Microstructure and growth rate of chemical vapour deposited TiN films in a vertical cold wall reactor

TiN films were grown on SUS304 substrates heated by an induction furnace in a vertical cold wall reactor. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction were used to characterize the microstructures of films obtained at different deposition conditions (temperature, gas flow rate and gas composition). Film structures obtained in the present vertical reactor had the following features compared with those in the tubular reactor: (1) Abnormally grown “star-shaped” crystals were observed on the surfaces of films deposited in the following ranges of total gas flow rate (Q_T), temperature (T) and partial pressures (P): 9.0×10⁻⁶ ≤ Q_T ≤ 1.6×10⁻⁵ m³ s⁻¹, 1223 ≤ T ≤ 1273 K, 0.92 ≤ P_TiCl4 ≤ 6.18 kPa, P_H2 = P_N2. The matrix grains were responsible for (211) preferred orientation. (2) Surface morphologies did not vary so much with P_TiCl4. On the other hand, a drastic change was brought about by adding HCl to the source gas, i.e., plate-shaped crystals dominated and the large “star-shaped” crystals were no longer present. (3) The apparent activation energy for deposition reaction was 230 kJ/mol (1173 ≤ T ≤ 1273 K) and 76.5 kJ/mol (1273 ≤ T ≤ 1373 K) at P_TiCl4 = 2.43 kPa and P_H2 = P_N2 = 49.45 kPa.     

Photo-assisted growth of ZnTe by metalorganic chemical vapour deposition

The metalorganic chemical vapour deposition (MOCVD) photo-assisted growth of ZnTe using a xenon lamp has been performed at atmospheric pressure under hydrogen as a carrier gas. Epitaxial growth was achieved on (100) GaAs, (100) GaSb and (100) ZnTe substrates with diethylzinc (DEZn) and diethyltellurium (DETe) as precursors. We have studied the growth rate as a function of the growth temperature, the partial pressure of precursors, the inlet partial pressure ratio R = VI/II, the light intensity and the energy of the irradiating photons. A growth rate enhancement has been observed for illuminated layers grown on GaAs and ZnTe substrates in comparison with those grown without illumination. We have not observed any measurable enhancement for layers grown onto (100) GaSb. The growth rate as a function of the light intensity increases for intensities higher than 20 mW / cm² and saturates for P > 120 mW / cm². We relate the growth rate enhancement to irradiating photons with an energy higher than the band gap of ZnTe at the growth temperature.     

The effect of hydrostatic pressure on the dielectric constants, and their temperature dependences, of phosphate and tellurite glasses

Measurements of the pressure dependence of the static dielectric constant of tellurite (pure TeO₂ and 67%TeO₂ + 33%WO₃) and samarium phosphate (5%Sm₂O₃ + 95%P₂O₅ and 15%Sm₂O₃ + 85%P₂O₅) glasses at elevated pressures (0–70 kbar) for a range of temperatures (77–380 K) are reported. The electrical properties under pressure have been determined from the low-frequency complex plane analysis of glass discs contained within a Bridgman opposed anvil cell. The most notable observation is that the pressure dependence of the static dielectric constant, of all glasses studied, is positive, for example for vitreous TeO₂ ln ε/P is equal to 4.41 × 10⁻¹¹ (Pa⁻¹) at 293 K. Behaviour of this type is common to a number of materials (plastics and chalcogenide glasses) for which it is not possible to define any long-range order. It is in direct contrast with the behaviour of crystalline insulators, for which ε/P is usually negative. The effect of pressure on the dielectric constant has been analysed using two different approaches based on the macroscopic Clausius-Mossotti equation. The effects of high pressure on the dielectric constant have been correlated with the temperature dependence of the dielectric constant at atmospheric pressure.     

Surface diffusion kinetics of GaAs and AlAs metalorganic vapor-phase epitaxy

We have investigated the surface kinetics during metalorganic vapor-phase epitaxy (MOVPE), using high-vacuum scanning tunneling microscopy (STM) observation of two-dimensional (2D) nuclei and denuded zones. Using Monte Carlo simulations based on the solid-on-solid model, from 2D nucleus densities we estimated the surface diffusion coefficients of GaAs and AlAs to be 2 × 10⁻⁶ and 1.5 × 10⁻⁷ cm²/s at 530°C, and the energy barriers for migration to be 0.62 and 0.8 eV, respectively. The 2D nucleus size in the [110] direction was about two times larger than that in the [ 10] direction. The size anisotropy is caused primarily by a difference in the lateral sticking probability (P_s) between steps along the [ 10] direction (A steps) and steps along the [110] direction (B steps). The P_s ratio was estimated to be more than 3:1. Denuded zone widths on upper terraces were 2 ± 0.5 times wider than those on lower terraces. This showed that P_s at descending steps was 10 to 3 × 10² times larger than P_s at ascending steps.     

n型GaAs欧姆接触电极制备工艺

目前,n型GaAs欧姆接触电极的制备方法以蒸镀法为主,然而该方法具有设备价格高、浪费电极材料的缺点。本文采用离子溅射法制备了n型GaAs的欧姆接触电极AuGeNi/Au,通过优化制备过程,可获得表面光滑平整、成分均匀无偏析的电极层。400 ℃氩气气氛下退火处理后,电极与GaAs之间由肖特基接触变为欧姆接触,极间电阻降为原来的1/20。退火温度在400~500 ℃时可得到很小的比接触电阻率(10^-6 Ω·cm²),有利于半导体器件工作稳定性的提高,降低能耗。退火温度低于400 ℃或高于500 ℃后比接触电阻率都较大,这分别与欧姆接触未形成以及Au-Ge合金的“球聚”有关。该制备方法和过程的优点为:设备成本低、流程简便、节省电极材料,具有良好的经济效益和实用价值,适合科研实验室使用。     

吡啶-2,6-二甲酸铅配位聚合物的绿色合成与表征

以吡啶-2,6-二甲酸(H₂pda)和乙酸铅为原料,用室温固相法合成配位聚合物[Pb(μ-pda)]_n (1),用元素分析、X射线粉末衍射和单晶衍射、红外光谱对聚合物1的组成和结构进行了表征,并研究其热稳定性和荧光性能。单晶结构显示,1属于单斜晶系,P2₁/n空间群,晶胞参数为a=0.980 84(11) nm,b=0.554 73(7) nm,c=1.433 62(16)nm,β=105.093(3)°。1的分子结构由2个Pb²⁺和2个pda^2-构成,含2个[Pb(μ-pda)]单元,每个Pb²⁺与来自pda^2-的6个氧原子和1个氮原子配位,形成了七配位的单帽三角棱柱构型。热稳定性研究表明,1在氮气气氛中的热分解反应包括配位聚合物骨架的坍塌和配体的氧化分解,热解残余物为PbO。荧光性能测试结果表明,该配位聚合物具有荧光性,其荧光可能来自配体内部的π^*→π电荷跃迁。     

Ion implantation effects in heavy metal fluoride glasses

Samples of a heavy metal fluoride glass (BInZnYbTGa) were subjected to argon and nitrogen irradiations of energies of 50 and 100 keV and fluences of 5×10¹⁶ and 1×10¹⁷ ions/cm². A 10 keV Ar irradiation at the ion dose of 1×10¹⁷/cm² was also performed. Modifications induced by the implants were characterized by nuclear microanalysis, electron spectroscopy, scanning electron microscopy and optical techniques. Surface precipitation of Th and Ba, as well as F and In depletion, were detected. Correlated modifications of the optical transmittance and reflectance were observed.     

高功率CO2激光器CVD金刚石窗口制备研究

本文研究制备了可应用于高功率CO2激光器的CVD金刚石窗口.首先使用环形天线-椭球谐振腔式MPCVD装置沉积制备直径2英寸(1英寸=2.54 cm)金刚石自支撑膜,然后将膜片双面抛光,激光切割成矩形基片,再采用蒸镀法在基片表面制备中心波长在10.6μm的增透膜,最终制备得到金刚石光学窗口.采用傅里叶红外透射谱、热导仪、...     

Preparation of TiB2 single crystals by the floating zone method

Single crystals of TiB₂ were prepared by the RF heated floating zone method. The growth rate was increased to 9 cm/h, to avoid violent evaporation. The obtained crystals, 1 cm in diameter and 6 cm long, had a stoichiometric composition and no subgrain boundaries. The product evaporated from the melt with a composition of B/Ti = 2.6 had a stoichiometric composition.     

Solvent effects on the growth kinetics of subtilisin crystals

The effects of salts on subtilisin crystallization were investigated. Three salts—NaCl, NaNO₃ and NaSCN—were selected to study the effects of different anions on growth kinetics of three subtilisin mutants—Properase^®, Purafect^® and Purafect^®OX. The effectiveness of salts in decreasing the solubility of Properase^® and Purafect^® subtilisin followed the reverse order of the Hofmeister series: SCN⁻>NO₃⁻>Cl⁻. The average length and diameter of crystals were measured during crystallization. The nature of salt changed the length/diameter ratio of crystals, indicating the changes in the relative growth rate of different crystal faces. The required supersaturation, (c−s)/s, for a given growth rate increased in the order of NaCl, NaNO₃ and NaSCN. The observed trend in required supersaturation indicates a kinetic effect and was counter to the trend for the solubility data. A rationale is provided based on the influence of ion binding and kinetics on the energetics of crystal growth and growth rate is correlated to the molar Gibbs free energy of hydration of the anion.     

Anomalous paramagnetism in pressure quenched CdS

Very large “paramagnetic” on positive magnetization has been observed in “pressure quenched” samples of CdS. Pressure quenching is a formative process involving pressure release rates ≈10⁶ bar s⁻¹.

The pressure quenched samples were prepared by pressure quenching at room temperature from above 30 kbar, i.e. from above the insulation-to-metal like transition. magnetization as a function of magnetic field was measured at 293 and 77 K using a vibrating specimen magnetometer. A linear M versus H behavior is observed in fields above a few hundred gauss, with values of χ = (M/H) ≈ 10^-4 cgs units. In some specimens saturation occurs, while in others the magnetization passes through a maximum. The maximum value of the magnetic moment M observed is of the order of tens of gauss.     

On the evaporation of EuS

The equilibrium evaporation of EuS was reinvestigated, giving the enthalphy of evaporation ΔH₂₉₈(2^nd law) = 215 kcal/mole by the 2^nd-law method and ΔH₂₉₈(3^rd law) = 221 kcal/mole by the 3^rd-law method.     

Raman spectroscopic study on the structure of ZnCl2---ZnX2 and ZnCl2---KX (X = Br, I) glasses

Raman spectra have been measured for ZnCl₂---ZnX₂ and ZnCl₂---KX (X = Br, I) glasses to investigate the structure of the glasses with varying composition. The assignment of each band was made, and the change of the spectra with composition was explained in terms of the bridging and non-bridging states of halide ions and the change of the tetrahedral units, ZnX_nCl_4−n²⁻ (n = 0–4), formed in the glasses. As the content of ZnX₂ in ZnCl₂---ZnX₂ glasses increases (20 → 80 mol%), the peak frequency of the Zn---Cl stretching mode increases (238 → 248 cm⁻¹ in X = I glasses, 238 → 259 cm⁻¹ in X = Br glasses) while the Zn---I and Zn---Br stretching frequencies decrease (173 → 120 cm⁻¹ for Zn---I, 196 → 157 cm⁻¹ for Zn---Br). The decrease of the Zn---I and Zn---Br band frequencies was attributed to the increase of the number n of the ZnX_nCl_4−n²⁻ tetrahedra. The increase of the Zn---Cl frequency suggests the existence of the bonding state of Cl⁻ ions which is intermediate between the bridging and the non-bridging states. In ZnCl₂---KX glasses, the Zn---Cl_non-bridging band at about 300 cm⁻¹ was observed in addition to the bands observed in ZnCl₂---ZnX₂ glasses. The addition of KX produces non-bridging anions while the tetrahedral units, ZnX_nCl_4−n²⁻ are also formed.     

Cs3Bi2I9晶体的生长及辐射探测性能

采用布里奇曼法成功制备出大尺寸(φ15 mm×50 mm)、高质量的全无机金属卤化物类钙钛矿Cs₃Bi₂I₉单晶。室温下,该晶体属于六方晶系,空间群为P6₃/mmc,密度为5.07 g/cm³,晶胞参数为a=b=0.840 nm,c=2.107 nm,熔点为632 ℃。采用粉末X射线衍射谱、紫外-可见-近红外漫反射光谱、I-V测试等表征该晶体的性质。制备Au/Cs₃Bi₂I₉/Au三明治型器件结构,采用飞行时间技术测试Cs₃Bi₂I₉晶体的载流子迁移率,得到Cs₃Bi₂I₉晶体的电子迁移率为4.33 cm²·V^-1·s^-1。根据Hecht单载流子方程拟合得到Cs₃Bi₂I₉晶体的载流子迁移率寿命积(μτ)为8.21×10^-5 cm²·V^-1,并且在500 V偏压下对α粒子的能量分辨率达到39%。     

High-quality InP grown by chemical beam epitaxy

InP films were grown by chemical beam epitaxy using trimethylindium (TMI) and pure phosphine (PH₃) in a flow control mode with hydrogen as the carrier gas, with the TMI flow rate fixed at 3 SCCM. Substrate temperatures were varied between 505 and 580°C and V/III ratios from 3 to 9. InP layers with high optical quality (intense and narrow excitonic transition lines) and high crystalline quality (narrow and symmetric X-ray diffraction peaks) could be grown only within a narrow parameter window around a substrate temperature of 545°C (δT_s ≤ 25°C) and a V/III ratio of 5.5 (δ(V/III) ≤ 2). Carrier densities of 8 × 10¹⁴ cm^-3 with mobilities of 70000 cm²/V.s measured at 77 K were obtained for growth conditions close to the edge of this parameter window towards low V/III ratios. The growth rate of inP was also clearly at its maximum in the given parameter window. Leaving the window, by changing either the growth temperature or the V/III ratio, significantly decreased the growth rate. This reduced growth rate was accompanied by a degradation in the crystalline quality. We also demonstrate that for higher TMI flow the parameter window shifts to higher growth temperatures. The InP could be doped effectively with Si in the range from 9 × 10¹⁵ to 3 × 10¹⁸ cm^-3.     

Structural, thermal and dielectric studies on a new solution grown 4-dimethylaminopyridinium dihydrogen phosphate crystal

Single crystals of 4-dimethylaminopyridinium dihydrogen phosphate (DMAPDP) (C₇H₁₃N₂PO₄) were grown by the solvent evaporation method. The three-dimensional structure was solved by the single-crystal X-ray diffraction method which belongs to triclinic crystal system and the molecular arrangements in the crystal were studied. The thermal behaviour was investigated using differential scanning calorimetry (DSC) and no phase transition was identified in the temperature region −150 to 230 °C. The thermal parameters—thermal diffusivity (), thermal effusivity (e), thermal conductivity (K) and heat capacity (C_p) of DMAPDP were measured by an improved photopyroelectric technique at room temperature. Dielectric constant and dielectric loss of the grown crystal were evaluated for the frequency range 1–200 KHz in the temperature region 28–135 °C. The Vicker's hardness was measured as 42.2 for a load of 98.07 mN. The laser induced surface damage threshold of DMAPDP crystal was found to be 4.8 GW/cm² with nanosecond Nd:YAG laser.     

Ag precipitation and optical behavior in Na2O---B2O3 glasses

Ag particles of different sizes in the nanometer range were produced in Na₂O---B₂O₃ glasses containing Ag₂O by the melt-quenching and heat-treatment method. The quenching rate was 10³ K s⁻¹ and the heat treatment was at 738 K for 2–300 h. The precipitation was dependent on diffusion limited growth. The optical absorption of Ag particles in the glasses was measured and correlated to the distribution of particle radii. The peak energy of the surface plasmon resonance was blue shifted and the width decreased with increasing average particle radius. These results are compared with previous data on similar systems.     

Changes in the refractive index of fused silica due to implantation of transition-metal ions

The changes in the refractive index of high purity silica glass produced by implantation of Ti⁺, Cr⁺, Mn⁺, Fe⁺ and Cu⁺ ions at 160 keV were measured using ellipsometry at a wavelength of 633 nm. Implantation doses ranged from 10¹⁵ to 6 × 10¹⁶ ions cm⁻². At the highest doses, a relative increase in refractive index of approximately 15% for implanted Cu ions and an increase of about half that for implanted Cr, Mn and Fe ions are observed. These variations in index probably result from colloid formation. For implanted Ti, virtually no change in the measured index of refraction was observed even at the highest doses.     

Ti/SnO2-IrO2电极的制备及其电化学降解对氯苯酚

电化学氧化法降解水中毒性有机物具有低碳、节能、清洁等优点,该技术的关键是开发高效、稳定、价格低廉的阳极。本文采用热分解法制备了Ti/SnO₂-IrO₂电极,对电极进行表征和电化学性能分析,并降解了对氯苯酚。考察不同因素(电流密度、目标污染物初始浓度、Cl^-浓度)对降解效果的影响。结果表明,Ti/SnO₂-IrO₂电极具有较长的寿命和良好的电化学性能。当电流密度为20 mA·cm^-2,对氯苯酚初始浓度为300 mg/L,Cl^-浓度为1 000 mg/L时,化学需氧量(COD)去除率可达89.02%,同时电极具有较低的能耗0.596 kWh·g^-1,表现出优异的催化性能。该电极具有一定的工业应用前景。     

新型镉(Ⅱ)配合物荧光探针的合成及性能

以8-氨基喹啉、1,5-萘二磺酸根为配体,NaN3为pH调节剂,与Cd(NO3)2通过水热反应,合成了一个新的一维链状镉配合物:[Cd(8-aql)2(1,5-nd)]2·H2O(1)(8-aql=8-氨基喹啉,1,5-nd=1,5-萘二磺酸根),并对其进行了元素分析、红外光谱和X-射线单晶衍射表征.配合物1属于单斜晶...