黄铜矿类半导体砷化锗镉晶体的研究进展

砷化锗镉,CdGeAs2,是三元的黄铜矿类半导体,具有非常高的非线性光学系数(236pm/V),这使得其作为CO2激光器倍频转换方面有突出的优势.长期以来生长晶体时由于存在严重的各向异性而使晶体开裂.砷化锗镉晶体在5.5μm处存在强吸收使得频率转化的效率非常低,此吸收是晶体内存在大量受体缺陷造成的.本文对晶体生长的几种方法和红外吸收进行论述,并提出掺杂予体的方法降低红外吸收.     

高能电子辐照和退火对磷锗锌晶体红外光学性质的影响

对采用改进的垂直布里奇曼法生长出的磷锗锌(ZnGeP2)单晶体样品,在300 K,10 MeV高能电子束下进行辐照实验,测试辐照前后其红外透过率.同时,对样品进行同成分粉末包裹退火处理,对比两种工艺对磷锗锌晶体红外透过率的影响.实验结果表明,退火和高能电子辐照都能对磷锗锌晶体的红外光学性质产生影响,提高其红外透过率.在本文的实验条件下,退火工艺对磷锗锌晶体红外透过率的提高更为明显.     

砷化锗镉晶体的合成与生长

砷化锗镉(CdGeAs2)晶体是一种重要的中远红外波段非线性光学晶体,非线性光学系数高达236pm/V[1]。此外,晶体的透光波段宽(2.4~18μm)[2],双折射率适中(ne-no=0.1)·K)[3],具有广泛的应用前景。本文采用单温区法合成了CdGeAs2多晶原料。采用可视温梯冷凝法生长了大尺寸,低吸收系     

激光晶体Zr∶Yb∶LiNbO3的生长及光谱性质研究

采用Czochralski技术分别生长了双掺Zr4+(1mol;,2mol;,3mol;)和Yb3+(0mol;,1mol;,1mol;)的Zr∶Yb∶LiNbO3晶体.测试了晶体的XRD图谱并与标准图谱进行了比较.测量了晶体的红外透射光谱,OH-的振动吸收峰分别位于3485 cm-1、3488 cm-1和3488 cm-1,当Zr4+浓度达到2mol;以后,继续增大Zr4+浓度,OH-的振动吸收峰不发生移动.研究了晶体的室温吸收、发射光谱和荧光寿命特性,表明Zr∶Yb∶LiNbO3晶体是一种潜在的可用来发展具有抗光损伤的新型激光晶体材料.     

Tm:YAG晶体的生长及吸收特性

采用提拉法生长出三种掺Tm3+浓度的Tm:YAG晶体.运用ICP-AEs测定Tm3+离子在Tm:YAG晶体中的分凝系数约为1.室温下测定了Tm:YAG晶体在190～900nm之间的吸收光谱及1000～4500cm-1范围内退火前后的红外吸收谱.测试结果表明,退火后3365cm-1处OH-1离子的吸收峰完全消失.说明在空气气氛下对Tm:YAG晶体进行退火处理改善了晶体的性能.     

光激电流法测量掺锗CZSi中的深能级

用光激电流法研究了Ｇｅ作为杂质掺入到Ｓｉ中可能引入的深能级，发现掺锗量小于或等于１．０ｗｔ％（重量比）时，不会在ＣＺＳｉ中引入与锗有关的深能级；锗的引入硅中点缺陷的深度。     

高掺镁铌酸锂晶体OH-吸收光谱的低温研究

本文测量了纯铌酸锂和高掺镁铌酸锂晶体的低温红外光谱,观察了OH-吸收峰的温度依赖特性.研究发现纯铌酸锂的OH-振动吸收峰基本不随温度而变化,而高掺镁铌酸锂晶体的OH-振动吸收峰的主峰峰位随温度的降低向高波数方向移动.通过分析两种晶体中不同的缺陷模型以及H+在晶格中的占位,我们提出高掺镁铌酸锂晶体中的H+紧邻高电性杂质缺陷(MgNb)3-分布,直接参与缺陷集团,完全不同于纯铌酸锂晶体中H+的分布情形,这造成了高掺镁铌酸锂晶体中OH-振动吸收峰随温度的变化.而集团内部缺陷之间相互作用随温度降低而增强的趋势是OH-振动吸收峰右移的主要原因.     

助熔剂坩埚下降法生长近化学计量比Co:LiNbO3晶体

以K2O为助熔剂,在较大的温度梯度(90～100℃/cm)条件下进行引种和晶体生长,应用坩埚下降法成功地生长出了初始CO2+掺杂浓度为0.5mol;的近化学计量比的铌酸锂晶体.测定了该晶体的红外光谱与吸收光谱,与同成份的LiNbO3晶体相比,其紫外吸收边向短波方向移动,OH-红外吸收峰的位置发生变化.观测到520,549,612nm三个分裂的尖吸收峰以及1400nm左右为发光中心的吸收带.从吸收特性可以判断,Co离子在铌酸锂晶体中呈现+2价.比较上部与下部晶体的吸收强度,可以推测出沿着晶体生长方向Co2+离子浓度逐渐降低,Co2+离子在晶体中有效的分凝系数大于1.     

四价掺杂铌酸锂晶体抗光折变性能研究

我们在同成份铌酸锂晶体中掺入四价离子铪,生长了掺杂浓度分别为2、4、6mol;的掺铪铌酸锂系列晶体.掺铪浓度达到4mol;时,晶体的抗光损伤能力为5×105W/cm2,比同成份纯铌酸锂晶体提高了4个数量级.应用全息法测得掺4、6mol;铪的铌酸锂晶体最大折射率变化为8.7×10-6,与高掺镁(6.5mol;)铌酸锂晶体的类似.晶体的红外吸收谱和紫外-可见光吸收谱也显示,掺杂浓度为4mol;时具有明显的阈值特征.由此可以确定铪离子在铌酸锂晶体中的阈值浓度约为4mol;.     

氧对饵掺杂硅纳米晶粒电子结构和光学性质的影响

采用第一性原理,对O与Er共掺杂硅纳米晶粒的电子结构及光学性质进行了计算.计算结果表明:O原子的掺杂没有影响Er掺硅纳米晶粒的禁带宽度;Er掺硅纳米晶粒结构在紫外区的吸收峰因O原子的掺入明显加强,红外区源于Er原子的吸收峰峰值减小.     

重掺硅衬底片的内吸除效应

本文研究了重掺p型(B)和重掺n型(P、As、Sb)硅单晶的内吸除效应.发现在本实验条件下,经过改进的内吸杂(IG)处理后,不同掺杂剂的重掺硅单晶片都出现了氧沉淀增强现象,但不同掺杂剂的重掺硅单晶中氧沉淀形态不同.且发现砷增强了硅片近表层区氧的外扩散.在相同的热处理条件下,不同掺杂剂的重掺硅清洁区宽度不同,重掺硼硅片的清洁区最窄,重掺砷的最宽.     

Infrared spectra of glassy Se containing small amounts of S,Te, As,or Ge

The infrared transmission spectra of glassy Se containing 2.5 and 5.0 at % S, Te, As or Ge as well as pure Se were measured in the wavenumber region 400-60 cm^?1 at room temperature. Besides the absorption bands reported already for pure Se, well-defined bands were founds at 355 cm^?1 and 168 cm^?1 for the addition of S, and at 205 cm^?1 for Te. These new absorption bands attributed to Se₃S₅ and Se₅Te₃ mixed rings, respectively. For As, a strong absorption band appeared at 240 cm^?1. The band near 135 cm^?1 began to broaden and shift to lower frequency with As content. Two shoulder bands near 307 cm^?1 and 278 cm^?1 and a separated band at 195 cm^?1 were found for Ge. With increasing Ge concentration the band at 135 cm^?1 broadened and shifted to lower frequency. An interpretation for the new bands is presented on the basis of a molecular model.     

Growth of Zn‐doped Germanium under Microgravity

The doping of germanium with zinc from a remote, temperature‐stabilized source was studied under microgravity. A nominally undoped Ge‐crystal was grown by the Gradient‐Freeze technique with the melt surface being in permanent contact with a gaseous atmosphere of zinc. The dopant and carrier concentrations in the solidified Germanium were measured by SIMS, Hall and resistance measurements and compared with the results of a terrestrial reference experiment as well as with concentration profiles calculated on the basis of the thermodynamics of the growth system. The results prove the possibility of vapour phase doping under microgravity. Moreover, the Zn‐concentration at the initial phase boundary even agrees well with the equilibrium value, strongly indicating a nearly homogeneous distribution of the dopant within the melt before the crystallization.     

Structural development in Ge-rich Ge–S glasses

The Raman spectra of Ge–S glasses in the Ge-rich region from Ge 33% to 46% have been investigated in order to know the structural development of the network glasses. From the detailed curve fits, we have found that there is an unassigned peak at 410 cm⁻¹ and it becomes larger with increasing Ge composition. To clarify the structural origin of the peak, we virtually constructed the atomic arrangement of the glassy state starting from the crystalline state through the liquid state and changed the composition gradually depleting the medium in sulfur. From the consideration of the structural modeling and the atomic orbital theory, we suggest that single Ge–S chain is a probable structural origin of the peak.     

Study on the oxygen concentration reduction in heavily Sb-doped silicon

It was determined that oxygen concentration in heavily Sb-doped silicon was about 40% lower than that in the lightly doped Czochralski grown silicon and decreased with increasing content of Sb by means of coincident elastic recoil detection analysis. Through thermodynamic calculation, the oxygen loss by evaporation from the free surface of melt is only due to the formation of SiO, and Sb₂O₃ evaporation can be neglected. The basic reason for oxygen concentration reduction in heavily Sb-doped CZSi was that oxygen solubility decreased when element Sb with larger radius doped degenerately into silicon crystal.     

Nondestructive concentration profiling of fiber optic preforms by analysis of Raman spectra

We have demonstrated that Raman scattering may be used to determine P and Ge concentration profiles of optical fiber preforms. For Ge, the technique has an absolute accuracy of about 0.5 mol.% Ge, and spatial resolution to 40 μm was achieved. When used in a nondestructive mode, spatial resolution of 100 μm is possible. The results clearly show that phosphorus as well as germanium burn out as the tube is collapsed, with the spatial extent of the phosphorus burnout region being about twice as great as that for germanium. Our measurements on a graded-P preform provide a determination of the Ge incorporation ratio across the preform with the surprising result that it increases toward the edge, where the temperature is higher and P content is lower.The spectra also provide clear evidence for two types of Ge sites in silica-germanium glasses, where one type of site, possibly associated with network defects, is predominantly occupied at low concentration. The 710 cm^?1 line associated with these defect sites is not detected when either P or B is present, and we speculate that this may be related to the dependence of the Ge incorporation ratio on the phosphorous concentration.     

Properties of Ge-doped,high-quality bulk GaN crystals fabricated by hydride vapor phase epitaxy

We investigated the properties of Ge-doped, high-quality bulk GaN crystals with Ge concentrations up to 2.4×10¹⁹ cm⁻³. The Ge-doped crystals were fabricated by hydride vapor phase epitaxy with GeCl₄ as the dopant source. Cathodoluminescence imaging revealed no increase in the dislocation density at even the highest Ge concentration, with values as low as 3.4×10⁶ cm⁻². The carrier concentration, as determined by Hall measurement, was almost identical to the combined concentration of Ge and unintentionally incorporated Si. The electron mobilities were 260 and 146 cm² V⁻¹ s⁻¹ for n=3.3×10¹⁸ and 3.35×10¹⁹ cm⁻³, respectively; these values are markedly larger than those reported in the past for Ge-doped GaN thin films. The optical absorption coefficient was quite small below the band gap energy; it slightly increased with increase in Ge concentration. Thermal conductivity, estimated by the laser-flash method, was virtually independent of Ge concentration, maintaining an excellent value around 2.0 W cm⁻¹ K⁻¹. Thermal expansion coefficients along the a- and m-axes were approximately constant at 5.0×10⁻⁶ K⁻¹ in the measured doping concentration range.     

Czochralski-growth of germanium crystals containing high concentrations of oxygen impurities

Oxygen-containing germanium (Ge) single crystals with low density of grown-in dislocations were grown by the Czochralski (CZ) technique from a Ge melt, both with and without a covering by boron oxide (B₂O₃) liquid. Interstitially dissolved oxygen concentrations in the crystals were determined by the absorption peak at 855 cm⁻¹ in the infrared absorption spectra at room temperature. It was found that oxygen concentration in a Ge crystal grown from melt partially or fully covered with B₂O₃ liquid was about 10¹⁶ cm⁻³ and was almost the same as that in a Ge crystal grown without B₂O₃. Oxygen concentration in a Ge crystal was enhanced to be greater than 10¹⁷ cm⁻³ by growing a crystal from a melt fully covered with B₂O₃; with the addition of germanium oxide powder, the maximum oxygen concentration achieved was 5.5×10¹⁷ cm⁻³. The effective segregation coefficients of oxygen in the present Ge crystal growth were roughly estimated to be between 1.0 and 1.4.     

Structure of liquids and glasses in the Ge–Se binary system

A summary is given of the partial structure factors that have been measured for liquids and glasses in the Ge–Se binary system by using diffraction methods. Information is presented on the pair correlation functions describing the atomic species and use is made of the Bhatia–Thornton formalism to separate those pair correlation functions describing the system topology from those that describe the chemical ordering. The information made available by the measured Bhatia–Thornton partial structure factors on the thermodynamic properties of Ge–Se mixtures is briefly summarized. The properties of the network structures formed in liquid and glassy Ge–Se compounds are investigated as a function of composition, temperature and pressure. For GeSe₂ at ambient pressure it is shown that the so-called first sharp diffraction peak, which appears in the measured diffraction patterns at a small scattering wavevector value of ≈1 Å⁻¹ and which is associated primarily with Ge–Ge correlations, does account for discernable features of the observed intermediate range order in both the liquid and glassy phase. The first sharp diffraction peak in the measured Ge–Ge partial structure factor for both phases is described by comparable parameters suggesting communality in the underlying intermediate range order which survives the glass transition. Homopolar bonds are found to be a feature in the structure of liquid GeSe and both liquid and glassy GeSe₂ with Ge–Ge and Se–Se distances in the ranges 2.33(3)–2.42(2) and 2.30(2)–2.34(2) Å, respectively.     

Fictive temperature measurement of alumino-silicate glasses using IR spectroscopy

A simple IR reflection method was used in a previous study to determine the fictive temperature of silica glasses and a soda-lime glass. The IR method is based upon the fact that the silica structural band of a glass takes a unique wavenumber at a particular fictive temperature. When this method was applied to an alumino-silicate glass in this study, however, the IR reflection peak wavenumber of the glass surface was found to be strongly affected by the reaction of the glass with water vapor in the atmosphere. Still, it was possible to measure the fictive temperature of the alumino-silicate glass using IR spectroscopy by taking an IR reflection of the bulk sample after eliminating the surface layer affected by the reaction with water vapor. The IR peak wavenumber of the silica structural band decreased with increasing fictive temperature for the alumino-silicate glass, similar to silica glass.