Maskless Lateral Epitaxial Growth of Gallium Nitride Using Dimethylhydrazine as a Nitrogen Precursor

Lateral epitaxial growth (LEG) is a key technology to improve the lifetime of III-V nitride-based laser diodes (LDs) by reducing the dislocation density in the materials. To increase the area of low dislocation density, the lateral growth rate needs to be increased. In addition, suppression of the vertical growth is strongly desired to avoid unnecessarily thick growth, which would result in cracks in the epitaxial film. This paper reports the maskless LEG of GaN with extremely high lateral-to-vertical growth rate ratio using dimethylhydrazine as a nitrogen precursor. The lateral growth only occurs from the sidewalls of the etched mesa stripes without any dielectric masks. The lateral growth rate toward the direction is extremely high, as high as 10 μm/h, while no vertical growth is observed on the top of unmasked mesa. The cross-sectional transmission electron microscopic image shows that the threading dislocations in the wing region extend only toward the lateral direction. Note that almost smooth coalescence between the wing regions is confirmed by atomic force microscopy. X-ray diffraction measurements reveal that this maskless LEG drastically improves the crystallographic twist down to 97 arc-s, which is as comparably low as that of a free-standing GaN substrate. The presented maskless LEG is advantageous for optical device applications.     

Ga掺杂ZnO薄膜的MOCVD生长及其特性

利用低压MOCVD技术在(0002)蓝宝石上外延获得高质量的ZnO∶Ga单晶薄膜,并研究了Ga的不同掺杂浓度对材料电学和光学特性的影响．当Ga/Zn气相摩尔比为3.2 at%时,ZnO(0002)峰半高宽仅为0.26°,载流子浓度高达2.47e19cm－3,透射率高于90%;当载流子浓度升高时,吸收边出现明显的Burstein-Moss蓝移效应．同时室温光致发光谱显示,紫外峰位随载流子浓度的增加而发生红移,峰形展宽,这和Ga高掺杂所引起的能带重整化效应有关．当Ga/Zn比达到6.3 at%时,由于高掺杂浓度下Ga的自补偿效应导致载流子浓度下降．     

MOCVD法制备磷掺杂p型ZnO薄膜

利用金属有机化学气相沉积方法在玻璃衬底上生长了掺磷的p型ZnO薄膜.实验采用二乙基锌作为锌源,高纯氧气和五氧化二磷粉末分别作为氧源及磷掺杂源.实验表明:生长温度为400～450℃时获得了p型ZnO薄膜,而且在420℃时,其电学性能最好,空穴浓度为1.61×1018cm-3,电阻率为4.64Ω·cm,迁移率为0.838cm2/(V·s).霍尔测试和低温光致发光谱证实了该ZnO薄膜的p型导电特性,并观察到薄膜位于3.354eV与中性受主束缚激子相关的发射峰.     

MOCVD法制备磷掺杂p型ZnO薄膜

利用金属有机化学气相沉积方法在玻璃衬底上生长了掺磷的p型ZnO薄膜.实验采用二乙基锌作为锌源,高纯氧气和五氧化二磷粉末分别作为氧源及磷掺杂源.实验表明:生长温度为400～450℃时获得了p型ZnO薄膜,而且在420℃时,其电学性能最好,空穴浓度为1.61×1018cm-3,电阻率为4.64Ω·cm,迁移率为0.838cm2/(V·s).霍尔测试和低温光致发光谱证实了该ZnO薄膜的p型导电特性,并观察到薄膜位于3.354eV与中性受主束缚激子相关的发射峰.     

Realization of intrinsic p-type ZnO thin films by metal organic chemical vapor deposition

P-type ZnO thin films were grown on sapphire substrates with and without nitrous oxide (N₂O) by metal organic chemical vapor deposition (MOCVD). The intrinsic p-type ZnO films were achieved by controlling the Zn:O ratio in the range of 0.05–0.2 without N₂O flow. Secondary ion mass spectroscopy (SIMS) showed that the films contained little or no nitrogen (N) impurities for all samples. The p-type behavior of the samples should be due to the intrinsic acceptor-like defects V_Zn, for ZnO film grown without nitrous oxide, and N, occupying O sites as acceptors for ZnO film grown with nitrous oxide. The best p-type ZnO film has low resistivity of 0.369 Ω-cm, high carrier density of 1.62×10¹⁹ cm⁻³, and mobility of 3.14 cm²/V-s. The obtained p-type ZnO films possess a transmittance of nearly 100% in the visible region and strong near-band-edge emission.     

低压MOCVD生长ZnO单晶薄膜的制备与性质

利用 LP-MOCVD生长技术 ,采用 Zn(C2 H5) 2 作 Zn源和 CO2 作氧源 ,在 (0 0 0 2 )蓝宝石衬底上获得了沿 c轴取向高度一致的 Zn O单晶薄膜。通过对其吸收谱的曲线拟合 ,得到室温下 Zn O薄膜的光学带隙为 3 .2 45e V。在样品的室温光荧光谱 (PL)中观察到对应于带边发射的较强的发光峰 ,对样品中蓝带的产生原因进行了讨论     

MOCVD制备用于薄膜太阳电池的ZnO薄膜研究

利用金属有机物化学气相沉积(MOCVD)生长技术,采用二乙基锌(DEZ)作Zn源和H2O作O源,使用B2H6 为掺杂气体,制备出了光电特性稳定的低电阻率、高透过率的ZnO薄膜。制备条件为:衬底温度160 ℃,DEZ的流量为342μmol/min,H2O流量为500μmol/min,反应气压为5×133.32 Pa,B2H6 流量为5 sccm,掺杂手段为气体掺杂。在薄膜面积为10 cm×10 cm、厚度为550 nm时,方块电阻为40Ω/□。透过率>85%。     

反应压力对MOCVD法沉积ZnO薄膜性质的影响

研究了反应压力对金属有机化学气相沉积(MOCVD)技术制备未掺杂ZnO薄膜的微观结构和光电特性影响.X射线衍射(XRD)和扫描电子镜(SEM)的研究结果表明,随着反应压力的降低,ZnO薄膜(002)择优峰的强度呈现相对减弱趋势,并且出现了较强的(110)峰;Hall测量表明,低的反应压力有助于提高薄膜电学特性.200 Pa时制备出的ZnO薄膜具有明显的"类金字塔"状绒面结构,电阻率为1.28×10-2 Ω·cm.实验中沉积的ZnO薄膜在600～2 600 nm内平均透过率超过80%,而短波长范围由于光散射作用,ZnO薄膜的垂直透过率有所下降.     

Interface properties of ZnO nanotips grown on Si substrates

ZnO nanotips have been grown on Si (100) using metalorganic chemical vapor deposition (MOCVD). The growth temperature is optimized for good crystallinity, morphology, and optical properties. ZnO nanotips exhibit a strong near band edge emission of ∼376 nm at room temperature with negligible green band emission. Pregrowth substrate treatment using diluted hydrofluoric acid (HF) and minimized oxygen exposure before the initial growth significantly reduces the interfacial SiO₂ thickness, while maintaining good morphology. An n-ZnO nanotips/p-Si diode is fabricated and its I–V characteristic is measured. The threshold voltage of the diode is found to be below 2.0 V with small reverse leakage current. The ZnO/p-Si diodes provide the possibility of integrating the ZnO nanotips with Si-based electronic devices.     

Influences of ZnO buffer layers on the quality of ZnO films synthesized by the metal-organic chemical vapor deposition process

High-quality ZnO thin films were prepared by metal-organic chemical vapor deposition (MOCVD) on a sapphire (a-Al₂O₃) substrate. The synthesis of ZnO films was performed over a substrate temperature of 400–700°C and at chamber pressures of 0.1–10 torr. The structural and optical properties of ZnO films were investigated in terms of deposition conditions, such as substrate temperature, working pressure, and the ratio of Zn precursor (Diethylzinc (DEZn)) to oxygen. The ZnO films, preferentially oriented to 34.42° diffraction because of the (002) plane, were obtained under processing conditions of 700°C and 3 torr. This film shows a full-width at half-maximum (FWHM) of 0.4–0.6°. The results of photoluminescence (PL) spectroscopy also show a strong near band-edge emission at 3.36 eV at 10 K as well as a very weak emission at deep levels around 2.5 eV at room temperature. In addition, we are interested in the introduction of ZnO buffer-layer growth by the sputtering process to reduce lattice mismatch stress. This paper addresses how to advance the crystalline and optical properties of film. The ZnO film grown with the aid of a buffer layer shows a FWHM of 0.06–0.1° in the x-ray diffraction (XRD) pattern. This result indicates that crystalline properties were highly improved by the ZnO buffer layers. The PL spectroscopy data of ZnO film also shows a strong near band-edge emission and very weak deep-level emission similar to films synthesized without a buffer layer. Accordingly, synthesized ZnO films with buffer layers indicate fairly good optical properties and low defect density as well as excellent crystallinity.     

Photoluminescent properties of ZnO thin films grown on SiO2/Si(100) by metal-organic chemical vapor deposition

We report on the photoluminescent (PL) properties of ZnO thin films grown on SiO₂/Si(100) substrates using low pressure metal-organic chemical vapor deposition. The growth temperature of the films was as low as 400°C. From the PL spectra of the films at 10–300 K, strong PL peaks due to free and bound excitons were observed. The origin of the near bandedge emission peaks was investigated measuring temperature-dependent PL spectra. In addition, the Zn O films demonstrated a stimulated emission peak at room temperature. Upon illumination with an excitation density of 1 MW/cm², a strong, sharp peak was observed at 3.181 eV.     

Growth of phosphorus-doped p-type ZnO thin films by MOCVD

Phosphorus-doped p-type ZnO thin films are prepared on glass substrates by metalorganic chemical vapor deposition (MOCVD). DEZn, O2, and P2O5 powders are used as reactant and dopant sources. The p-type ZnO films are grown at a temperature between 673 K and 723 K. The best p-type sample has a low resistivity of A strong emission peak at 3.354 eV corresponding to neutral acceptor bound excitons is observed at 77 K in the photoluminescence spectra, which further verifies the p-type characteristics of the films.     

Metalorganic chemical vapor deposition and characterization of ZnO materials

Zinc oxide is attracting growing interest for potential applications in electronics, optoelectronics, photonics, and chemical and biochemical sensing, among other applications. We report herein our efforts in the growth and characterization of p- and n-type ZnO materials by metalorganic chemical vapor deposition (MOCVD), focusing on recent nitrogen-doped films grown using diethyl zinc as the zinc precursor and nitric oxide (NO) as the dopant. Characterization results, including resistivity, Hall measurements, photoluminescence, and SIMS, are reported and discussed. Electrical behavior was observed to be dependent on illumination, atmosphere, and heat treatment, especially for p-type material.     

Fast and Reversible Wettability Transitions on ZnO Nanostructures

Surface wettability is an important property of solid/liquid interfaces. Recently, the control of contact angle (CA) has been used to drive liquid droplets in micro- or nanosize channels on biochemical and environmental sensing chips, where a faster CA transition rate is desirable for the prompt control of liquid movement. We studied the CA between water droplet and zinc oxide (ZnO) nanotips grown by metalorganic chemical vapor deposition (MOCVD). ZnO was grown as epitaxial films on r-plane sapphire, or as vertically aligned nanotips on various substrates, including silicon, c-plane sapphire, and glass. It is demonstrated that by using ultraviolet (UV) illumination and oxygen annealing, the CA on ZnO nanotips can be changed between 0° and 130°, whereas the CA on the ZnO films only varies between 37° and 100°. The fast transition rates also have been observed. (Received October 16, 2006; accepted January 23, 2007)     

氧源的射频离化对ZnO MOCVD材料生长与性质的影响

在不同温度条件下，利用低压金属有机源化学气相沉积（LP-MOCVD）系统制备ZnO薄膜，对在氧源离化和非离化两种状态下生长的ZnO薄膜材料进行了相关的研究比较．通过X射线衍射（XRD）、原子力显微镜（AFM）、低温光致发光谱等方法研究了离化参数与生长速率、晶体质量、表面结构以及光学特性之间的相互关系，研究发现射频等离子体离化对薄膜生长速率等参数有明显的影响，通过优化相关离化实验参数可以极大的改进和提高材料的结构和光学性质．     

Nonalloyed Al ohmic contacts to MgxZn1−xO

Al nonalloyed ohmic contacts were fabricated and characterized on Mg_xZn_1−xO (0≤×≤0.34) epilayers, which were grown on R-plane sapphire substrates by metal organic chemical vapor deposition (MOCVD). Specific contact resistances were evaluated by the transmission line method (TLM). A specific contact resistance of 2.5×10⁻⁵ Ωcm² was obtained for Al contact to ZnO with an electron concentration of 1.6×10¹⁷ cm⁻³. The current flow mechanism was studied by investigating the dependence of specific contact resistances on electron concentration and on temperature. For Al contact to Mg_0.34Zn_0.66O, specific contact resistance values are two orders of magnitude larger than that of Al ohmic contacts to ZnO.     

Controllable p-Type Doping of 2D WSe2 via Vanadium Substitution

Scalable substitutional doping of 2D transition metal dichalcogenides is a prerequisite to developing next-generation logic and memory devices based on 2D materials. To date, doping efforts are still nascent. Here, scalable growth and vanadium (V) doping of 2D WSe₂ at front-end-of-line and back-end-of-line compatible temperatures of 800 and 400 °C, respectively, is reported. A combination of experimental and theoretical studies confirm that vanadium atoms substitutionally replace tungsten in WSe₂, which results in p-type doping via the introduction of discrete defect levels that lie close to the valence band maxima. The p-type nature of the V dopants is further verified by constructed field-effect transistors, where hole conduction becomes dominant with increasing vanadium concentration. Hence, this study presents a method to precisely control the density of intentionally introduced impurities, which is indispensable in the production of electronic-grade wafer-scale extrinsic 2D semiconductors.     

Ultraviolet detectors based on epitaxial ZnO films grown by MOCVD

High-quality zinc oxide (ZnO) films were epitaxially grown on R-plane sapphire substrates by metalorganic chemical vapor deposition at temperatures in the range of 350°C to 600°C. In-situ nitrogen compensation doping was performed using NH₃. Microstructural and optical properties of the films, as well as the N-doping effects, were studied. The metal-semiconductor-metal ultraviolet sensitive photodetectors were fabricated on N-doped epitaxial ZnO films. The detector showed fast photoresponse, with a rise time of 1 μs and a fall time of 1.5 μs. Low-frequency photoresponsivity, on the order of 400 A/W at 5 V bias, was obtained.     

GaN基材料及其外延生长技术研究

介绍了GaN基材料的基本特性、三种主要外延生长技术(MOCVD、MBE、HVPE)、衬底材料的选择及缓冲层技术;分析得出目前存在的GaN体单晶技术不完善、外延成本高、衬底缺陷及接触电阻大等主要问题制约了研究的进一步发展;指出今后的研究重点是完善GaN体单晶材料的生长工艺,以利于深入研究GaN的物理特性及有效地解决衬底问题,研究缓冲层的材料、厚度、组分等以提高GaN薄膜质量。     

基于AlN和GaN形核层的AlGaN/GaN HEMT外延材料和器件对比

使用金属有机物化学气相淀积(MOCVD)方法在蓝宝石衬底上分别采用AlN和GaN作为形核层生长了AlGaN/GaN高电子迁移率晶体管(HEMT)外延材料,并进行了器件制备和性能分析.通过原子力显微镜(AFM)、高分辨率X射线双晶衍射仪(HR-XRD)和二次离子质谱仪(SIMS)等仪器对两种样品进行了对比分析,结果表明采用AlN形核层的GaN外延材料具有更低的位错密度,且缓冲层中氧元素的拖尾现象得到有效地抑制.器件直流特性显示,与基于GaN形核层的器件相比,基于AlN形核层的器件泄漏电流低3个数量级.脉冲Ⅰ-Ⅴ测试发现基于GaN形核层的HEMT器件受缓冲层陷阱影响较大,而基于AlN形核层的HEMT器件缓冲层陷阱作用不明显.