离子从无序分布到有序分布的转变得到解释。4.研究发现,在基片温度150°C时,蒸发锗组分x为0.18的碲锗铅材料可以获得在中波红外大气窗口(3~5μm)同时具有最大折射率值n和最小消光系数k的碲锗铅薄膜。为了探讨碲锗铅作为高折射率材料取代锗的可能性,使用其作为高折射率材料设计制作了一个中心波长为4μm的全介质Fabry-Perot滤光片。相比使用锗作为高折射率材料的滤光片,其具有更为优异的带宽性能和截止深度。
[Abstract]:In order to meet the needs of the numerical weather forecast, the atmospheric vertical detector used for remote sensing detection of atmospheric temperature, humidity and composition uses infrared narrow band filter to accurately separate the infrared spectral channels to accurately extract the optical information of the spectral channels. The design and manufacture of the infrared narrow band filter is based on the suitable selection of the film layer. On the basis of the material, the high refractive index thin film material will be able to reduce the number of the film effectively, reduce the difficulty of the product design and manufacture, and improve the reliability of the product in the bad environment. It is of great significance for the study of the infrared high refractive index material. Lead telluride (PbTe) is the highest refractive index of the infrared. Material. Although our unique lead telluride material has been applied to the design and manufacture of infrared bandpass filter for many years, it plays an important role in the space remote sensing task. However, because of its intrinsic nature, the mechanical strength is low, the "edge" in the process of cutting and cutting of the filters made up of it is the main part of this study. The purpose and content is to study the mechanical properties of the pseudo two element alloy solid solution - tellurium lead thin film formed by the other IV-VI group of narrow band gap semiconductors germanium telluride. It is hoped that the mechanical strength of the high refractive index coating material of the infrared band pass filter can be improved by "solid solution strengthening". The material applied to the infrared band pass filter is based on the material with excellent performance. As tellurium and germanium lead is a pseudo two element solid solution with ferroelectric phase change characteristics. The x value of germanium component determines the physical properties of the material. Therefore, how to control the heterogeneity of the component distribution due to the solute segregation problem is also the same One of the main contents of this study is that the infrared bandpass filter is made by thermal evaporation technology. Therefore, the application of tellurium and germanium lead material in the production of infrared bandpass filter is to study the difference between the film composition and the source and material components of the evaporated tellurium and germanium lead material and the composition of the film. The basic absorption edge of tellurium and germanium lead is moved to the short wave with the increase of germanium telluride content. Using this basic absorption edge tunability and the high refraction advantage of tellurium and germanium lead, the high refractive index of the medium wave infrared can be separated from the present use. Germanium materials are used to reduce the number of layers of bandpass filters. It is also one of the main contents of this study to investigate the performance of tellurium and germanium lead film in the medium wave infrared and the possibility of replacing germanium as a high refractive index material. In this study, the following results have been obtained: 1. through the segregation and segregation of components in the process of Bridgman crystal growth and its control, The growth process of tellurium and germanium lead material is numerically simulated and analyzed. The process parameters of material growth are optimized and the objective of controlling the distribution uniformity of material components is realized. On this basis, two kinds of tellurium and germanium lead materials which can meet the needs of the production of infrared band pass filter are grown. It is better than the mechanical properties of lead telluride to solve the problem of the "edge collapse" of the filter product in the engineering application, and the medium wave infrared tellurium and germanium lead materials use the refractive index value of the germanium and the tunability of the basic absorption edge of the lead telluride film, in order to partially replace the present medium wave infrared high refractive index germanium material and reduce the required film. The influence of the number and incidence angle on the spectral properties of the filter.2. found that the hardness of the tellurium film can be increased by 5 times more, the young's modulus can be increased by more than 2 times, the adhesion of the film to the germanium substrate can be increased by more than 3 times, and the relationship between the hardness of tellurium and germanium lead film and the grain size follows the Hall-Petch. In addition, from the principle of solid solution strengthening, the basic principle of ferroelectric phase transition of tellurium and germanium lead, the relationship between strong localized elastic strain field and dislocation migration rate explain the hardness and Young's modulus of tellurium, germanium and lead film at room temperature, the adhesion of the film and germanium substrate with the change mechanism of germanium concentration in the source materials.3. lead telluride and germanium telluride The difference between the vapor pressure difference and the composition of the tellurium and germanium lead film deposited by thermal evaporation is not consistent with the source material. It is found that this inconsistency is also related to the substrate temperature. At the appropriate substrate temperature, the composition of the films deposited by the electron beam evaporation tellurium lead material is close to that of the source material. This consistency can be explained as the consistency. The low thermal conductivity of lead telluride based semiconductor material causes the "ablation" characteristic of the electron beam evaporation. It is also found that the tellurium concentration in the thin films decreases gradually with the increase of germanium concentration, and the tellurium rich characteristics of the thin films are changed to tellurium deficiency. This component correlation can be attributed to the radius of the germanium ion less than the lead ion radius, Ge The bond energy of -Te is weaker than the bond energy of Pb-Te, and the germanium ions that replace the lead ions deviate from the cell center to cause their distance from the adjacent tellurium ions. In addition, the high pressure phase of germanium telluride and tellurium appeared in the tellurium tellurium lead film with rhombic structure at room temperature. The transition from disordered distribution to ordered distribution of germanium substitutional ions from lead-iron phase transition is explained by.4. study. It is found that, when the substrate temperature is 150 C, the tellurium, germanium, lead material, which has x of X of 0.18, can obtain the tellurium and germanium lead film with the maximum refractive index n and the minimum extinction coefficient K in the medium wave infrared atmosphere window (3~5 mu m). As the possibility of replacing germanium with high refractive index material, tellurium and germanium lead is used as a high refractive index material to design and produce a full medium Fabry-Perot filter with a central wavelength of 4 m. Compared with the filter with high refractive index material with germanium, it has more excellent bandwidth performance and cut-off depth.
【学位授予单位】：中国科学院研究生院(上海技术物理研究所)
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TN304.24;TB383.2
本文编号：2126736
[Abstract]:In order to meet the needs of the numerical weather forecast, the atmospheric vertical detector used for remote sensing detection of atmospheric temperature, humidity and composition uses infrared narrow band filter to accurately separate the infrared spectral channels to accurately extract the optical information of the spectral channels. The design and manufacture of the infrared narrow band filter is based on the suitable selection of the film layer. On the basis of the material, the high refractive index thin film material will be able to reduce the number of the film effectively, reduce the difficulty of the product design and manufacture, and improve the reliability of the product in the bad environment. It is of great significance for the study of the infrared high refractive index material. Lead telluride (PbTe) is the highest refractive index of the infrared. Material. Although our unique lead telluride material has been applied to the design and manufacture of infrared bandpass filter for many years, it plays an important role in the space remote sensing task. However, because of its intrinsic nature, the mechanical strength is low, the "edge" in the process of cutting and cutting of the filters made up of it is the main part of this study. The purpose and content is to study the mechanical properties of the pseudo two element alloy solid solution - tellurium lead thin film formed by the other IV-VI group of narrow band gap semiconductors germanium telluride. It is hoped that the mechanical strength of the high refractive index coating material of the infrared band pass filter can be improved by "solid solution strengthening". The material applied to the infrared band pass filter is based on the material with excellent performance. As tellurium and germanium lead is a pseudo two element solid solution with ferroelectric phase change characteristics. The x value of germanium component determines the physical properties of the material. Therefore, how to control the heterogeneity of the component distribution due to the solute segregation problem is also the same One of the main contents of this study is that the infrared bandpass filter is made by thermal evaporation technology. Therefore, the application of tellurium and germanium lead material in the production of infrared bandpass filter is to study the difference between the film composition and the source and material components of the evaporated tellurium and germanium lead material and the composition of the film. The basic absorption edge of tellurium and germanium lead is moved to the short wave with the increase of germanium telluride content. Using this basic absorption edge tunability and the high refraction advantage of tellurium and germanium lead, the high refractive index of the medium wave infrared can be separated from the present use. Germanium materials are used to reduce the number of layers of bandpass filters. It is also one of the main contents of this study to investigate the performance of tellurium and germanium lead film in the medium wave infrared and the possibility of replacing germanium as a high refractive index material. In this study, the following results have been obtained: 1. through the segregation and segregation of components in the process of Bridgman crystal growth and its control, The growth process of tellurium and germanium lead material is numerically simulated and analyzed. The process parameters of material growth are optimized and the objective of controlling the distribution uniformity of material components is realized. On this basis, two kinds of tellurium and germanium lead materials which can meet the needs of the production of infrared band pass filter are grown. It is better than the mechanical properties of lead telluride to solve the problem of the "edge collapse" of the filter product in the engineering application, and the medium wave infrared tellurium and germanium lead materials use the refractive index value of the germanium and the tunability of the basic absorption edge of the lead telluride film, in order to partially replace the present medium wave infrared high refractive index germanium material and reduce the required film. The influence of the number and incidence angle on the spectral properties of the filter.2. found that the hardness of the tellurium film can be increased by 5 times more, the young's modulus can be increased by more than 2 times, the adhesion of the film to the germanium substrate can be increased by more than 3 times, and the relationship between the hardness of tellurium and germanium lead film and the grain size follows the Hall-Petch. In addition, from the principle of solid solution strengthening, the basic principle of ferroelectric phase transition of tellurium and germanium lead, the relationship between strong localized elastic strain field and dislocation migration rate explain the hardness and Young's modulus of tellurium, germanium and lead film at room temperature, the adhesion of the film and germanium substrate with the change mechanism of germanium concentration in the source materials.3. lead telluride and germanium telluride The difference between the vapor pressure difference and the composition of the tellurium and germanium lead film deposited by thermal evaporation is not consistent with the source material. It is found that this inconsistency is also related to the substrate temperature. At the appropriate substrate temperature, the composition of the films deposited by the electron beam evaporation tellurium lead material is close to that of the source material. This consistency can be explained as the consistency. The low thermal conductivity of lead telluride based semiconductor material causes the "ablation" characteristic of the electron beam evaporation. It is also found that the tellurium concentration in the thin films decreases gradually with the increase of germanium concentration, and the tellurium rich characteristics of the thin films are changed to tellurium deficiency. This component correlation can be attributed to the radius of the germanium ion less than the lead ion radius, Ge The bond energy of -Te is weaker than the bond energy of Pb-Te, and the germanium ions that replace the lead ions deviate from the cell center to cause their distance from the adjacent tellurium ions. In addition, the high pressure phase of germanium telluride and tellurium appeared in the tellurium tellurium lead film with rhombic structure at room temperature. The transition from disordered distribution to ordered distribution of germanium substitutional ions from lead-iron phase transition is explained by.4. study. It is found that, when the substrate temperature is 150 C, the tellurium, germanium, lead material, which has x of X of 0.18, can obtain the tellurium and germanium lead film with the maximum refractive index n and the minimum extinction coefficient K in the medium wave infrared atmosphere window (3~5 mu m). As the possibility of replacing germanium with high refractive index material, tellurium and germanium lead is used as a high refractive index material to design and produce a full medium Fabry-Perot filter with a central wavelength of 4 m. Compared with the filter with high refractive index material with germanium, it has more excellent bandwidth performance and cut-off depth.
【学位授予单位】：中国科学院研究生院(上海技术物理研究所)
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TN304.24;TB383.2
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1 谢平;红外高折射率材料碲锗铅的生长、性能及应用研究[D];中国科学院研究生院(上海技术物理研究所);2016年
，本文编号：2126736
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