Chemical vapor deposition (CVD)-synthesized zinc sulfide (ZnS) is a key material for high-performance infrared optical systems. However, the process is prone to Abnormal Cellular Growth defects, which compromise material uniformity and optical performance. This study systematically investigates the formation mechanism and suppression pathways of Abnormal Cellular Growth in CVD ZnS through multiscale experimental analysis and theoretical modeling. Experiments employed high-purity zinc and hydrogen sulfide reacting in a graphite deposition chamber to produce polycrystalline ZnS, followed by hot isostatic pressing (HIP) post-treatment. Results indicate that Abnormal Cellular Growth is primarily driven by interface instability, influenced by temperature gradients, solute segregation, and interfacial energy coupling. Temperature non-uniformity within the deposition chamber and high deposition rates exacerbate solute enrichment, inducing cellular structures. The study further proposes a three-tiered synergistic control strategy—“root-cause prevention, process regulation, and end-of-line treatment”—significantly suppressing defect generation by optimizing substrate conditions, purifying the gas phase environment, and adjusting process parameters and post-treatment. The resulting material exhibits over 70% transmittance in the visible-infrared spectrum with markedly enhanced reliability. This research provides a theoretical framework and practical process pathway for understanding and controlling anomalous CVD ZnS growth, holding significant value for advancing the fabrication of high-performance infrared materials.

相变存储器具有非挥发性、存储密度高、循环寿命长、元件尺寸小、功耗低、抗辐射干扰等诸多优点,被认为是最具潜力的下一代存储器.硫系化合物材料在电压驱动下,可在高阻态和低阻态之间可逆转换,这一特性使之作为相变存储和阈值开关材料广泛地应用于相变存储领域.本文简要介绍了硫系化合物材料特性及作为相变存储和阈值开关材料的工作原理,综述了近年来硫系化合物在相变存储和阈值开关领域的应用、材料研究进展,展望了硫系化合物材料在相变存储领域的研究和发展趋势.

硫化锌(ZnS)具有较高的红外透过率及良好的力学、热学和光学等综合性能,经热等静压透明化处理后得到的多光谱硫化锌(m-CVDZnS)透射范围更宽(0.3～13μm),满足复合制导的需求,是红外双波段飞行器观察窗口和头罩的关键材料.而m-CVDZnS多晶中的残余应力直接影响窗口和头罩的光学均匀性和光学成像质量.本工作在热等静压设备中对CVDZnS多晶样品进行原位退火,采用的保护气体Ar气达到热等静压高温恒温所需压力后,退火过程不再进行充压或泄压(带压退火).退火样品为多个尺寸约120 mm×165 mm×10.2 mm的m-CVDZnS多晶抛光样品,典型带压退火的优化工艺如下:高温退火条件采用990℃/150 MPa,结合600℃恒温和慢降温至室温退火.样品应力双折射测量结果表明,带压退火处理使残余应力明显减小,应力双折射平均值从12～13 nm/cm减少到3～5 nm/cm,降幅约100％;退火处理后应力分布均匀性明显提高.

In this paper, X-ray diffraction, selective area electron diffraction, and transmission electron microscope (TEM) were used to study the twins at different positions and textures in different direction in CVDZnS. It was found that the CVDZnS twin showed streaks under TEM. The narrower the streaks, the higher the content of twins, and the content of twins in CVDZnS normal layer was higher than that in bright layer. There are textures in CVDZnS, and the main texture of P surface (perpendicular to the direction of growth) is different from S surface (parallel to the growth direction of surface). The main texture in P is {010} 〈001〉, and the S is {101} 〈 $$\overline{1} \overline{3}$$ 1〉.

本文采用化学气相沉积法(CVD)制备出CVD-ZnS晶体,并通过一系列的测试和分析解释了CVD-ZnS异常大晶粒的再结晶机制.使用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、电子衍射对石墨基板底部的CVD-ZnS异常大晶粒与正常区域晶粒的微观形貌进行观察,结果发现在靠近石墨基板底部与沉积方向相同的CVD-ZnS晶粒尺寸要比该方向上正常区域的晶粒大,异常大晶粒区的晶粒尺寸为50～100μmn,晶界较宽,然而并没有表现出晶粒形态扩张伸长;其次在CVD-ZnS材料正常区域可以观测到明暗带,底部异常大晶粒区域则无此现象;另外在沉积温度为900～1000K条件下,立方相是稳定的相,由于反应物浓度分布不均匀会导致堆垛层错、孪晶界和位错堆积组成的层位畸变发生.能谱(EDS)测试分析表明,在垂直于沉积方向上距离基板底部～9 mm的正常晶粒与距离石墨基板底部～0.3 mm的异常大晶粒相比,元素组成一致,在化学计量配比上S/Zn略大于1.X射线衍射(XRD)表征分析得出异常大晶粒再结晶过程中主要是以立方相形式存在,有少量六方相,并且确定异常大晶粒再结晶的优先取向是s(111).

Using FLUENT software to simulate the gas flow pattern of CVDZnSe under different nozzle structures including annular single nozzle, four-hole single nozzle and porous multi nozzles, it was found that the gas flow pattern distribution of the annular single-nozzle is up sparse and down dense, and a significant back-flow phenomenon occurs at the gas inlet, whereas the gas flow pattern of the four-hole single-nozzle has better uniformity and the pattern of the porous multi-nozzle is up dense and down sparse. Moreover, neither single-nozzle with four holes nor porous multi-nozzle shows back-flow phenomenon at the inlet. The characteristics of ZnSe prepared by chemical vapor deposition(CVD)method under different nozzle structures are analyzed by EDS, indicating that the stoichiometric ratio of CVDZnSe prepared by using a four-hole single-nozzle is close to "1 '', with Zn/Se ratio of B-1# standing at 0.94 and the ratio of B-2# 0.93. In addition, the optical transmittance test of 6 samples shows that the Zn/Se ratio near "1 '' is more conducive to improving the optical transmission for 8-14 mu m. As a result, the four-hole single nozzle is more conducive to improving the uniformity of the gas flow pattern distribution and preparing CVDZnSe in a stoichiometric ratio.

CVDZnS was successfully prepared by chemical vapor deposition (CVD) and treated with hot isostatic pressure (HIP) and non-hot isostatic pressure (HIP). Both materials were characterized by X-ray diffraction, showing that CVDZnS is polycrystalline with a small amount of hexagonal crystal structure and HIPZnS is completely isotropic cubic structure. Besides, it also indicates that the preferred orientation of HIPZnS is sphalerite (111) for perpendicular or parallel to the growth direction. Surface morphology is performed by scanning electron microscopy and metalloscope and it is found that the S or P-orientation grain size after HIP treatment increased significantly. The average transverse and longitudinal grain size of HIPZnS in S-orientation is 55–60 μm, and the average transverse and longitudinal grain size in P-orientation is 40–45 μm. EDTA test showed the Zn/S ratio of CVDZnS is 0.9449 or 0.9511, and the Zn/S ratio of HIPZnS is 0.9899 or 0.9935, indicating that hot isostatic pressing is more likely to promote the secondary growth of ZnS toward stoichiometry. Optical properties of CVDZnS and HIPZnS were carried out by FTIR Spectrometer, showing that HIPZnS in S-orientation has an excellent optical performance at 2–13 μm compared to the P-orientation and an average transmittance of ≥ 72.5% at 2–10 μm.

ZnS-reinforced ZnS/ZnSe composites are prepared by chemical vapor deposition. Scanning electron microscope, transmittance, and bending strength are used to characterize the samples. The schematic diagram of the transmittance model of the double-layer composite window is used to calculate the theoretical transmittance, and the measured value of the transmittance of ZnS/ZnSe composite material is in good agreement with the calculated value. The effects of interface layer on the optical and mechanical properties of materials are studied in detail. It is found that the interface can affect the transmittance of the composites, but it still maintains a high transmittance, and the influence of interface layer on the transmittance of visible band is more serious than that of infrared band. Moreover, the mechanical properties of the new composite material are significantly improved (35%).

通过控制H2S流量(2±1)L/min、氩气流量(35±2)L/min,在不同沉积温度[(650±10)、670±10)、700±10)℃)]、不同沉积压力[(5000±200)、7000±200)、9000±200)Pa)]工艺条件下采用化学气相沉积法制备出原生ZnS(CVDZnS)样品.利用X射线衍射、金相显微镜、Spectrμm100 Fourier红外变换光谱仪对CVDZnS样品分别进行了物相分析、微观晶粒形貌观察以及2～15μm波段的红外透过率测试.结果表明:CVDZnS主要以立方相形式存在,有少量六方相,沉积生长的优先取向为s(111);金相分析表明在沉积压力为(5000±200)和(7000±200)Pa时,随着温度的升高平均晶粒尺寸有增大趋势,最大平均纵向晶粒尺寸值为15.5μm.平均纵向晶粒尺寸和平均横向晶粒尺寸的比值越接近"1",对于提高材料弯曲强度越有利.确定了在沉积温度为(670±10)℃、沉积压力为(7000±200)Pa工艺条件下,制备的CVDZnS可以有效提高2～5、7～10μm的平均透过率(～72.15％),降低6.0μm左右的吸收.

本文介绍了ZnSe晶体的制备方法及其重要应用背景,系统地总结了化学气相沉积法(CVD)制备ZnSe过程中产生的各类缺陷,包括云雾、孔洞和微裂纹、夹杂、分层和胞状物.采用SEM、体视显微镜、金相显微镜、傅里叶光谱仪等方法对缺陷进行了表征.结合国内外文献和检测结果,对各类缺陷可能的产生机理及抑制方法进行了阐述与分析.

In the chemical vapor deposited zinc sulfide, it often appears obvious light and dark growth bands along the growth direction, which will affect the homogeneity of optical properties of CVD ZnS and the efficiency of subsequent heat treatment. X-ray diffraction, Metallographic microscope and SEM were used to detect the crystal structure, grain size and microstructure, and the concentration of Zn and S in different bands was tested by EDTA titration, XRF, ICP and HF-combustion IR absorption spectrometric method. Results: Compared to the normal band, the grain size in the bright band was significantly larger, and the concentration of hexagonal phase in the bright band was lower, while the concentration ratio of Zn and S in the CVD ZnS did not have the regularity in the different bands. Combining with relevant knowledge about characteristics of the deposition process and crystal growth theory, the paper analyzes the formation mechanism of growth bands in CVD ZnS, and find that the main factor is the mutation of the concentration of the reactants in the deposition surface, affect the crystal nucleation rate and growth rate, eventually lead to the different grain morphologies, and even showing up the macroscopic growth bands. Compared with the actual process parameters, we have confirmed it and found out the main causes of mutation of the reactant concentration, this will have important guiding significance to the improvement of product quality in the future.

采用化学气相沉积法(CVD)制备大尺寸ZnS晶体(CVD-ZnS),利用扫描电子显微镜、透射电子显微镜、X射线衍射分析对CVD-ZnS内部的胞状结构进行表征,表明胞状生长现象能改变CVD-ZnS材料内部的晶粒生长方向、分布方式,但对材料内部的物相、元素分布并未造成显著影响;通过对胞状物密集区的光学均匀性检测,分别为2.71×10-5和2.85×10-5,均方根值分别为6.46×10-6和4.98×10-6,正常区域的样品光学均匀性为9.53×10-6,均方根值为1.51 ×10-6,表明胞状物的存在会降低CVD-ZnS材料的光学均匀性;采用三点弯曲法测试材料弯曲强度,四组弯曲强度数据表明CVD-ZnS正常区的弯曲强度明显高于CVD-ZnS胞状物密集区.

Abnormal large grains influencing highly the optical and electrical properties are commonly observed in the bottom part of CVD-ZnS layers. We have analyzed the films using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and infrared transmittance tests. Compared to normal grains, more homogeneous and simpler structures have been observed in abnormal large grains in CVD-ZnS. In addition to the obvious difference in sizes, the crystalline outline and interior structure of normal and abnormal large grains are found to be markedly different. Distorted structures and stacking faults, such as wurtzite phase and polytypes of ZnS, are not detected in the large grain areas. Preferred orientation of abnormal large grains is found to be sphalerite (1 1 1). These results could be explained as due to the recrystallization mechanism of abnormal large grains. Samples with large grains show lower infrared absorption band (at 6.2 mu m wavelength) compared to samples with normal size grains. However, the infrared transmittance is found to be lower for the samples with large grains. Microstructure patterns show the presence of plenty of microdefects in boundaries between large grains, which indicates that the recrystallization in the volume with large grains is not as perfect as the recrystallization in hot isostatic pressure process (HIP).

Chemical vapor-deposited zinc selenide samples were subjected to hot isostatic pressing (HIP) conditions in argon. X-ray diffraction, metalloscope, transmission spectra and so on were used to characterize the samples. The effects of HIP temperature (700 °C, 800 °C and 900 °C) and time (10 h, 20 h and 30 h) on the structure, microstructure and optical properties were studied. The results indicated that hot isostatic pressed (HIPed) ZnSe has recrystallized after HIP, the grain size increased significantly with the increase in HIP temperature, and the hot isostatic pressing eliminates the impurities in the material and makes the material evenly distributed. Both the samples HIPed at 900 °C for 10 h and HIPed at 800 °C for 30 h will result in the appearance of large grains; the samples HIPed at 800 °C for 20 h perform the best in transmission at same pressure (80 MPa).

介绍了化学气相沉积法(CVD)制备ZnS过程中,CVD工艺对材料相关力学性能的影响和控制方法.通过X射线衍射分析、扫描电镜和金相显微镜等手段研究了不同工艺下制备的ZnS样品材料的内部结构和缺陷,提出了ZnS生长过程中晶粒尺寸和材料缺陷的控制方法.研究结果表明,设计合理的喷嘴结构,营造稳定的CVD生长环境,提高CVD ZnS毛坯一致性,抑制材料缺陷形成,有助于提升ZnS材料力学相关性能.

A versatile template biomaterial was facilely obtained by ultraviolet (UV) photocrosslinking approach using protein molecules as building blocks. As-formed photocrosslinked protein hydrogel matrix (PPHM) was proved to be composed of covalently bound and dense packing protein molecules. Therefore, the PPHM was endowed with highly smooth topograghy with an average roughness of approximately 5 nm, and was self-supporting and flexible. The PPHM could be easily functionalized by doping Fe3O4 magnetic nanoparticles inside the protein hydrogel. Further, PPHM was experimentally demonstrated to be used as a applicable template for biomineralization.

Gold-silver (Au-Ag) alloy nanostructures were fabricated on substrate by the highly intense femtosecond laser pulses through a wet photochemical reduction without introducing additional reducing agent. The nanostructures can not only retain the characteristic of metallic materials, but also realize the assembling pattern of arbitrary subtle shape. The formation of Au-Ag alloy nanostructures was confirmed by energy dispersive X-ray (EDX) diffraction, indicating the fabricated nanostructures were different in the ratio of gold to silver for different molar ratios in the solution. The composite metal material was applied for catalysis of hydrogen peroxide and an ideal result was achieved.

Superparamagnetic and surface-modified Fe3O4 nanoparticles were synthesized via high-temperature hydrolysis method. With the Fe3O4 nanoparticles as seed, silica stick grows on one side of nanoparticle via a non-classic controlled nucleation and growth method, and Janus-magnetic-mesoporous nanoparticles were achieved. The length of silica nanostick in Janus nanoparticle can be controlled by the amount of added TEOS. But the length of silica nanostick in primary growth process is limited, a secondary growth is important to increase the length of silica nanostick. Due to the mesoporous characteristic of silica nanostick, a loading and releasing experiment was conducted, and a sustained-releasing process of doxorubicin was verified.

The goal of creation of large-area deep sub-wavelength nanostructures by femtosecond laser irradiation onto various materials is being hindered by the limited coherence length. Here, we report solution of the problem by light field tailoring of the incident beam with a phase mask, which serves generation of wavelets. Direct interference between the wavelets, here the first-order diffracted beams, and interference between a wavelet and its induced waves such as surface plasmon polariton are responsible for creation of microgratings and superimposed nanogratings, respectively. The principle of wavelets interference enables extension of uniformly induced hybrid structures containing deep sub-wavelength nanofeatures to macro-dimension.

A double-layer coatings structure on the surface of ms-ZnS substrate is designed and fabricated. The outer face of the ms-ZnS is coated with DLC/BP as high performance protective and antireflective coatings, and the inner face is coated with YbF3 and ZnS as high efficient antireflective coatings. The transmittance, nano-hardness and environmental durability of the coated ms-ZnS are measured by FTIR spectroscopy, nano-hardness tester and simulative harsh environmental test specified by MIL-48616, respectively. It shows that, in the waveband of 8–12 μm, the measured maximum transmittance is about 93.3% and the average transmittance is about 87.9%. After coated with DLC/BP, the nano-hardness of ms-ZnS samples increases from 2.5 to 19.5 GPa. The coated ms-ZnS passes the environmental tests, which indicates that it can meet the demands of (long-wave infrared) LWIR electro-optics systems working in harsh environment.