氧化钇薄膜反应溅射法生长、性能及红外光学应用研究

发布时间：2018-03-03 14:42

本文选题：氧化钇薄膜　切入点：反应溅射法　出处：《哈尔滨工业大学》2016年博士论文　论文类型：学位论文

【摘要】：随着航空航天技术跨入超高音速阶段,红外窗口和头罩元件经受着气动热/力等极端使役环境,使得窗口元件的增透保护显得尤为重要,因此研制与红外窗口匹配的红外增透保护材料尤为迫切。稀土氧化物是一类十分重要且复杂的氧化物族系,拥有着丰富的物理和化学性能,因此广泛地活跃于科技和工业界,引起了学者的广泛兴趣,开展了大量的探索性研究工作。稀土氧化物涵盖镧系氧化物,原子序数Z从57到71,以及钪(Z=21)和钇(Z=39)氧化物,这是由于它们具有相似的外层电子结构。稀土氧化物表现出一致的共性以及个体性(来源于内层4f轨道电子的差异)。基于氧化钇优异的高温稳定物性、抗失稳强度以及与红外材料匹配等优点,它已成为红外窗口和整流罩增透保护的优选薄膜材料,唤起了氧化钇薄膜材料的基础研究和红外应用研究的热潮。二维薄膜材料因其在厚度与其他方向存在巨大差异,所以呈现出不同于块体材料的奇异结构与物性。薄膜材料的性能由两种因素决定:一是材料自身属性;二是材料制备方法和工艺条件。反应磁控溅射法因其具有较高的沉积速率、优质的成膜质量、设备简单并易扩展等优点,成为薄膜生长与研究领域不可或缺的技术手段之一。本文选取物理气相沉积技术-反应磁控溅射法为手段,实现氧化钇薄膜的制备、表征及物化性能研究,最后开展了氧化钇红外增透保护薄膜应用研究。本论文可分为以下几个部分:首先,测试并获得金属钇靶显著的反应滞后回线,通过控制不同氩气分压和抽气速率来调控反应滞后回线。较之氩气压强,在500 l/s高抽气速率下消除了反应滞后回线,获得了金属-过渡-中毒三种稳定溅射模式。理论研究结果表明,高抽气速率可显著减缓靶表面氧化物的生成速率,消除了滞后现象。其次,基于直流磁控溅射法(DCMS),研究了溅射模式以及衬底不同区域对于薄膜生长的影响规律。结果表明,氧化钇薄膜的沉积速率依赖于靶表面不同的溅射模式以及其溅射产额。在金属溅射模式下薄膜的优先生长取向为立方(111)晶面,然而在靶中毒模式下,薄膜以立方(421)为择优晶面。在过渡模式下,出现了立方和单斜两相混合态。局域输氧法使得衬底中心区域为立方(111)优先生长晶面,边缘区域以单斜(40-2)晶面占主导。排除了等离子体不均匀性对薄膜晶相的影响并明确了低氧分压是产生单斜相的原因。利用射频磁控溅射法(RFMS),研究了氧气流量、温度和偏压对于薄膜的协同影响规律。与直流磁控溅射不同,射频磁控溅射的滞后现象并不明显。逐渐增加氧气分压使得薄膜晶体结构由立方(111)择优取向转变为非晶态。无论衬底温度如何,负偏压使得薄膜生长存在正常沉积区和刻蚀区。在氧气分压一定时,高温和低偏压有利于立方相的生长,低温和高偏压有利于单斜相的生长,这两种技术途径调控薄膜的缺陷产生和愈合过程。低氧分压和偏压使得薄膜面外方向O/Y/O周期排列缺失氧原子层而转变为O/Y周期性排列,导致了立方相向单斜相的转变,并伴随着结晶度的劣化。在金属模式下,薄膜为柱状晶,然而在中毒模式下柱状特征消失。柱状晶的生长不依赖于薄膜的晶相而是依赖于薄膜的结晶度。薄膜的表面粗糙度不仅依赖于溅射模式,还由偏压决定。在金属模式下薄膜具有较大粗糙度,然而中毒模式下薄膜表面平滑;在正常薄膜沉积区域,粗糙度具有较大值,然而,刻蚀区薄膜具有较小的粗糙度归因于氩离子的刻蚀作用。而后,研究了薄膜的光、力、电及润湿性能。光学性能与薄膜的结晶度和晶相紧密联系在一起。金属模式下,薄膜具有较高的折射率,中毒模式反之。温度对于折射率的增强作用表现于立方结晶度的提高,而偏压则为结晶度和立方-单斜相转化的双重增强作用。薄膜的致密度与与折射率有着相类似的规律,空隙率反之。金属模式下,薄膜具有较高的硬度、模量和弹塑比,中毒态劣化了力学性能。温度与偏压都可提高薄膜的力学性能。优异的力学性能来源于薄膜面外方向结晶度的提高,较少的缺陷滑移源强化了力学性能。薄膜表面的成分和微观结构是决定薄膜表面润湿性的两种因素。对于物理气相沉积法制备的薄膜而言,蒸馏水和乙二醇的接触角与粗糙度关系不大,而与表面成分相关。缺氧态表面的润湿性较小,这是因为缺氧态的表面更容易与(OH)相连。温度和负偏压的升高对于薄膜介电常数提高具有积极作用,与负偏压相比温度增加的幅度更大,这是由于立方相与单斜相相比具有较小的缺陷。最后,侧重于研究氧化钇薄膜红外窗口的增透/保护性能。理论和实验结果表明硫化锌双面镀氧化钇薄膜的透过率高达93%。XPS剖面结果显示偏压有助于减小界面吸附氧比例从而强化了界面结合。具有低发射率的氧化钇薄膜可有效抑制高温下硫化锌和蓝宝石窗口的发射率。
[Abstract]:Along with the development of aerospace technology in hypersonic phase, infrared windows and domes with pneumatic elements subjected to extreme heat / force causative environment, makes the window element antireflection and protection is particularly important, therefore, with the development of Infrared Antireflective and protective materials of the infrared window is particularly urgent. Rare earth oxide is a kind of very important and complex the oxide family, has a wealth of physical and chemical properties, it is widely active in science and technology and the industry, attracted the interest of scholars, carried out a lot of research work. The rare earth oxide covering Lanthanide Oxides, atomic number Z from 57 to 71, as well as scandium and yttrium (Z=21) (Z=39) oxide, this is because they have similar structure. The outer electrons of rare earth oxides showed consistent commonness and individuality (difference comes from the inner 4f orbit electrons). High temperature stability of yttrium oxide based on excellent The anti buckling strength, and matching and infrared material advantages, it has become the preferred film material in infrared window and dome antireflection and protection, arouse research foundation of yttrium oxide thin film materials and infrared application research upsurge. The two-dimensional film materials because of its to differ in thickness and the other side, so showing a singular the structure and property is different from bulk materials. Material properties are determined by two factors: one is the material itself; two is the method and condition of material preparation. Reactive magnetron sputtering deposition rate due to its high film quality, high quality, simple equipment and has the advantages of easy to expand, become one of the essential technical means of thin film growth and research. This paper selects physical vapor deposition technology - reactive magnetron sputtering method, the yttrium oxide thin film preparation, characterization and physicochemical properties of the research, finally The application of yttrium oxide Infrared Antireflective and protective film. This thesis can be divided into the following parts: first, test and get the obvious reaction of yttrium metal target hysteresis loop, by controlling different argon partial pressure and pumping speed to control the reaction hysteresis loop. Compared with argon pressure, high pumping rate at 500 l/s eliminating the response hysteresis, the transition metal poisoning - three stable sputtering mode. The theoretical results show that the formation rate of high pumping rate can significantly reduce the oxide of the target surface, eliminate the hysteresis phenomenon. Secondly, DC magnetron sputtering (DCMS), based on the study of sputtering mode and substrate for different regions influence of film growth. The results show that the deposition rate of yttrium oxide thin film depends on the sputtering target surface and different amount of sputtering. The film on the metal sputtering mode and to take long for Mr. Li Square (111) surface, but in the target poisoning mode, film in cubic (421) preferred plane. In transition mode, the cubic and monoclinic phase mixed state. Local oxygen method makes the substrate center cubic (111) preferred crystal surface, edge region (40-2) single crystal the surface is dominant. Exclusion of plasma inhomogeneities on the film phase and the influence of oxygen partial pressure is generated. The reason of monoclinic phase by RF magnetron sputtering (RFMS), the oxygen flow rate, temperature and bias for the synergistic effect of the films. Unlike DC magnetron sputtering, hysteresis of RF magnetron sputtering is not obvious. Gradually increase the oxygen partial pressure makes the film crystal structure from cubic (111) preferred orientation into amorphous state. No matter how the negative bias of substrate temperature, which makes the film growth of normal sedimentary zone and etching area. The partial pressure of oxygen in a high. Mild low bias in favor of the growth of the cubic phase, low temperature and high bias in favor of monoclinic phase growth process generated defects of the two approaches to control of the film and healing. Low oxygen partial pressure and bias makes the film plane direction O/Y/O periodic lack of oxygen atoms into O/Y layer and periodic arrangement, LED to the cubic monoclinic phase transition, accompanied by the deterioration of crystallinity. The metal pattern, film is columnar crystal, however in the poisoning mode columnar features disappear. The growth of columnar crystal depends on the crystal but depends on the crystallinity of the films. The surface roughness of the thin film not only rely on in sputtering mode, but also by the bias in mode decision. The metal film has large surface roughness, but smooth film poisoning in normal mode; thin film deposition area, surface roughness has great value, however, the rough etching films with smaller area The role of etching due to argon ion. Then, on the film's light, power, electrical and optical properties and wettability. The crystallization degree and the film closely together. The metal model, refraction film has higher rate of poisoning model and vice versa. Temperature on refractive index enhancement in cubic crystal the improvement of the degree of bias, and for the enhancement of the crystallinity and the double cubic monoclinic phase transformation. The film density is similar with the law and the refractive index, void ratio and vice versa. The metal mode, the film has high hardness, elastic modulus and ratio of toxic state degradation mechanical properties of temperature. With the bias voltage can improve the mechanical properties of the films. The source of excellent mechanical properties to improve the crystallinity of thin film plane direction, strengthen the source slip defect less mechanical properties. The film surface composition and microstructure of film surface is determined Two factors of wettability. For physical vapor deposition of thin films is concerned, little distilled water and glycol contact angle and roughness, and correlated with surface composition. Anoxic surface wettability is small, this is because the surface of anoxic (OH) more easily with increasing temperature and connected. Negative bias for thin film dielectric constant improvement has a positive effect, compared with the negative bias temperature increases, this is due to the cubic and monoclinic phases compared with smaller defects. Finally, focuses on the study of Yttrium Oxide Thin Film Infrared Antireflection window / protection performance. Theoretical and experimental results show that yttrium oxide thin film of zinc sulfide through the double plating rate is as high as 93%.XPS profile showed that bias is helpful in reducing the adsorption oxygen ratio which enhanced the interfacial bonding with yttrium oxide thin film with low emissivity can effectively suppress the high temperature of zinc sulfide and blue The emissivity of the gem window.

【学位授予单位】：哈尔滨工业大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TB383.2

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