Thermal conductivity of ZnSe by molecular dynamics simulation

Molecular dynamics simulation using the new fit of the empirical Tersoff Potential is applied to study the thermal properties of ZnSe at and below the room temperature. The resulting diffusivity and thermal conductivity are compared with the photoacoustic measurements on the grown ZnSe crystal. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

SIMS and Raman characterizations of ZnO:N thin films grown by MOCVD

Nitrogen was incorporated into ZnO films grown by metalorganic chemical vapour deposition (MOCVD) on ZnO substrates using DMZn-TEN, tert-butanol and diallylamine, respectively, as zinc, oxygen and doping sources. The carrier gas was either hydrogen or nitrogen and the partial pressure ratio (R_VI/II) was varied in order to favor the nitrogen incorporation and/or reduce carbon related defects. The ZnO films have been characterized by Micro-Raman scattering and SIMS measurements. SIMS measurements confirm the nitrogen incorporation with concentrations extending from ∼10¹⁹ cm⁻³ to ∼4×10²⁰ cm⁻³. Raman spectra show nitrogen local vibration modes in films grown at low R_VI/II ratio and using H₂ as carrier gas. However, a vibration band attributed to carbon clusters dominates the Raman spectra for films grown with N₂ carrier. The contribution of N complexes was discussed. The strain was calculated for the as-grown and annealed films and it changes from tensile to compressive after annealing.     

CVD法生长ZnSe的工艺分析

采用单质Se为原料(Zn-Se-H2-Ar体系)来生长CVD ZnSe,初步分析了这种工艺的机理,并详细分析了各种工艺参数对生长ZnSe的影响.这些工艺参数包括沉积腔的温度和压力,Zn坩埚和Se坩埚的温度,各路载流气体的流量.对这些工艺参数进行调整和精确控制,并控制好Zn蒸气和Se蒸气气嘴处的ZnSe生长形态,生长出了质量良好的ZnSe多晶体,透过率超过70;.     

Growth of BiSrCaCuO thin films by MOCVD

Thermodynamic analysis of the system Bi–Sr–Ca–Cu–O–C–H–Ar using the Gibbs energy minimization method was performed to propose feasible deposition conditions for the growth of superconducting Bi-2212 films. The results show that the films containing Bi-2212 can be prepared at temperatures above 1000 K under reduced pressure with the input ratio Bi : Sr : C a : Cu close to 2 : 2 : 1 : 2. The growth experiments were carried out in a cold-wall RF-heated quartz reactor at temperatures of 800 and 850°C and a total pressure of 1 kPa. 2,2,6,6-tetramethyl-3,5-heptanedionates of Cu, Ca and Sr and triphenylbismuth were used as metal precursors. The films were characterized by X-ray diffraction, electron microprobe analysis and scanning electron microscopy. The highest critical temperature determined by measuring the AC magnetic response was 71 K.     

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。     

MOCVD生长低阈值电流GaInP/AlGaInP650nm激光器

通过MOCVD外延实现了限制层高铝组分及高掺杂,制作出低阈值电流密度的压应变多量子阱激光器材料,后工艺制备了低阈值电流基横模弱折射率脊形波导激光器.该激光器阈值电流最低达到6.2mA,这是我们所见报道的650nm AlGaInP红光激光器的最低阈值电流. 在25mA 工作电流下,基横模连续输出功率达到18mW.     

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;.     

MOCVD法在(220)CaF2衬底上生长ZnO薄膜及其性能研究

采用金属有机化学汽相沉积(MOCVD)法在(220)CaF2衬底上外延生长ZnO薄膜.利用X射线衍射(XRD)、紫外-可见光谱和光致发光谱(PL)对ZnO薄膜的结构和光学性能进行了分析.XRD结果表明,所制备的ZnO薄膜结晶性能良好,具有高度的(002)的择优取向,002衍射峰的半高宽(FMHM)为0.115°.所制备的ZnO薄膜透明,透过率超过85;.在常温的(He-Cd激光器)PL谱中,只有378.5 nm的带边发射.用同步辐射光源测试的真空紫外光谱中,在低温20K时,出现218 nm、368 nm、418 nm、554 nm发光峰,其中368 nm峰强度随着温度的升高强度逐渐下降,到常温时几乎消失.     

MOCVD生长温度对氧化锌薄膜结构及发光性能的影响

利用甲醇做氧源,采用金属有机物化学气相沉积(MOCVD)工艺在硅(111)衬底上生长了一系列的氧化锌薄膜,生长温度为400～600 ℃.薄膜的表面形貌及晶体质量分别利用场发射扫描电镜及X射线衍射仪进行了测量.研究表明:随着生长温度的降低,在X射线衍射图谱中氧化锌(101)峰取代了(002)峰成为了主峰.这可能是由于温度过低使得甲醇未完全分解,而甲醇分子抑制了氧化锌沿c轴极性过快的生长所致.室温光致发光光谱结果表明在较高生长温度下获得的样品具有良好的光学性质,发光强度随着温度的降低而降低.     

径向流动MOCVD输运过程的数值模拟和反应器优化

针对三重进口径向流动行星式MOCVD反应器的输运过程进行二维数值模拟研究,探讨有关行星式反应器流道高度和托盘直径能否继续扩大,如何控制基片上方温场和浓度场为最佳分布这样一些本质问题,同时寻找反应器的优化条件.模拟结果发现:(1)通过对反应器形状进行优化,使进口处流道趋向于流线的形状,可以大大地削弱甚至消除由流道扩张引起的涡旋;(2)在影响对流涡旋的几何参数中,反应腔高度起主要作用,而反应腔直径影响较小.对于优化后的反应器,发生对流涡旋的临界高度提高到2～2.5cm,对应的反应器直径增加到40cm;(3)在相同温差、不同衬底温度的条件下,反应器内的流动形态不同.衬底温度高,对流涡旋较弱;衬底温度低,对流涡旋较强.其原因在于气体的粘滞力随温度升高从而抑制了浮升力的作用;(4)衬底上方均匀的流场对应均匀的温场和较高的反应物浓度,热扩散则使TMGa在衬底处的浓度降低.     

在MOCVD系统中用预淀积In纳米点低温下合成生长InN

利用低压金属有机化学气相淀积(LP-MOCVD)系统,在(0001)蓝宝石衬底上采用预淀积In纳米点技术低温合成制备了立方相的InN薄膜.首先以TMIn作源在蓝宝石衬底表面预淀积了一层金属In纳米点,然后在一定条件下合成生长InN薄膜.X射线衍射谱(XRD)和X射线光电子发射谱(XPS)显示适当的预淀积In不仅能够促进InN的生长,同时还能够抑制金属In在InN薄膜中的聚集.原子力显微镜(AFM)观察表明,金属In纳米点不仅增强了成核密度,而且促进了InN岛的兼并.自由能计算表明预淀积的In优先和NH3分解得到的NH与N基反应生成InN.我们认为这种优先生成的InN为接下来InN的生长提供了成核位,从而促进了InN的生长.     

以S、Se为原料的CVD ZnS、CVD ZnSe的化学反应分析

本文详细分析了用单质硫或单质硒为原料,在Zn-S-H2-Ar体系或Zn-Se-H2-Ar体系中化学气相沉积生长 ZnS和ZnSe晶体所发生的化学反应,认为在这两种化学气相沉积过程中所发生的化学反应是以锌蒸汽与硫或硒蒸汽反应来实现的.计算出了上述反应的△H、△S和△G这些热力学函数,并将该△G与采用H2S气体(Zn-H2S-Ar体系)和H2Se气体(Zn-H2Se-Ar体系)为原料的CVD ZnS和ZnSe做了对比.实验结果表明,以单质Se为原料生长的CVD ZnSe比以H2Se为原料的CVD ZnSe的努普硬度有显著的提高.     

Growth of hexagonal and cubic InN nanowires using MOCVD with different growth temperatures

We have performed a detailed investigation of the metal-organic chemical vapor deposition (MOCVD) growth and characterization of InN nanowires formed on Si(1 1 1) substrates under nitrogen rich conditions. The growth of InN nanowires has been demonstrated by using an ion beam sputtered (∼10 nm) Au seeding layer prior to the initiation of growth. We tried to vary the growth temperature and pressure in order to obtain an optimum growth condition for InN nanowires. The InN nanowires were grown on the Au+In solid solution droplets caused by annealing in a nitrogen ambient at 700 °C. By applying this technique, we have achieved the formation of InN nanowires that are relatively free of dislocations and stacking faults. Scanning electron microscopy (SEM) showed wires with diameters of 90–200 nm and lengths varying between 3 and 5 μm. Hexagonal and cubic structure is verified by high resolution X-ray diffraction (HR-XRD) spectrum. Raman measurements show that these wurtzite InN nanowires have sharp peaks E₂ (high) at 491 cm⁻¹ and A₁ (LO) at 591 cm⁻¹.     

Properties of ZnO films grown on (0 0 0 1) sapphire substrate using H2O and N2O as O precursors by atmospheric pressure MOCVD

In this paper, we compare the properties of ZnO thin films (0 0 0 1) sapphire substrate using diethylzinc (DEZn) as the Zn precursor and deionized water (H₂O) and nitrous oxide (N₂O) as the O precursors, respectively in the main ZnO layer growth by atmospheric pressure metal–organic chemical vapor deposition (AP-MOCVD) technique. Surface morphology studied by atomic force microscopy (AFM) showed that the N₂O-grown ZnO film had a hexagonal columnar structure with about 8 μm grain diameter and the relatively rougher surface compared to that of H₂O-grown ZnO film. The full-widths at half-maximum (FWHMs) of the (0 0 0 2) and () ω-rocking curves of the N₂O-grown ZnO film by double-crystal X-ray diffractometry (DCXRD) measurement were 260 and 350 arcsec, respectively, indicating the smaller mosaicity and lower dislocation density of the film compared to H₂O-grown ZnO film. Compared to H₂O-grown ZnO film, the free exciton A (FX_A) and its three phonon replicas could be clearly observed, the donor-bound exciton A⁰X (I₁₀):3.353 eV dominated the 10 K photoluminescence (PL) spectrum of N₂O-grown ZnO film and the hydrogen-related donor-bound exciton D⁰X (I₄):3.363 eV was disappeared. The electron mobility (80 cm²/V s) of N₂O-grown ZnO film has been significantly improved by room temperature Hall measurement compared to that of H₂O-grown ZnO film.     

Growth of GaN/AlN and AlGaN by MOCVD using triethylgallium and tritertiarybutylaluminium

Films of aluminium nitride (AIN) with thicknesses in the range from 200 to 3600 Å have been deposited at 1050°C by low-pressure MOCVD. Using an alternative precursor, tritertiarybutylaluminium (^tBu₃Al), and ammonia (NH₃), we have grown AlN on sapphire (c-Al₂O₃). At a growth rate of 0.35 μm/h, the FWHM of the rocking curve measured by X-ray diffraction was 150 arcsec. Therefore, we used the thin AlN films as buffer layers for the deposition of gallium nitride (GaN) at 950°C using triethylgallium (Et₃Ga). Aluminium gallium nitride (Al_xGa_1−xN) with aluminium contents x from 0 to 0.5 were grown using a mixture of Et₃Ga and ^tBu₃Al. The strctural and optical properties of GaN, AlGaN and AlN were verified by X-ray diffraction (XRD), spectrally resolved photoconductivity (SPC), photothermal deflection (PDS) and photoluminescence spectroscopies.     

Room-temperature luminescence study on the effect of Mg activation annealing on p-GaN layers grown by MOCVD

An Mg-doped p-GaN layer was grown by the metalorganic chemical vapor deposition method. The dissociation extent of hydrogen-passivated Mg acceptors in the p-GaN layer through Mg activation annealing was estimated by using room-temperature cathodoluminescence (CL) spectroscopy. The CL measurement revealed that the CL spectra intensities tend to increase with increasing the activation annealing temperature. The sample annealed at 925 °C showed the most intense emission and the narrowest width among the emission peaks. Consequently, it was the most excellent dissociation extent of Mg–H complexes caused by the Mg activation annealing. The hole concentration under this optimum condition was 1.3×10¹⁷ cm⁻³ at room temperature. The photoluminescence (PL) measurement showed a 2.8 eV band having characteristically a broad peak in heavily Mg-doped GaN at room temperature. By analyzing the PL results, we learned that this band was associated with the deep donor–acceptor pair (DAP) emission rather than with the emission caused by the transition from the conduction band to deep acceptor level. The four emission peaks in the resolved 2.8 eV band were emitted by transiting from deep donor levels of 0.14, 0.26, 0.40, and 0.62 eV below the conduction band to the shallow Mg acceptor level of 0.22 eV above the valence band.     

Structural and optical properties of Zn(Mg,Cd)O alloy films grown by remote-plasma-enhanced MOCVD

We report the structural and optical properties of wurtzite-structure Zn(Mg,Cd)O ternary alloys. Wurtzite (0 0 0 1) Zn_1−xCd_xO and Mg_yZn_1−yO films were grown on (11–20) sapphire substrates using remote-plasma-enhanced metalorganic chemical vapor deposition. The large bowing parameters of Zn_1−xCd_xO and Mg_yZn_1−yO ternary alloys are 3.0 and 3.5, respectively, which reflects the large difference of each binary’s electronegativity. We have analyzed the broadening of photoluminescence (PL) in Zn(Mg,Cd)O alloys on alloy content by taking into account the statistical alloy fluctuation and the localization of the exciton, and have clarified that the localization of the exciton strongly affects to PL full-width at half-maximum (FWHM) in Zn(Mg,Cd)O alloys. The alloy broadenings in steady-state PL of Zn(Mg,Cd)O alloys are in good agreement with the calculated tendency by the theoretical model based on the statistical alloy fluctuation, while PL FWHM of Zn_1−xCd_xO is three times larger than the calculated results. Moreover, as another way to confirm alloy broadening, we also have done time-resolved PL measurements and derived the localized depth of the exciton in ZnO-based system, indicating a good agreement with the tendency of PL FWHM broadening.     

X-ray and cathodoluminescence study on the effect of intentional long time annealing of the InGaN/GaN multiple quantum wells grown by MOCVD

GaN-based InGaN/GaN multiple quantum wells (MQWs) structure having a high-quality epilayer and coherent periodicity was grown by metalorganic chemical vapor deposition. After thermal annealing of InGaN/GaN MQWs, the increase in temperature and annealing time caused the intermixing between the barrier and the wells, which in turn caused a decrease in periodicity on the high-resolution X-ray diffraction patterns. Thereby, we confirmed that the structural performance of InGaN MQWs is successively degrading with increasing thermal annealing temperature. Especially, InGaN MQWs of the sample annealed at 950 °C were profoundly damaged. The cathodoluminescence (CL) measurement indicated that MQWs emission intensity decreases with increasing thermal annealing temperature. Thus, the integrated CL intensity ratio of InGaN MQWs to GaN dramatically decreased while thermal annealing temperatures increased. This result caused the intermixing in MQWs to deteriorate the active layer performance. Furthermore, the peak position of MQWs showed a tendency of the red shift after high thermal annealing. It is suggested that the annealing-induced red shift in MQWs is attributed to the reduction of the inhomogeneity of the In content in the MQWs leading to the reduction of the quantized energies. Consequently, it indicates that the high temperature and the long-time thermal annealing would be inevitably followed by the structural destruction of InGaN MQWs.     

Photoluminescence characteristics of Mg- and Si-doped GaN thin films grown by MOCVD technique

We have studied the optical, structural and surface morphology of doped and undoped GaN thin films. The p- and n-type thin films have been successfully prepared by low-pressure MOCVD technique by doping with Mg and Si, respectively. The different carrier concentrations were obtained in the GaN thin films by varying dopant concentrations. Photoluminescence (PL) studies were carried to find the defect levels in the doped and undoped GaN thin films at low temperature. In the undoped GaN thin films, a low intensity and broad yellow band peak was observed. The donor–acceptor pair (DAP) emission and its phonon replicas were observed in both the Si or Mg lightly doped GaN thin films. The dominance of the blue and the yellow emissions increased in the PL spectra, as the carrier concentration was increased. The XRD and SEM analyses were employed to study the structural and surface morphology of the films, respectively. Both the doped and the undoped films exhibited hexagonal structure and polycrystalline nature. Mg-doped GaN thin films showed columnar structure whereas Si-doped films exhibited spherical shape grains.     

大气开放式MOCVD氧化镁薄膜的生长及表征

以2,4-乙酰丙酮化镁为前驱体,衬底温度为480℃,采用MOCVD工艺,分别在玻璃、氧化铝陶瓷、单晶Si(111)和Si(100)衬底上生长了取向生长的氧化镁薄膜。X射线衍射结果表明,无论是采用玻璃、氧化铝、单晶Si(111)和Si(100)衬底,氧化镁薄膜都是沿着(100)晶面取向生长。通过扫描电镜观察得到,在单晶Si(100)衬底上生长的氧化镁薄膜表面平整致密。模拟卢瑟福背散射结果显示,沉积时间超过70min时,界面处发生硅向氧化镁层少量扩散现象。