化学气相沉积ZnS、ZnSe研究进展

化学气相沉积(CVD)ZnS、ZnSe具有较高的红外透过率及良好的光学、力学性能，是红外军用探测系统首选的红外光学材料。大尺寸、高均匀性ZnS、ZnSe材料的制备是未来研究的重要课题。本文介绍了CVD的原理及在沉积过程中存在的主要问题，阐述了高性能红外材料必备的光学性能，综述和分析了CVD ZnS、CVD ZnSe的研究进展，以及这两种材料主要缺陷形成机理与工艺控制研究。旨在改进生产工艺参数，为批量化制备高性能ZnS、ZnSe材料提供理论参考，以满足其在军事领域上的应用。     

ZnSe单晶生长及性能研究

采用物理气相输运法对ZnSe(4N)多晶原料在850℃±10℃进行提纯,再用高压坩埚下降法在1530℃、氩气保护气氛下生长出高质量ZnSe单晶体.研究了提纯过程温度的选择以及氧含量和压力对于晶体生长的影响.对生长出的单晶体进行均匀性测试表明ZnSe单晶完整性和均匀性良好.对ZnSe单晶进行光学性能测试分析表明ZnSe单晶的折射率高,吸收系数低,红外透过率大于70;.     

CVT一步生长的ZnSe单晶的光电特性研究

本文采用化学气相输运(CVT)法,由Zn(5N)和Se(5N)一步直接生长了片状ZnSe单晶,并对其结构特性和光电性能进行分析。研究表明,生长出的ZnSe单晶仅显露(111)面,红外透过率约为40%～42%,具有较高的结晶质量。该ZnSe单晶可与In电极形成良好的欧姆接触,其体电阻率约为7.3×109Ω.cm。     

ZnSe和Cr∶ ZnSe单晶的温梯法制备及光学性能研究

采用温度梯度法(TGT)生长了直径为32 mm大尺寸ZnSe晶体.对生长出的ZnSe单晶进行了光学性能分析.采用磁控溅射方法在ZnSe晶体上镀铬膜,通过热扩散方法成功制备出中红外Cr∶ ZnSe激光晶体,并研究了Cr∶ZnSe晶体的光谱性能.吸收光谱测试观察到了Cr2+(3d4)取代四面体配位Zn2的5T2→5E能级的跃迁在1800nm的吸收带.77 K低温的光致发光光谱表明Cr∶ ZnSe晶体具有中心波长位于2.2 μm的宽谱带发射特征.     

单源真空蒸发法制备ZnSe薄膜的实验研究

本文采用单源真空蒸发法制备了ZnSe薄膜,利用电子探针、X射线粉晶衍射等现代测试手段研究了蒸发温度(700～1050 ℃)、基片温度(0～200 ℃)、基片材料(单晶硅、玻璃)以及热处理温度(300～400 ℃)等因素的改变对ZnSe薄膜的成份和结构的影响规律,建立了单源真空蒸发沉积ZnSe薄膜及热处理的实验方法.     

过渡金属离子掺杂Ⅱ-Ⅵ族中红外激光陶瓷研究进展

2~5 μm中红外激光在民用和军事领域的应用十分广泛。直接泵浦中红外激光增益介质材料是产生中红外激光的主要方式之一,二价过渡金属离子Cr²⁺或Fe²⁺掺杂的ZnS或ZnSe (TM²⁺∶Ⅱ-Ⅵ)材料以其独特的光谱特性成为目前最具发展前景的中红外激光增益材料之一。本文首先归纳了TM²⁺∶Ⅱ-Ⅵ材料的主要制备技术路线,然后重点介绍了采用激光陶瓷技术制备TM²⁺∶Ⅱ-Ⅵ材料的研究进展,最后对TM²⁺∶Ⅱ-Ⅵ陶瓷的原料制备与烧结技术的优化进行了展望。希望以此促进TM²⁺∶Ⅱ-Ⅵ激光陶瓷材料的发展,为获得高性能的TM²⁺∶Ⅱ-Ⅵ中红外激光器奠定关键材料基础。     

红外窗口和整流罩材料研究现状与发展趋势

介绍红外窗口的三个综合性能评价因子:热破裂品质因子、光畸变品质因子、抗热冲击品质因子;并用它们评价了氟化镁、尖晶石、氮氧化铝、蓝宝石、硫化锌和硒化锌、金刚石等主要的红外窗口和整流罩材料;综述其国内外的研究现状,并对其未来的发展趋势发表了自己的观点.     

中红外激光陶瓷的研究进展与展望

波段为2～5tμm的中红外激光在国防、医疗、通信等方面有着特殊的重要应用,而直接产生中红外激光的增益介质主要包括气体激光介质、半导体、稀土离子或者过渡金属离子掺杂的化合物.本文首先介绍应用于中红外波段的发光离子(包括Tm3,Ho3+,Er3+等稀土离子和Cr2+,Fe2等过渡金属离子)光谱特性,然后重点介绍氧化物(包括石榴石和倍半氧化物)和Ⅱ-Ⅵ族化合物(主要是ZnS/ZnSe)两大类中红外激光陶瓷材料的制备与激光性能.最后,对这两大类中红外激光陶瓷中存在的问题进行了分析,并对其发展方向进行了展望.     

单质直接气相生长ZnSe单晶

本文直接以高纯Zn、Se单质为原料,加入少量碘单质作为反应输运剂,用化学气相输运(CVT)的方法一步成功的生长出了ZnSe单晶.采用XRD、EDS、紫外可见分光光度计和光致发光(PL)技术研究了生长的ZnSe晶体的结构、成份以及光学特性.结果表明,生长的ZnSe单晶具有较好结晶性能,成份接近理想的化学计量比,在500～2000nm范围内透过率达到65;～70;,在1.9～2.5 eV范围内存在与Zn空位和杂质能级相关的发光带.由Zn和Se单质在输运剂I2的辅助下一步直接生长ZnSe单晶是可行的.     

微乳液法制备不同形貌低维硒化锌纳米晶

利用微乳液法,实现了多晶硒化锌纳米空心球、单晶硒化锌纳米棒以及ZnSe量子点的低温合成.通过调整Triton X-100/环己烷/水体系中表面活性剂Triton X-100的浓度分别制备出直径在120 nm左右,壁厚在6nm左右的ZnSe多晶纳米空心球体、长度达1μm的单晶纳米棒和直径位于4～6nm的ZnSe量子点.紫外可见吸收光谱显示不同形貌ZnSe纳米结构的吸收特征具有较大的差别.     

MOVPE Growth of Wide Band-Gap II—VI Compounds for Near-UV and Deep-Blue Light Emitting Devices

We report on the growth by metalorganic vapour phase epitaxy of high structural and optical quality ZnS, ZnSe and ZnS/ZnSe multiple quantum well (MQW) based heterostructures for applications to laser diodes operating in the 400 nm spectral region. High purity ^tBuSH, ^tBu₂Se and the adduct Me₂Zn:Et₃N were used as precursors of S, Se and Zn, respectively. The effect of the different MOVPE growth parameters on the growth rates and structural properties of the epilayers is reported, showing that the crystallinity of both ZnS and ZnSe is limited by the kinetics of the incorporation of Zn, S and Se species at the growing surface. Very good structural and optical quality ZnS and ZnSe epilayers are obtained under optimized growth conditions, for which also dominant (excitonic) band-edge emissions are reported. The excellent ZnS and ZnSe obtained by our MOVPE growth matches the stringent requirements needed to achieve high quality ZnS/ZnSe MQWs. Their structural properties under optimized MOVPE conditions are shown to be limited mostly by the formation of microtwins, a result of the intrinsic high lattice mismatch involved into the ZnS/ZnSe heterostructure. Despite the large amount of defects found, the optical quality of the MQWs turned out to be high, which made possible the full characterization of their electronic and lasing properties. In particular, photopumped lasing emission up to 50 K in the 3.0 eV energy region are reported for the present MQWs heterostructures under power excitation density above 100 kW/cm².     

Wide bandgap II–VI compounds grown by MOMBE

Recent developments of MOMBE for wide bandgap II–VI compounds are reviewed by considering both film properties and a novel growth technique such as atomic layer epitaxy (ALE). MOMBE using dimethylzinc and hydrogen has enabled growth of p-type ZnSe doped with nitrogen by using ammonia as a dopant source. Ideal ALE was obtained for ZnSe by using various gas source conditions. Furthermore, applications of MOMBE of II–VI compounds to the growth of strained layer superlattices are also reviewed.     

Metalorganic chemical vapor epitaxy and doping of ZnMgSSe heterostructures for blue emitting devices

Blue-green semiconductor laser diodes operating at room temperature are still the domain of wide bandgap II–VI compound semiconductors. CW operation at room temperature and hours of lifetime were reported. However, the conductivity control, defect generation and the ohmic contacts still need improvement. Therefore we focused our work on the MOVPE growth and the optimization of ZnMgSSe/ZnSSe/ZnSe heterostructures as well as on nitrogen doping of ZnSe. To verify the layer quality characterization was carried out by X-ray diffraction, electron probe microanalysis, electrical measurements and photoluminescence. ZnMgSSe/ZnSSe/ZnSe and ZnSSe/ZnSe quantum wells and superlattices were grown to investigate structural as well as interface properties. Electron beam and optical pumping was used to clarify the laser mechanism and to clarify the suitability of a MOVPE process to grow laser quality material. The electrical compensation of ZnSe doped with nitrogen is still controversially discussed whereas high n-type doping with chlorine was reproducible achieved. ZnSe: N doped at different growth conditions (II/VI ratio, growth temperature, nitrogen supply) using N₂ excited in a plasma source or by the use of nitrogen containing precursors was investigated to study the compensation mechanisms.     

热等静压处理对CVD ZnS/ZnSe复合材料性质的影响

对利用化学气相沉积(CVD)制备的ZnS/ZnSe复合材料进行了显微结构和光学性质的测试和分析.研究表明,热等静压过程使得CVD ZnS/ZnSe晶体内部晶粒尺寸明显增大,减少或消除了内部缺陷,提高了材料的光学透过率.     

ZnSe薄膜的化学反应辅助热壁外延法生长及特性研究

本文通过将新型化学气相反应促进剂Zn(NH4)3Cl5引入到热壁外延系统中,以二元素单质Zn和Se为原料,直接在Si(111)衬底上生长了高质量的ZnSe晶体薄膜,薄膜成分接近理想化学计量比。研究了主要工艺参数对薄膜生长形貌和性能的影响。采用SEM、AFM、EDS和PL谱技术研究了生长的ZnSe薄膜的形貌、成分和发光特性。研究结果表明,热壁温度和生长时间是影响ZnSe薄膜形貌的主要因素;气相反应促进剂在薄膜生长和调节成分方面扮演了关键角色,Zn(NH4)3Cl5的存在使得Zn(g)和Se2(g)合成ZnSe晶体的反应转变为气固非一致反应,从而更容易获得近乎理想化学计量比的ZnSe薄膜。ZnSe薄膜在氦镉激光激发下,室温下PL谱由近带边发射和(VZn-ClSe)组合的SA发光组成,而在飞秒激光激发下,仅在481nm处显示出强烈的双光子发射峰。     

Growth process studies by reflectance anisotropy spectroscopy on MOVPE ZnSe

The growth of ZnSe on GaAs by metal organic vapour phase epitaxy (MOVPE) has been studied using reflectance anisotropy spectroscopy (RAS). The RA spectra of ZnSe are significantly different for growth on initially Se- or Zn-exposed GaAs surfaces. The Se-terminated GaAs (001) RA spectrum has Se-dimer-related features at 3.3 and 5.1 eV, and the large, high energy peak dominates during ZnSe growth on this surface. Transmission electron microscopy (TEM) analysis has been used to show that these large RA signals arise from anisotropic surface corrugation of the growing ZnSe epilayer. Under initially Zn-stabilised growth conditions, the ZnSe epilayer RA spectrum is largely featureless, showing only a weak peak at 4.7 eV and a dip at 5.1 eV. The corresponding surface anisotropy is greatly reduced in comparison with growth from the initially Se-terminated surface. These observations reveal RAS to the an important technique for ensuring the desired initial GaAs surface since the grown ZnSe surface morphology is critically dependent on the pre-growth substrate surface treatment. However, as the characteristic ZnSe RA spectra are relatively insensitive to changes in substrate temperature and VI–II ratio, RAS is of more limited use as an in-growth surface probe for MOVPE-grown ZnSe.     

Initial growth behavior of GaAs on ZnSe in MOVPE

We have used atomic force microscopy to investigate the initial stages of the growth of GaAs on ZnSe by metalorganic vapor phase epitaxy. Underlying ZnSe with an atomically flat surface is achieved by growth at 450°C and post-growth annealing at the same temperature. The growth modes of GaAs on the ZnSe surface strongly depend on growth temperatures. The growth carried out at 450°C is 2-dimensional, while that at 550°C is highly 3-dimensional (3D), where the 3D islands are elongated in the [110] direction. The growth behavior, unlike homoepitaxy, is well interpreted in terms of low sticking coefficient and anisotropic lateral growth rate in the heterovalent heteroepitaxy.     

On the thermal and optical properties of ZnSe and doped ZnSe crystals grown by PVT

Single crystals of ZnSe, phosphorus-doped ZnSe and phosphorus with Gallium-doped ZnSe have been grown by physical vapour transport technique. The thermal properties like thermal diffusivity, effusivity and conductivity are studied using photoacoustic spectroscopy and differential scanning calorimetry, for the use of substrate. Their optical properties are also studied using Raman, photoluminescence and photocurrent for the study of the site symmetry of the phosphorus. Our measurements reveal the possibility of phosphorus going to deep level thus reducing to C_3v level.     

Studies in the growth of ZnSe on GaAs(001)

This paper reports a study of the molecular beam epitaxial (MBE) growth of ZnSe on GaAs substrates using elemental sources. Growth rates of ZnSe as a function of Se:Zn flux ratio for constant Zn flux were determined over a wider range of values than previously reported. Careful measurements of atomic fluxes and sample thickness lead to a determination of the sticking coefficients of Zn and Se which are at variance with many previously reported values. The temperature dependence of the sticking coefficients of Zn and Se has been measured carefully and provides evidence for a greater desorption of Zn from the growing surface than previously thought, an effect which persists at low growth temperatures. Measurements at high flux ratios support the use of a precursor model to describe MBE growth of ZnSe on GaAs substrates.