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.     

改善玻璃衬底上ZnO薄膜特性的方法

利用磁控溅射法在玻璃衬底上淀积铝掺杂氧化锌(AZO)薄膜作为缓冲层,在其上制备了ZnO薄膜。重点研究了AZO薄膜作为缓冲层对玻璃衬底上ZnO薄膜特性的影响。扫描电子显微镜(SEM)图像和X射线衍射(XRD)图谱分析结果表明,玻璃衬底上加入厚度为1μm的AZO缓冲层后,提高了衬底材料和ZnO薄膜之间的晶格匹配程度,有助于增大ZnO薄膜晶粒尺寸,提高其(002)取向择优生长特性、薄膜结晶特性及晶格结构完整性。室温下的透射光谱结果表明玻璃/AZO和玻璃衬底上ZnO薄膜的透光特性没有显著不同。光致发光(PL)谱研究结果表明AZO缓冲层可以有效阻止衬底表面硅原子从ZnO薄膜中"俘获"氧原子,减少ZnO薄膜中的缺陷,改善ZnO薄膜的结晶质量。     

Improvement in crystal quality of ZnO film on Si substrate by using a homo-buffer layer

ZnO thin films without and with a homo-buffer layer have been prepared on Si(1 1 1) substrates by pulsed laser deposition (PLD) under various conditions. Photoluminescence (PL) measurement indicates that the optical quality of ZnO thin film is dramatically improved by introducing oxygen into the growth chamber. The sample deposited at 60 Pa possesses the best optical properties among the oxygen pressure range studied. X-ray diffraction (XRD) results show that the films directly deposited on Si are of polycrystalline ZnO structures. A low-temperature (500 °C) deposited ZnO buffer layer was used to enhance the crystal quality of the ZnO film. Compared to the film without the buffer layer, the film with the buffer layer exhibits aligned spotty reflection high-energy electron diffraction (RHEED) pattern and stronger near-band-edge emission (NBE) with a smaller full-width at half-maximum (FWHM) of 98 meV. The structural properties of ZnO buffer layers grown at different temperatures were investigated by RHEED patterns. It is suggested that the present characteristics of the ZnO epilayer may be raised further by elevating the growth temperature of buffer layer to 600 °C.     

两步法生长ZnO纳米棒的结构及其发光特性

应用两步法在玻璃衬底上制备了高度取向的ZnO纳米棒,并研究了衬底和反应时间等参数对其结构及发光特性的影响。从样品的扫描电镜(SEM)图中发现,利用脉冲激光沉积(PLD)方法在玻璃衬底上生长一层ZnO薄膜作为修饰层,可以明显提高水热法生长的ZnO纳米棒的结晶质量。样品的SEM和光致发光(PL)谱表明,在有ZnO修饰层的玻璃衬底上生长的ZnO纳米棒分布均匀,排列致密,取向性好;缺陷发光的发光强度约是激子发光峰的2倍,且随着反应时间增长,样品的缺陷发光增强而激子发光减弱。     

适用SAW器件的ZnO/Ti/Si薄膜制备及缺陷分析

在Si(100)衬底和Ti/Si(100)衬底上分别制备了ZnO薄膜,探讨了Ti缓冲层对ZnO薄膜结构和缺陷的影响,利用X射线衍射(XRD)测试了ZnO薄膜的晶体结构及择优取向,利用原子力显微镜(AFM)观察ZnO薄膜的表面粗糙度(RMS),利用光致发光(PL)光谱检测了ZnO薄膜的缺陷,利用四探针法测试了ZnO薄膜的电阻率。结果表明,在Ti/Si(100)衬底上、衬底温度350℃的条件下,制备的ZnO薄膜表面光滑、缺陷少、电阻率高且具有高C轴取向。本文这一工作对于压电薄膜缺陷分析及高性能ZnO的声表面波(SAW)器件研制有重要意义。     

GaN缓冲层对生长InN薄膜的影响

采用金属有机物化学气相沉积(MOCVD)方法生长六方相InN薄膜，利用氮化镓(GaN)缓冲层技术制备了高质量薄膜，得到了其能带带隙0.7eV附近对应的光致发光光谱(PL). 通过比较未采用缓冲层，同时采用低温和高温GaN缓冲层，以及低温GaN缓冲层结合高温退火三种生长过程，发现低温GaN缓冲层结合高温退火过程能够得到更优表面形貌和晶体质量的InN薄膜，同时表征了材料的电学性质和光学性质. 通过对InN薄膜生长模式的讨论，解释了薄膜表面形貌和晶体结构的差异.     

Epitaxial growth of ZnO on GaN/sapphire substrate by radio-frequency magnetron sputtering

Zinc oxide (ZnO) thin films were grown on n-GaN/sapphire substrates by radio-frequency (RF) magnetron sputtering. The films were grown at substrate temperatures ranging from 400 to 700 ℃ for 1 h at a RF power of 80 W in pure Ar gas ambient. The effect of the substrate temperature on the structural and optical properties of these films was investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL) spectra. XRD results indicated that ZnO films exhibited wurtzite symmetry and c-axis orientation when grown epitaxially on n-GaN/sapphire. The best crystalline quality of the ZnO film is obtained at a growth temperature of 600 ℃. AFM results indicate that the growth mode and degree of epitaxy strongly depend on the substrate temperature. In PL measurement, the intensity of ultraviolet emission increased initially with the rise of the substrate temperature, and then decreased with the temperature. The highest UV intensity is obtained for the film grown at 600 ℃ with best crystallization.     

溅射ZnO薄膜钝化GaAs表面性能的研究

为了改善GaAs(110)与自身 氧化物界面由于高表面态密度而引起的费米能级钉扎(pinning)问题 ,提出采用射频磁控溅射技 术在GaAs(110)衬底上沉积一定厚度 ZnO薄膜作为钝化层,并利用光 致发光(PL)光谱和X射线光电子能谱(XPS) 等方法对ZnO薄膜的光学特性及钝化性能进行表征。实验结果表明,经ZnO薄膜钝化后的 GaAs样品,其本征PL峰强度提高112.5%,杂质峰强度下降82.4%。XPS光谱分析表明,Ga和As原子的比值从1.47降低 到0.94,ZnO钝化层能 够抑制Ga和As的氧化物形成。因此,在GaAs表面沉积ZnO薄膜是一种可行的GaAs表面钝化 方法。     

以ZnO为空穴缓冲层的高效率有机电致发光器件

研制了在传统双层有机电致发光器件(OLED) ITO/NPB/AlQ/Al的阳极与空穴传输层间加入ZnO缓冲层的新型器件.研究了加入缓冲层后对OLED性能的影响,并比较了新型与传统OLED的性能,结果表明,新型器件比传统器件的耐压能力有了显著提高;当电压达到7 V时,发光效率提高了35%.分析认为,ZnO缓冲层的加入,改善了界面, 减少了漏电流,并且阻碍了空穴的注入,有利于改善空穴和电子的注入平衡,提高复合效率.     

Growth of Polarity-Controlled ZnO Films on (0001) Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

The polarity control of ZnO films grown on (0001) Al₂O₃ substrates by plasma-assisted molecular-beam epitaxy (P-MBE) was achieved by using a novel CrN buffer layer. Zn-polar ZnO films were obtained by using a Zn-terminated CrN buffer layer, while O-polar ZnO films were achieved by using a Cr₂O₃ layer formed by O-plasma exposure of a CrN layer. The mechanism of polarity control was proposed. Optical and structural quality of ZnO films was characterized by high-resolution X-ray diffraction and photoluminescence (PL) spectroscopy. Low-temperature PL spectra of Zn-polar and O-polar samples show dominant bound exciton (I₈) and strong free exciton emissions. Finally, one-dimensional periodic structures consisting of Zn-polar and O-polar ZnO films were simultaneously grown on the same substrate. The periodic inversion of polarity was confirmed in terms of growth rate, surface morphology, and piezo response microscopy (PRM) measurement.     

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     

ZnO nanotips grown on Si substrates by metal-organic chemical-vapor deposition

The ZnO nanotips are grown on silicon and silicon-on-sapphire (SOS) substrates using the metal-organic chemical-vapor deposition (MOCVD) technique. The ZnO nanotips are found to be single crystal and vertically aligned along the c-axis. In-situ Ga doping is carried out during the MOCVD growth. The ZnO nanotips display strong near-band edge photoluminescence (PL) emission with negligible deep-level emission. Free excitonic emission dominates the 77-K PL spectrum of the as-grown, undoped ZnO nanotips, indicating good optical properties and a low defect concentration of the nanotips. The increase of PL intensity from Ga doping is attributed to Ga-related impurity band emission. Photoluminescence quenching is also observed because of heavy Ga doping. ZnO nanotips grown on Si can be patterned through photolithography and etching processes, providing the potential for integrating ZnO nanotip arrays with Si devices.     

在ZnO/Si衬底上ZnCdSe/ZnSe多量子阱的生长与光学特性

在经NH3等离子体氮化的Si(100)衬底上。用等离子体增强化学气相淀积(PECVD)的方法生长了ZnO缓冲层，经X射线衍射(XRD)测量，得到了单一取向的ZnO(0002)膜。在此ZnO缓冲层上利用低压金属有机化学气相淀积(LP-MOCVD)方法生长了较高质量的ZnCdSe／ZnSe量子阱。通过不同阱宽的ZnCdSe／ZnSe量子阱生长和测量，得到了多级共振拉曼峰。从发光谱中可见，在1520nm附近有很强的发光，而在未覆盖ZnO的Si衬底上直接生长的ZnCdSe／ZnSe量子阱结构，其光致发光(PL)谱未见发光。可见，在氮化的Si衬底上覆盖ZnO膜生长的ZnCdSe/ZnSe量子阱质量较好。是一种在Si衬底上生长Ⅱ-Ⅵ族化合物半导体材料的有效方法。     

氧压对ZnO薄膜电阻温度系数的影响

采用脉冲激光沉积(PLD)技术,在不同氧气氛下,在Si(lll)衬底上生长了ZnO薄膜,使用X线衍射仪分析了ZnO薄膜的结晶质量.计算了不同氧气氛下生长的ZnO薄膜的电阻温度系数(TCR)值,发现随着氧分压降低,ZnO薄膜的TCR值增大;ZnO薄膜的TCR值最高可达-8%/K.这为研究ZnO薄膜的导电特性提供了新的途径,开辟了ZnO薄膜在室温非制冷红外微测辐射热计材料中的应用潜力.     

Morphology and growth mechanism of aligned ZnO nanorods grown by catalyst-free MOCVD

We report on ZnO nanorods grown by catalyst-free metal-organic chemical vapour deposition (MOCVD) in a commercial Epigress reactor using diethylzinc and N₂O as precursors. Well-aligned ZnO nanorods with uniform diameter, length and density have been grown perpendicularly to the sapphire (0 0 0 1) surface. Scanning electron microscopy (SEM) has been used to observe the morphology of the ZnO nanorods and X-ray diffraction and transmission electron microscopy (TEM) to investigate the crystalline structure of the nanorods. TEM observation as well as photoluminescence measurements confirm the very good crystalline quality of the nanorods. SEM observation on samples that have been prepared with various deposition times has been used in order to investigate the growth mechanism. Three types of ZnO morphologies have been identified: a thin two-dimensional ZnO layer formed at the sapphire surface, covered by three-dimensional hexagonal-shaped islands and hexagonal nanorods on top of them.     

ZnO材料的生长及表征

氧化锌材料是新一代宽禁带光电子半导体材料和场致发射材料，通过等离子体分子束外延设备，在a-plane的蓝宝石衬底上生长了高质量的氧化锌外延材料。在生长过程中用反射高能电子束衍射仪(RHEED)，研究了生长时材料薄膜的表面形貌。为了使材料更好地应用于器件，研究了材料的掺杂性质。研究了给体束缚激子(Donor bound exeiton (DX))、自由激子(Free exciton(EX))和受体束缚激子(Aeeeptor bound exciton (AX))随温度变化的发光过程。用紫外-可见透射光谱研究了ZnO薄膜材料的透射光谱性质。结果表明，用分子束外延生长设备成功地生长了高质量的氧化锌薄膜材料。     

Synthesis of PbS:ZnO nanotrees by thermal evaporation:morphological, structural and optical properties

Nanotrees ZnO films are synthesized by thermal evaporation method on silicon and glass substrates. PbS powder (5 wt%) is used to obtain the nanostructure and growth modifications. ZnO films are compared with non-doped ones (ZnO film was dense structure without nanotrees). The deposited PbS:ZnO films exhibit polycrystalline orientation using X-ray diffraction (XRD), but the films without doping was less crystalline quality. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology. SEM images (surface and cross section) was confirmed the nanotrees form for doped ZnO film. Energy dispersive X-ray detector (EDX) was used to verify the composition of prepared films. Ultraviolet-visible (UV-Vis), photoluminescence (PL) and micro Raman techniques were used to investigate the optical properties. The PL spectra intensities were found to increase for PbS:ZnO nanotrees. Up to our knowledge, no work has been published regarding the obtained ZnO nanotrees using PbS as dopant via simple thermal evaporation method.     

利用ZnO缓冲层制备AlN薄膜

采用脉冲激光淀积 (PL D)技术 ,利用 Zn O作为缓冲层 ,在 Si(10 0 )衬底上生长出 Al N薄膜。X-射线衍射图谱表明 ,该 Al N薄膜具有 c轴取向特性。X-光电子能谱测试表明 ,要获得接近理想化学配比的 Al N薄膜 ,需要高真空淀积气氛或合适的 N2 气氛 ;同时还表明 ,Al N薄膜表面容易形成保护性氧化层。剖面透射电子显微镜显微照相显示该 Al N/ Zn O/ Si(10 0 )多层结构清晰可辨 ,层与层之间的界面非常平整。原子力显微镜分析表明 ,采用 Zn O缓冲层可改善 Al N薄膜的表面粗糙度 (RMS=1nm)     

Growth and electronic properties of ZnO epilayers by plasma-assisted molecular beam epitaxy

ZnO thin films were grown on c-plane sapphire substrates by plasma-assisted molecular beam epitaxy (MBE). The crystalline properties of the layers as measured by x-ray diffraction were found to improve with lower growth temperatures, where the full-width at half-maximum (FWHM) of the x-ray rocking curves was shown to be in the range of 100 to 1,100 arcsec. The electronic properties were found to improve for higher growth temperatures, with n-type carrier concentration and electron mobility in the range of 1×10¹⁷ −5×10¹⁸ cm⁻³ and 80–36 cm²/Vs, respectively. Photoluminescence (PL) measurements indicated that growth at higher temperatures provided superior band edge radiative emission, while growth at lower temperatures resulted in significant deep level radiative emission centered at 2.35 eV. Photoconductive decay measurements exhibit a slow decay indicating the presence of hole traps, where Zn vacancies are believed to be the source of both the slow decay and the deep level emission observed in PL spectra.     

在家用微波炉中合成四针状ZnO

将锌粉和石墨粉以一定比例混合放入家用微波炉中,在微波辐照下燃烧生成了白色松软的ZnO膜,将此薄膜用扫描电子显微镜(SEM)、能量损失谱(EDS)、透射电子显微镜(TEM)和X射线衍射光谱(XRD)分析其成分和形貌。结果显示,该ZnO为单晶四针状晶须,晶须直径为20~50nm,分析了它的生长机理并测试其场发射特性,得到该ZnO的开启场强较低为3.88V/μm,相应的电流密度为10μA/cm2,在场强为5.7V/μm时达到最大发射电流密度为0.39mA/cm2。