硫镓银晶体的化学腐蚀研究

采用改进的垂直布里奇曼(Bridgman)法自发成核生长AgGaS2晶体,在生长初期对生长安瓿籽晶袋进行上提回熔,生长出外观完整、无裂纹的大尺寸AgCaS2单晶体.采用XRD对晶体进行分析,获得了(112)、(001)和(101)面的高强度尖锐衍射峰.采用不同配比的腐蚀剂对晶体(101)、(112)及(001)晶面进行化学腐蚀,然后采用金相显微镜和扫描电镜观察,结果显示,(101)晶面蚀坑为清晰的近似三角形的四边形蚀坑,(112)晶面蚀坑为清晰的近似三角锥形,(001)晶面则呈现互相垂直的腐蚀线.初步分析了不同蚀坑的形成原因,计算出(101)和(112)面蚀坑密度约为105/cm2数量级.结果表明,改进方法生长出的大尺寸AgGaS2单晶体结构完整、位错密度低,质量较好.     

硒铟镓银单晶体(112)面蚀坑形貌观察

研究出一种能在室温下对AgGa0.8In0.2Se2晶体(112)面进行择优腐蚀的新腐蚀液配方,提出了一种适合AgGa0.8In0.2Se2晶体择优腐蚀的新工艺。采用改进的Bridgman法生长出AgGa0.8In0.2Se2晶体,对晶体进行定向切割出(112)面晶片;然后对晶片进行研磨、机械抛光,使其表面平整无划痕;再将晶片用新腐蚀液,浓HNO3(65%～68%)∶浓HCl(35%～38%)=1∶2.5(体积比),在室温下腐蚀5min,同时进行超声振荡。采用金相显微镜对腐蚀后的晶片表面进行观察,发现清晰的蚀坑形貌,形状近似为正三角形,并对(112)面蚀坑的形成及其形貌成因进行了理论分析。     

CdGeAs2单晶体的腐蚀研究

报道了一种新型的CdGeAs2晶体择优腐蚀剂,配方为:H2O2(30;): NH4OH(含NH325;-28;): NH4Cl(5mol/L): H2O=1 mL: 1.5 mL: 1.5 mL: 2 mL.将经机械研磨、物理抛光和溴甲醇化学抛光处理后的表面平整无划痕的CdGeAs2晶片,在40 ℃下超声振荡腐蚀数分钟,采用金相显微镜和SEM进行蚀坑观察.结果表明,新型腐蚀剂对CdGeAs2晶体(204)和(112)晶面择优腐蚀效果显著,蚀坑取向一致,具有很强的立体感;(204)晶面蚀坑呈三角锥形,(112)晶面蚀坑呈五边形,从晶体结构上对蚀坑形成机理进行了分析讨论.     

碲锌镉单晶体的(110)面蚀坑形貌观察

本文报道了一种能够在室温下择优腐蚀碲锌镉(CZT)单晶体(110)晶面的腐蚀液配方,并对富Cd生长的CZT晶体蚀坑形貌进行了扫描电镜观察.结果表明晶体(110)面腐蚀坑形状为三角形,并初步对蚀坑的成因进行了分析,估算出CZT(110)面蚀坑密度约为103～105/cm2数量级.这说明富Cd原料的改进布里奇曼法可以生长出低蚀坑密度的CZT单晶体.     

磷锗锌单晶体的腐蚀研究

报道了一种新的ZnGeP2晶体择优腐蚀剂及其腐蚀工艺,即先采用研磨、物理机械抛光和HCl+HNO3热化学抛光获得表面平整无划痕的ZnGeP2晶片,然后将晶片在室温下采用HF(40;):HNO3(65;):CH3COOH(99.5;):H2O:I2=2 mL:2 mL:1 mL:1 mL:4 mg腐蚀剂超声振荡腐蚀8 min;在扫描电镜下观察到ZGP(110)和(204)晶面的腐蚀坑,蚀坑形貌清晰,具有立体感,(110)晶面蚀坑呈四边形,(204)晶面蚀坑呈五边形,取向一致,蚀坑密度(EPD)约为104/cm2.从理论上对蚀坑形貌的形成机理进行了分析.     

Yb: Lu_3Al_5O_(12)晶体的生长及缺陷研究

采用提拉法生长Yb~(3+)掺杂浓度为10 at;的Yb: Lu_3Al_5O_(12)(Yb: LuAG)晶体.对晶体的结晶质量、晶胞参数、分凝系数等进行了表征.采用化学腐蚀的方法,利用光学显微镜和扫描电镜相结合研究了晶体中的缺陷.结果表明晶体具有较好的结晶质量,Yb~(3+)的掺入不会改变LuAG的晶体结构.观察到Yb: LuAG晶体(111)面上呈三角锥形的位错蚀坑和由小面引起的晶体应力双折射现象,并提出了减少缺陷,提高晶体质量的方法.     

提拉法Ti:LiAlO2晶体的生长、缺陷及N2退火研究

本文采用提拉法成功地生长了钛掺杂浓度为0.1%原子分数的LiAlO2单晶体,借助光学显微镜,结合化学腐蚀法,对Ti:LiAlO2晶体(100)面空气退火前后的缺陷特征进行了研究,用AFM观测了(100)面晶片在不同温度下流动N2气氛退火过的表面形貌。结果表明:Ti:LiAlO2晶体(100)面的位错腐蚀坑是底面为平行四边形的锥形坑,位错密度约为5.0×104cm-2,900℃空气退火后晶片表面的位错腐蚀坑变大;N2退火能显著影响晶片的表面形貌,当退火温度为900℃时,晶片的均方根粗糙度(RMS)达到最低值。     

中远红外非线性光学晶体AgGaS2、AgGaSe2和AgGa1-xInxSe2研究进展

综合报道了本实验室关于黄铜矿类I-III-VI2型系列晶体的研究进展。采用两温区气相输运温度振荡法合成出高纯、单相、致密的多晶材料,在三温区立式炉中用坩埚旋转下降法生长出AgGaS2、AgGaSe2和AgGa1-xInxSe2等系列单晶体,X射线单晶衍射谱和回摆谱表明晶体的结晶性好,结构完整;红外透过率接近理论值,吸收系数低于0.017 cm-1,表明生长的晶体光学质量高。研究出一种新的能对AgGa1-xInxSe2晶体(112)晶面进行择优腐蚀的腐蚀剂:(30 g CrO3+10 mL H2O)∶H4PO4(85%)∶HNO3(65～68%)∶HF(40%)=10∶10∶10∶2(体积比),在60℃下腐蚀40 min,能够清晰地显示出AgGa1-xInxSe2晶体(112)面取向一致的三角形腐蚀坑,边界清晰,蚀坑密度大约为105/cm2数量级。采用自行研制的晶体定向切割新方法,加工出AgGa1-xInxSe2-OPO器件,获得了3～5μm的激光输出,光-光转换效率达21%。     

激光晶体位错蚀坑的SEM研究

利用扫描电镜(SEM)及能谱(EDS)技术研究激光晶体缺陷,给出了经腐蚀过后Nd: YAG晶体表面位错蚀坑的清晰图片和元素分布定量信息,同时进行了对比实验,并对实验结果进行了分析.结果表明:Nd: YAG晶体位错腐蚀坑呈三角锥状,腐蚀坑杂质元素分布较多,主要元素含量偏离晶体完整区成份;位错腐蚀坑稀疏区与密堆区元素分布及含量不同.并讨论了位错成因.     

近红外半导体材料HgInTe的缺陷腐蚀

研究了HgInTe的腐蚀工艺,探索出一种适合于HgInTe的腐蚀液,并对腐蚀原理做了分析.利用该腐蚀液对HgInTe晶体内部的缺陷种类和分布进行了研究.结果表明,垂直轴向切割的HgInTe晶片腐蚀后的位错蚀坑呈近等腰三角形.在本实验条件下,位错蚀坑密度EPD(etch-pit density)约在105/cm2数量级.HgInTe晶体中的位错墙主要以边重叠和角重叠两种方式排列而成.HgInTe中存在少量由内应力引起的微裂纹.该腐蚀液能有效地显示HgInTe晶体不同晶面的多种缺陷,腐蚀效果较好.     

高温闪烁晶体Ce:YAP的化学腐蚀形貌

本文报导了Ce:YAP晶体位错蚀坑的腐蚀条件;同时报导了几个主要晶面的位错蚀坑形貌,(100)面呈扁豆形,(010)面呈菱形,(101)面呈椭圆形,这些形状与各自晶面的对称性一致.通过蚀坑形貌在晶体横截面内观察到了小面生长核心区和熔质尾迹等缺陷,并分析了其成因.     

石榴子石晶体碱腐蚀像及其与酸腐蚀像的对比

本文采用NaOH-KOH混合熔融物和KOH溶液对石榴子石晶体各种不同的结晶学方向的晶面(切面)进行腐蚀实验,建立了石榴子石碱腐蚀像的立体模型,并与酸(HF溶液)腐蚀像模型进行对比.研究发现碱腐蚀像与酸腐蚀像一样能很好的反映晶体的对称特点,并发现在{ 100}、{110}晶面(切面)上碱腐蚀像与酸腐蚀像相同,而在{120}、{221}、{111}、{211}晶面(切面)上,碱腐蚀像与酸腐蚀像不同.该研究可以用来对石榴子石族矿物进行结晶学定向,同时具有揭示矿物所处地质环境酸碱性的指示意义.     

Wet KOH etching of freestanding AlN single crystals

We investigated defect-selective wet chemical etching of freestanding aluminum nitride (AlN) single crystals and polished cuts in a molten NaOH–KOH eutectic at temperatures ranging from 240 to 400 °C. Due to the strong anisotropy of the AlN wurtzite structure, different AlN faces get etched at very different etching rates. On as-grown rhombohedral and prismatic facets, defect-related etching features could not be traced, as etching these facets was found to mainly emphasize features present already on the un-etched surface. On nitrogen polar basal planes, hexagonal pyramids/hillocks exceeding 100 μm in diameter may form within seconds of etching at 240 °C. They sometimes are arranged in lines and clusters, thus we attribute them to defects on the surface, presumably originating in the bulk material. On aluminum polar basal planes, the etch pit density which saturates after approx. 2–3 min of total etching time at 350 °C equals the density of a certain type of dislocations (presumably screw dislocations) threading the surface. Smaller etch pits form around annealed indentations, in the vicinity of some bigger etch pits after repeated etching, and sometimes also isolated on the surface area. Although alternate explanations exist, we attribute these etch pits to threading mixed and edge dislocations. This paper features etching parameters optimized for different planes and models on the formation of etching features especially on the polar faces. Finally, the issue of reliability and reproducibility of defect detection and evaluation by wet chemical etching is addressed.     

连续离子层吸附反应(SILAR)法制备AgGaS2纳米薄膜及性能表征

采用连续离子层吸附反应(SILAR)法,通过500℃退火在玻璃衬底上制备出AgGaS2纳米薄膜.使用X射线衍射(XRD)、扫描电镜(SEM)、X射线能谱(EDS)、紫外可见(UV-Vis)谱和光致发光(PL)谱等对纳米薄膜的物相、形貌、化学配比和光学性能进行了定性和定量表征.XRD测试结果表明,实验获得产物为黄铜矿结构AgGaS2,并观测到(112)面和(224)面.使用Scherrer公式估算了AgGaS2产物的晶粒平均粒度大小约为30 nm.SEM观测到的AgGaS2纳米薄膜外形均匀一致,沉积紧密,薄膜沉积的纳米平均颗粒直径约为18～ 26 nm.EDS测试结果显示AgGaS2纳米薄膜中Ag、Ga和S三元素的原子相对百分含量为25.12;,26.66;和49.93;,其化学计量比几近于1∶1∶2物质的量比.通过紫外可见透过光谱得到截止波长为470.1 nm,禁带宽度为2.64 eV.室温PL测试发现发光中心在456 nm,与AgGaS2晶体发光中心相比产生了约40nm的蓝移.以上结果充分表明SILAR法是一种制备AgGaS2纳米薄膜的有效方式.     

热交换法生长c面取向大尺寸蓝宝石晶体的研究

本文使用热交换法直接生长c面取向,尺寸为φ170 mm× 160 mm,重12 kg的蓝宝石晶体.晶体无色透明,内部无散射颗粒.沿c面(0001)方向的晶棒锥光图可观察到同心圆簇的干涉条纹,仅中心较小区域因内应力存在,干涉条纹发生扭曲.将抛光的晶片进行化学腐蚀后,通过金相显微镜检测位错腐蚀坑形貌图,结果显示,腐蚀坑呈三角形,平均位错密度较低,为1.98 × 103 Pits/cm2,X射线衍射半峰宽较小,晶体结构完整.     

The effect of HF/NH4F etching on the morphology of surface fractures on fused silica

The effects of HF/NH₄F, wet chemical etching on the morphology of individual surface fractures (indentations, scratches) and of an ensemble of surface fractures (ground surfaces) on fused silica glass has been characterized. For the individual surface fractures, a series of static or dynamic (sliding) Vickers and Brinnell indenters were used to create radial, lateral, Hertzian cone and trailing indentation fractures on a set of polished fused silica substrates which were subsequently etched. After short etch times, the visibility of both surface and subsurface cracks is significantly enhanced when observed by optical microscopy. This is attributed to the increased width of the cracks following etching, allowing for greater optical scatter at the fracture interface. The removal of material during etching was found to be isotropic except in areas where the etchant has difficulty penetrating or in areas that exhibit significant plastic deformation/densification. Isolated fractures continue to etch, but will never be completely removed since the bottom and top of the crack both etch at the same rate. The etching behavior of ensembles of closely spaced cracks, such as those produced during grinding, has also been characterized. This was done using a second set of fused silica samples that were ground using either fixed or loose abrasives. The resulting samples were etched and both the etch rate and the morphology of the surfaces were monitored as a function of time. Etching results in the formation of a series of open cracks or cusps, each corresponding to the individual fractures originally on the surface of the substrate. During extended etching, the individual cusps coalesce with one another, providing a means of reducing the depth of subsurface damage and the peak-to-valley roughness. In addition, the material removal rate of the ground surfaces was found to scale with the surface area of the cracks as a function of etch time. The initial removal rate for the ground surface was typically 3.5× the bulk etch rate. The evolving morphology of ground surfaces during etching was simulated using an isotropic finite difference model. This model illustrates the importance that the initial distributions of fracture sizes and spatial locations have on the evolution of roughness and the rate at which material is removed during the etching process. The etching of ground surfaces can be used during optical fabrication to convert subsurface damage into surface roughness thereby reducing the time required to produce polished surfaces that are free of subsurface damage.     

The K2S2O8–KOH photoetching system for GaN

A recently developed photoetching system for n-type GaN, a KOH solution containing the strong oxidizing agent potassium peroxydisulphate (K₂S₂O₈), was studied in detail. By careful selection of the etching parameters, such as the ratio of components and the hydrodynamics, two distinct modes were defined: defect-selective etching (denoted by KSO-D) and polishing (KSO-P). Both photoetching methods can be used under open-circuit (electroless) conditions. Well-defined dislocation-related etch whiskers are formed during KSO-D etching. All types of dislocations are revealed, and this was confirmed by cross-sectional TEM examination of the etched samples. Extended electrically active defects are also clearly revealed. The known relationship between etch rate and carrier concentration for photoetching of GaN in KOH solutions was confirmed for KSO-D etch using Raman measurements. It is shown that during KSO-P etching diffusion is the rate-limiting step, i.e. this etch is suitable for polishing of GaN. Some constraints of the KSO etching system for GaN are discussed and peculiar etch features, so far not understood, are described.     

Selective etching of ZnTe in HF:H2O2:H2O solution: Interpretation of extended defect‐related etch figures

HF:H₂O₂:H₂O solution (40%wt.HF: 30wt.%H₂O₂: H₂O, 3:2:1 by volume) was used to reveal extended defects (line, face and volume defects) in bulk ZnTe crystals grown from Te solution. The etch patterns were analyzed based on their size, shape and distribution. The etch figures, both in the shape of pits and hillocks with high resolution, show forms controlled by the symmetries of the respective faces were produced. Two different sizes of pits were observed, the larger‐size pits correspond to dislocations penetrating the surface, however, the smaller‐size texture pits are produced on the defect‐free region, which serve as standard pits on respect faces. The face defects, such as grain boundaries, sub‐grain boundaries, dislocation walls, twins and stacking faults, can be all displayed clearly. Another essential feature of the etchant is that, it can effectively dissolve Te‐rich phase (Te inclusion/precipitates), which makes it promising to reveal the shape of this volume defect.