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.     

Growth of GaN Films on Si (100) Buffered with ZnO by Ion-Beam-Assisted Filtered Cathodic Vacuum Arc Technique

GaN films have been fabricated on Si (100) substrates with ZnO buffer layers by an ion-beam-assisted filtered cathodic vacuum arc (I-FCVA) technique at␣450°C. GaN films are highly (002)-oriented with a hexagonal structure examined by X-ray diffraction. The room-temperature photoluminescence spectrum of the GaN film exhibits a strong and sharp band-edge emission peak at 3.36 eV. The obtained results demonstrate the potential of the I-FCVA technique for the fabrication of high-quality GaN layers on Si substrates.     

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.     

Effect of substrate temperature on the properties of ZnO thin films prepared by spray pyrolysis

Sprayed ZnO films were grown on glass at different substrate temperatures from 200 °C to 500 °C and their structural, optical and electrical properties were investigated. All films are polycrystalline with hexagonal wurtzite structure. ZnO films at substrate temperatures above 400 °C appear to be better crystalized with (002) plane as preferential orientation. Optical transmission spectrum shows that ZnO films have high transmission (above 80%) in visible region for substrate temperatures above 400 °C. Photoluminescence spectra at room temperature show an ultraviolet emission and two visible emissions at 2.82 eV and 2.37 eV. The resistivity of ZnO films increases with increasing substrate temperatures (above 400 °C). The ZnO film deposited at 400 °C shows highest figure of merit.     

Effect of Lattice Mismatch on Luminescence of ZnO/Si Hetero-Structure

研究了ZnO薄膜中应力对发光的影响.实验样品为ZnO体单晶、在Si基片上直接生长的ZnO薄膜以及通过SiC过渡层在Si基片上生长的ZnO薄膜.测量了这三种样品的X射线衍射图形、喇曼光谱和光致发光光谱.由X射线衍射图形可以看出,由于SiC过渡层缓解了ZnO与Si之间的晶格失配,使得通过SiC过渡层在Si上生长的ZnO薄膜的结晶质量好于直接在Si上生长的ZnO薄膜的质量.进一步通过喇曼谱测量发现,与ZnO体单晶相比,直接在Si上生长的ZnO薄膜的E2(high)峰红移1.9cm-1,根据喇曼谱峰位移与应力的关系可以推出薄膜中存在0.4GPa的张应力;而通过SiC过渡层在Si上生长的ZnO薄膜的E2(high)峰红移0.9cm-1,对应着0.2GPa的张应力.对照X射线衍射图形的结果可以看出,薄膜中张应力的大小与薄膜的结晶质量密切相关,表明张应力来源于外延层和基片间的晶格失配,晶格失配越大,外延层中产生的张应力越大.有无SiC过渡层的两种薄膜样品的PL光谱中都存在紫外和绿光两种谱带,随样品热处理时氧气分压增加,两种样品都出现绿光增强的相似的变化规律,但有SiC过渡层的样品的变化幅度较小.这一结果说明,绿色发光中心与薄膜的质量,也就是与薄膜中存在的张应力大小有关.在以往研究中得出的非故意掺杂ZnO薄膜的绿色发光中心来源于氧反位缺陷(Ozn),文中研究的结果正好可以解释氧反位缺陷形成的原因.由于薄膜中存在张应力,使得样品的能量升高,其结果必然会产生缺陷来释放张应力,以便降低系统能量.而氧离子半径大于锌离子半径,氧替位锌有利于释放张应力,也就是说,在存在张应力的情况下,Ozn的形成能降低.这一结果进一步证明Si上生长的ZnO薄膜中的绿色发光中心与氧反位缺陷有关.     

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.     

应力对ZnO/Si异质结构的光致发光的影响

研究了ZnO薄膜中应力对发光的影响.实验样品为ZnO体单晶、在Si基片上直接生长的ZnO薄膜以及通过SiC过渡层在Si基片上生长的ZnO薄膜.测量了这三种样品的X射线衍射图形、喇曼光谱和光致发光光谱.由X射线衍射图形可以看出,由于SiC过渡层缓解了ZnO与Si之间的晶格失配,使得通过SiC过渡层在Si上生长的ZnO薄膜的结晶质量好于直接在Si上生长的ZnO薄膜的质量.进一步通过喇曼谱测量发现,与ZnO体单晶相比,直接在Si上生长的ZnO薄膜的E2(high)峰红移1.9cm-1,根据喇曼谱峰位移与应力的关系可以推出薄膜中存在0.4GPa的张应力;而通过SiC过渡层在Si上生长的ZnO薄膜的E2(high)峰红移0.9cm-1,对应着0.2GPa的张应力.对照X射线衍射图形的结果可以看出,薄膜中张应力的大小与薄膜的结晶质量密切相关,表明张应力来源于外延层和基片间的晶格失配,晶格失配越大,外延层中产生的张应力越大.有无SiC过渡层的两种薄膜样品的PL光谱中都存在紫外和绿光两种谱带,随样品热处理时氧气分压增加,两种样品都出现绿光增强的相似的变化规律,但有SiC过渡层的样品的变化幅度较小.这一结果说明,绿色发光中心与薄膜的质量,也就是与薄膜中存在的张应力大小有关.在以往研究中得出的非故意掺杂ZnO薄膜的绿色发光中心来源于氧反位缺陷(Ozn),文中研究的结果正好可以解释氧反位缺陷形成的原因.由于薄膜中存在张应力,使得样品的能量升高,其结果必然会产生缺陷来释放张应力,以便降低系统能量.而氧离子半径大于锌离子半径,氧替位锌有利于释放张应力,也就是说,在存在张应力的情况下,Ozn的形成能降低.这一结果进一步证明Si上生长的ZnO薄膜中的绿色发光中心与氧反位缺陷有关.     

The Transparent Conductive Properties of Manganese-Doped Zinc Oxide Films Deposited by Chemical Bath Deposition

Manganese-doped zinc oxide (Mn-doped ZnO) thin films were prepared using chemical bath deposition (CBD), and the impacts of the manganese dopant concentration on the structure, electrical resistivity, optical transmission, and magnetic properties were investigated using x-ray diffractometry, Hall-effect measurements, ultraviolet–visible–near-infrared (UV–Vis–IR) spectrophotometry, and vibrating sample magnetometry (VSM), respectively. The concentration of the manganese dopant in the ZnO thin film critically impacted the resulting properties, and the 4.0 at.% Mn-doped ZnO film had a resistivity of 5.8 × 10⁻² Ωcm, transmittance of 75.6% in the visible light range, and bandgap of 3.30 eV when the film was annealed at 600°C in an Ar + H₂ atmosphere. Annealing the film could enhance its magnetic properties such that the film had a saturation magnetization of 21.0 emu/cm³ and a coercivity of 45.7 Oe after annealing at 600°C. Because of these electrical, optical, and magnetic properties, Mn-doped thin films are promising for use in spintronic devices.     

Room-temperature ferromagnetic ordering in Mn-doped ZnO thin films grown by pulsed laser deposition

The ferromagnetic ordering in Mn-doped ZnO thin films grown by pulsed laser deposition (PLD) as a function of oxygen pressure and substrate temperature has been investigated. Room-temperature ferromagnetic behaviors in the Mn-doped ZnO films grown at 700°C and 800°C under 10⁻¹ torr in oxygen pressure were found, whereas ferromagnetic ordering in the films grown under 10⁻³ torr disappeared at 300 K. The large positive magnetoresistance (MR), ∼10%, was observed at 5 K at low fields and small negative MR was observed at high fields, irrespective of oxygen pressure. In particular, anomalous Hall effect (AHE) in the Mn-doped ZnO film grown at 700°C under 10⁻¹ Torr has been observed up to 210 K. In this work, the observed AHE is believed to be further direct evidence demonstrating that the Mn-doped ZnO thin films are ferromagnetic.     

脉冲激光沉积法制备氧化锌薄膜

ZnO是一种新型的Ⅱ-Ⅵ族半导体材料,具有优良的晶格、光学和电学性能,其显著的特点是在紫外波段存在受激发射。利用脉冲激光沉积法(PLD)在氧气氛中烧蚀锌靶制备了纳米晶氧化锌薄膜,衬底为石英玻璃,晶粒尺寸约为28-35 nm。X射线衍射(XRD)结果和光致发光(PL)光谱的测量表明,当衬底温度在100-250℃范围内时,所获得的ZnO薄膜具有c轴的择优取向,所有样品的强紫外发射中心均在378-385 nm范围内,深能级发射中心约518-558 nm,衬底温度为200℃时,得到了单一的紫外光发射(没有深能级发光)。这归因于其较高的结晶质量。     

热氧化磁控溅射金属锌膜制备ZnO纳米棒

利用射频磁控溅射技术在Si(111)衬底上制备金属锌膜 ,在空气中退火热氧化合成了一维ZnO纳米棒。用X射线衍射 (XRD) ,扫描电子显微镜 (SEM) ,透射电子显微镜 (TEM)和光致发光谱 (PL)对样品进行了结构、形貌及光学特性分析。结果表明 :ZnO纳米棒为六方纤锌矿结构单晶相 ,直径在 30～ 6 0nm左右 ,其长度可达5～ 8μm左右。在 2 80nm波长光激发下 ,有很强的 372nm带边紫外光发射和较微弱的 5 16nm深能级绿光发射 ,说明合成的单晶ZnO纳米棒的质量较高     

PLD法生长Al2O3基ZnO薄膜的特性

在不同衬底温度下,用脉冲激光沉积法(PLD),在Al2O3(0001)平面上生长了ZnO薄膜。研究了衬底温度对其结晶质量、电学性质以及发光性质的影响。结果显示:XRD在2θ为34°处出现了唯一的ZnO(0002)衍射峰;ZnO薄膜的电阻率随衬底温度的升高而增大;在衬底温度为500℃时,出现了位于410nm附近的特殊的光致发光(PL)峰。     

Nanostructured ZnO Films for Room Temperature Ammonia Sensing

Zinc oxide (ZnO) thin films have been deposited by a reactive dc magnetron sputtering technique onto a thoroughly cleaned glass substrate at room temperature. X-ray diffraction revealed that the deposited film was polycrystalline in nature. The field emission scanning electron micrograph (FE-SEM) showed the uniform formation of a rugby ball-shaped ZnO nanostructure. Energy dispersive x-ray analysis (EDX) confirmed that the film was stoichiometric and the direct band gap of the film, determined using UV–Vis spectroscopy, was 3.29 eV. The ZnO nanostructured film exhibited better sensing towards ammonia (NH₃) at room temperature (～30°C). The fabricated ZnO film based sensor was capable of detecting NH₃ at as low as 5 ppm, and its parameters, such as response, selectivity, stability, and response/recovery time, were also investigated.     

利用P-MBE在Si(111)衬底上生长氧化锌薄膜及其光学性质的研究

在Si(111)衬底上利用等离子体辅助分子束外延(P-MBE)生长氧化锌(ZnO)薄膜,研究了在不同衬底生长温度下(350～750℃)制备的ZnO薄膜的结构和光学性质．随着衬底温度的升高,样品的X射线及光致发光的半高宽度都是先变小后变大,衬底温度为550℃样品的结构及光学性质都比较好,这表明550℃为在Si(111)衬底上生长ZnO薄膜的最佳衬底温度;同时,我们还通过550℃样品的变温光致发光谱(81～300K)研究了ZnO薄膜室温紫外发光峰的来源,证明其来源于自由激子发射．     

Effects of Growth Temperature on Properties of Nonpolar <Emphasis Type="Italic">a</Emphasis>-Plane ZnO Films on GaN Templates by Pulsed Laser Deposition

In this work, a-plane GaN/r-sapphire templates have been used to grow nonpolar a-plane ZnO films by pulsed laser deposition. The ZnO film growth temperature was varied in the range of 400°C to 600°C, and the effect of growth temperature on the properties of the ZnO thin films was investigated using x-ray diffraction, atomic force microscopy, photoluminescence (PL) spectroscopy, and Raman measurements. The results show that the crystal quality, surface morphology, strain states, and optical properties of a-plane ZnO films are strongly correlated with the deposition temperature. It is found that the crystallinity of the ZnO films gets better and the surface roughness decreases with increasing growth temperature. At a growth temperature of 600°C, the a-ZnO films display the best crystal quality with x-ray (11[`2]0) (11\bar{2}0) omega scan full-width at half-maximum values of 0.28° and 0.41° on axis (11[`2]0) (11\bar{2}0) at azimuth 0° and 90°, respectively. Furthermore, the PL spectrum measured at 83 K is dominated by neutral donor-bound excitons and free-electron-to-bound (e-A ₀) emission, and relatively intense LO-phonon replicas of (e-A ₀) have also been observed in the a-plane ZnO. The dominance of the free exciton and the appearance of its replicas strongly indicate the high quality of the film.     

用MOCVD方法在GaAs衬底上低温生长ZnO薄膜

采用二乙基锌(DEZn)和水(H2O)作为生长源,利用金属有机化学气相沉积(MOCVD)的方法,在100～400℃低温范围内,在GaAs(001)衬底上制备了ZnO薄膜.利用X射线衍射(XRD),室温PL,AFM,SEM研究了薄膜的晶体结构特性、发光特性及表面形貌特性.XRD分析表明ZnO薄膜具有很强的c轴取向,(002)峰的FWHM平均值为0.3°.当生长温度达到400℃时从SEM测量结果可以观察到薄膜表面呈六角状结晶.随着生长温度的升高,薄膜的晶粒尺寸变大,结晶质量得到提高但同时表面变粗糙.室温PL测量显示薄膜在370nm附近有强的近带边发射,没有观测到深能级发射峰.     

Effect of annealing on the morphology and optoelectrical characteristics of ZnO thin films grown by plasma-assisted molecular beam epitaxy

The dependence of characteristics of plasma-assisted molecular beam epitaxy-grown ZnO thin films on different postgrowth annealing conditions was investigated. It was found that, under oxygen atmosphere, annealing temperature can profoundly affect the morphological, electrical, and optical properties of ZnO thin films. In particular, the surface morphology changed from a relatively smooth surface before annealing to various island morphologies after annealing above 800°C for samples grown directly on sapphire without a buffer layer. It is speculated that intrinsic stress due to lattice mismatch drives the island formation and the high temperature provides the energy needed for this surface rearrangement. Single-field Hall-effect measurement showed that the carrier concentration improved by an order of magnitude and the mobility increased from about 30 cm²/Vs to ∼70 cm²/Vs by annealing at 750°C. Variable-field Hall effect shows that a model with two carriers, one a degenerate low-mobility electron and the other a higher mobility non-degenerate electron, is needed to explain the transport properties of the thin film. Analysis indicates that annealing at 750°C decreased the carrier concentration and increased the mobility for the high-mobility carrier. Annealing also led to a significant improvement in photoluminescence, with temperatures of ∼750–850°C yielding the best results.     

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     

Shallow and Deep Centers in As-Grown and Annealed MgZnO/ZnO Structures with Quantum Wells

Shallow and deep centers in ZnO(P)/MgZnO/ZnO/MgZnO/ZnO(Ga) structures grown by pulsed laser deposition on sapphire were studied before and after annealing in oxygen atmosphere at high temperatures of 850°C to 950°C. In both as-grown and annealed structures, microcathodoluminescence spectra in the near-bandgap region demonstrate a blue-shift by 0.13 eV compared with bulk ZnO films, indicating carrier confinement in the MgZnO/ZnO/MgZnO quantum well (QW). Annealing strongly decreases the concentration of shallow uncompensated donors from ~10¹⁷ cm⁻³ to ~10¹⁶ cm⁻³ and makes it possible to probe the region of the QW by capacitance–voltage (C–V) profiling. This profiling confirms charge accumulation in the QW. The dominant electron traps in the as-grown films are the well-known traps with activation energies of 0.3 eV and 0.8 eV. After annealing, the electron traps observed in the structure have activation energies of 0.14 eV, 0.33 eV, and 0.57 eV, with the Fermi level in the n-ZnO(P) pinned by the 0.14-eV traps. The annealing also introduces deep compensating defects that decrease the intensity of band-edge luminescence and produce a deep luminescence defect band at 2.2 eV. In addition, a defect vibrational band becomes visible in Raman spectra near 650 cm⁻¹. No conversion to p-type conductivity was detected. The results are compared with the data for the structures successfully converted to p-type, and possible reasons for the observed differences are discussed.     

Optical and Magnetic Properties of ZnO:V Prepared by Ion Implantation

We report on the optical and magnetic properties of the magnetic semiconductor Zn(V)O fabricated by implantation of 195 keV ₅₁V⁺ ions into bulk ZnO:Al grown by a hydrothermal technique. Two sets of the samples, containing N _d –N _a ∼ 10¹⁵ cm⁻³ and 10¹⁸ cm⁻³, were implanted to doses of 1 × 10¹⁵ cm⁻², 3 × 10¹⁵ cm⁻², and 1 × 10¹⁶ cm⁻². The ion implantation was performed at 573 K. To remove irradiation-induced defects, the samples were annealed in air at 1073 K. Photoluminescence (PL) measurements of Zn(V)O films were carried out at temperatures from 10 K to 300 K. The effects of implantation dose and free carrier concentration on the magnetic properties of Zn(V)O were studied using a superconducting quantum interference device magnetometer. Ferromagnetism has been observed in annealed highly conductive samples implanted to 1 × 10¹⁶ cm⁻². The PL studies of ZnO bulk samples implanted with V⁺ have revealed that thermal annealing at 1073 K restores to a large extent the optical quality of the material. A new emission line centered at 3.307 eV has been found in the PL spectrum of the highly conductive samples implanted to the dose of 1 × 10¹⁶ cm⁻², which is most probably due to complexes involving V ions.