Organometallic chemistry related to applications for microelectronics in Japan

This is meant to be a brief overview of the developments of research activities in Japan on organometallic compounds related to their use in electronic and optoelectronic devices. The importance of organometallic compounds in the deposition of metal and semiconductor films for the fabrication of many electronic and opto-electronic devices cannot be exaggerated. Their scope has now extended to thin-film electronic ceramics and high-temperature oxide superconductors. A variety of organometallic compounds have been used as source materials in many types of processing procedures, such as metal–organic chemical vapor deposition (MOCVD), metalorganic vapor-phase epitaxy (MOVPE), metal–organic molecular-beam epitaxy (MOMBE), etc. Deposited materials include silicon, Group III–V and II–VI compound semiconductors, metals, superconducting oxides and other inorganic materials. Organometallic compounds are utilized as such in many electronic and optoelectronic devices; examples are conducting and semiconducting materials, photovoltaic, photochromic, electrochromic and nonlinear optical materials. This review consists of two parts: (I) research related to the fabrication of semiconductor, metal and inorganic materials; and (II) research related to the direct use of organometallic materials and basic fundamental research.     

Coexistence properties of phase separation and CuPt-ordering in InGaAsP grown on GaAs substrates by organometallic vapor phase epitaxy

CuPt-ordering and phase separation were directly investigated in In_1-xGa_xAs_yP_1-y with a low arsenic content grown by organometallic vapor phase epitaxy on GaAs substrates. CuPt-ordering and phase separation in samples grown at the substrate temperatures of 630 and 690 °C were characterized by transmission electron diffraction and transmission electron microscopy. Although the immiscibility of InGaAsP was enhanced at the lower substrate temperature, the sample grown at 630 °C showed less phase separation than the 690 °C-grown sample. The degree of CuPt-ordering was significantly enhanced in the sample grown at 630 °C. The results demonstrated that the CuPt-ordering originating from surface reconstruction of P(2×4) suppressed the phase separation even in the miscibility gap. The detailed characterization of the phase separation clearly revealed a vertical composition modulation (VCM) in InGaAsP for the first time. The mechanism of the VCM formation is discussed based on the modulated-strain field on the surface.     

InGaAsP multiple quantum well edge-emitting light-emitting diode showing low coherence characteristics using selective-area metalorganic vapor phase epitaxy

Low coherence multiple-quantum well edge-emitting light-emitting diodes were obtained using selective-area metalorganic vapor-phase epitaxial growth, which utilized growth rate enhancement on an open stripe region between mask stripes. An optical absorption region, which was controlled by selective-area growth, was introduced to suppress optical feedback. At a driving current of 100 mA and an ambient temperature of 25°C, a power of 55 μW was coupled into a single-mode fiber, and a broad spectrum without spectral ripple was observed. Low coherence characteristics and very small temperature dependence were obtained in the temperature range from -40°C to 85°C. The modulation bandwidth was 210 MHz at a bias current of 100 mA.     

MOVPE生长GaN的表面反应机理

利用量子化学的 DFT 理论,对 MOVPE 生长 GaN 薄膜的表面初始反应机理进行研究。通过计算GaCH3和NH3在GaN(0001)-Ga面的4种吸附位的能量曲线发现,GaCH3在各吸附位的吸附能差值不大,因此容易在表面迁移;而NH3在各吸附位的吸附能差值较大,最稳定吸附位为Top位,迁移到其他位置需要克服较大能垒。在此基础上,提出了以NH3和 GaCH3为表面生长基元,在GaN(0001)-Ga面连续生长,最终形成环状核心的二维生长机理：在环状核心形成过程中,第1个GaN核生长需要3个NH3和1个GaCH3,可表示为Ga( NH2)3。第2个GaN核生长可利用已有的1个N作为配位原子,故只需2个NH3和1个GaCH3。2个GaN核可表示为( NH2)2 Ga-NH-Ga( NH2)2。第3个GaN核生长可利用已有的2个N作为配位原子,故只需要1个NH3和1个GaCH3。3个GaN核构成环状核心,可表示为Ga3( NH)3( NH2)3。后续的生长将重复第2个核和第3个核的生长过程,从而实现GaN薄膜的连续台阶生长。     

Thermodynamic analysis of Si doping in GaN

Equilibrium calculations of Si-doping in GaN are investigated using the Gemini code. The method of the calculation is based on the minimisation of the Gibbs free energy. Experimental growth conditions are used for the calculation. The variables are the amount of the dopant and the temperature. The results show the formation of a solid Si₃N₄ compound with a certain quantity of the input SiH₄, that is the silicon precursor in our MOVPE system. Si₃N₄ formation can explain the limitation of Si incorporation and the surface roughening as revealed by MOVPE Si doped layers.     

Carrier dynamics in strain-induced InGaAsP/InP quantum dots

Carrier dynamics of strain-induced InGaAsP/InP quantum dots (QDs) is investigated. In this structure, self-assembled InAs islands on the surface act as stressors and create a lateral confinement potential in the near surface InGaAsP/InP quantum well. Photoluminescence (PL) measurements reveal that decreasing the distance from the QD to the surface significantly diminishes the QD–PL intensity, presumably due to surface states of the InAs islands. Moreover, time-resolved measurements show a faster decay of the QD–PL with decreasing distance. To analyze the carrier dynamics, rate equation model is applied and surface state-related transitions are taken into account. The model is found to agree with measurements, and thus provides a possible explanation for the observed temporal behavior of the carriers.     

InP的MOVPE生长

我们利用自制的常压MOVPE设备和国产的三甲基钢以及进口的磷烷生长了InP外延材料,其77K迂移率为65300cm²/V·s,据我们所知这是国内迄今为止用各种方法获得的InP薄膜的最大低温迁移率值。     

Heteroepitaxial growth of thin InAs layers on GaAs(1 0 0) misoriented substrates: A structural and morphological comparison

Thin InAs epilayers were grown on GaAs(1 0 0) substrates exactly oriented and misoriented toward [1 1 1]A direction by atmospheric pressure metalorganic vapor phase epitaxy. InAs growth was monitored by in situ spectral reflectivity. Structural quality of InAs layers were studied by using high-resolution X-ray diffraction. No crystallographic tilting of the layers with respect to any kind of these substrates was found for all thicknesses. This result is discussed in terms of In-rich growth environment. InAs layers grown on 2° misoriented substrate provide an improved crystalline quality. Surface roughness of InAs layers depend on layer thickness and substrate misorientation.     

MOVPE生长GaN薄膜的表面吸附和扩散研究

利用量子化学计算方法,对MOVPE生长GaN薄膜的表面反应进行研究.特别针对反应前体GaCH3(简称MMG)在理想、H覆盖和NH2覆盖GaN(0001)面的吸附和扩散进行计算分析.通过建立3×3 超晶胞模型,优化计算了MMG在三种不同覆盖表面的稳定吸附位、吸附能和电子布居,搜寻了MMG在稳定吸附位之间的扩散能垒.计算结果表明:对于三种表面,MMG的稳定吸附位均为T4位和H3位,H3位比T4位略微稳定.MMG在NH2覆盖表面吸附能最大,在H覆盖表面吸附能最小,在理想表面吸附能居中.MMG中的Ga与不同的表面原子形成的化学键的键强的大小顺序为:Ga-N>Ga-Ga>Ga-H.相比于理想表面和H覆盖表面,MMG在NH2覆盖表面的扩散能垒最大,因此表面过量的NH2会抑制MMG的扩散.     

Effects of substrate temperature upon the properties of ZnMgTe layer grown by MOVPE

The effects of substrate temperature upon the optical property, composition and surface morphology have been investigated on nominally undoped Zn_1−xMg_xTe layers grown on (1 0 0) ZnTe substrates by atmospheric pressure metal organic vapor phase epitaxy (MOVPE). It was found that Mg composition increases with decreasing substrate temperature. The result of low temperature photoluminescence (PL) measurement suggests that the optical quality of Zn_1−xMg_xTe layers becomes better with decreasing substrate temperature. On the other hand, there is a narrow range of optimal substrate temperature for a smooth surface morphology. For all the layers, a two-mode behavior with ZnTe- and MgTe-like longitudinal optical phonon modes was confirmed by Raman scattering.