ZnO:Ga透明电极LED的制备及性能分析

基于本实验室的实验条件,采用射频磁控溅射、等离子干法刻蚀等技术成功制备出具有ZnO∶Ga(GZO)透明电极的LED芯片。实验研究了相同工艺条件制备的ITO透明电极LED芯片和GZO透明电极LED芯片,对比实验结果表明GZO薄膜沉积工艺简单,其器件性能与ITO电极LED相当。相同条件下制备的GZO薄膜可见光波段透过率约90%,而ITO仅为75%。实验室制备的LED器件均具有较高的阈值电压,一方面p-GaN与ZnO的禁带宽度相差4.13 eV,接触势垒大,另一方面器件制备过程中的等离子体损伤薄膜表面和器件性能。     

Characteristics of Ga-doped ZnO films deposited by pulsed DC magnetron sputtering at low temperature

Characteristics of Ga-doped ZnO (GZO) transparent conductive oxide films have been investigated based on the absorption behavior and chemical states of dopant Ga in the film. GZO samples were prepared by pulsed DC magnetron sputtering at 423 K by varying the sputtering power from 0.6 to 2.4 kW and the Ga₂O₃ concentration in the targets from 0.6 to 5.7 wt%. Absorption spectra of the GZO films in the visible to ultraviolet range were characterized by long absorption tails and shoulders near the absorption edges indicating the presence of impurity states or bands that overlap with the conduction band. X-ray photoelectron spectroscopy and X-ray diffraction revealed that substantial portion of the dopant exists as finely dispersed or amorphous metallic Ga and oxide of Ga, which would be related to the formation of the impurity bands or states, especially in the samples with lower Ga content. Presence of these species is correlated to the limited doping efficiency observed in the GZO films.     

Dye-Sensitized Solar Cells Combining ZnO Nanotip Arrays and Nonliquid Gel Electrolytes

We present a dye-sensitized solar cell (DSSC) using a nanostructured ZnO photoelectrode and a gel electrolyte. The photoelectrode consists of well-aligned ZnO nanotips on a Ga-doped ZnO (GZO) transparent conducting film. The GZO film (400 nm, sheet resistance ~25 Ω/sq, transmittance over 85% in the visible wavelength) and ZnO nanotips (3.2 μm length) are sequentially grown on a glass substrate using metalorganic chemical vapor deposition. The ZnO photoelectrode is sensitized with dye N719 and impregnated with N-methyl pyrolidinone (NMP) gelled with poly(vinyl-difluoroethylene-hexafluoropropylene) copolymer (PVDF-HFP). The cell exhibits an open-circuit voltage of 726 mV and a power conversion efficiency of 0.89% under one sun illumination. The aging testing shows that the cell using a gel electrolyte has better stability than its liquid electrolyte counterpart.     

基于皮秒激光诱导击穿光谱技术的镓酸锌薄膜的快速定量分析研究

采用射频磁控溅射方法在不同的溅射功率下制备了掺杂Ga元素的ZnO透明导电薄膜材料(ZnGa₂O₄, GZO),在GZO薄膜的制备过程中,溅射功率会对样品的组分配比产生影响,从而导致GZO薄膜的性能产生差异。文中利用皮秒激光诱导击穿光谱技术(PS-LIBS)对GZO薄膜进行了微烧蚀分析,对GZO薄膜的关键元素浓度比进行了快速定量分析研究。结果表明GZO薄膜的光学性能与元素谱线强度比之间存在一定的联系,随着溅射功率的增加,Zn/Ga的谱线强度比值与浓度比呈现出一致的变化,Ga元素的含量与样品的禁带宽度变化一致。同时,使用玻耳兹曼斜线法与斯塔克展宽法对等离子体温度与电子密度进行了计算。所有结果表明,PS-LIBS技术可以实现GZO薄膜关键组分配比的快速分析,为磁控溅射法制备GZO薄膜的工艺现场的快速性能分析、制备参数的实时优化提供了技术参考。     

Optical and structural characteristics of Ga-doped ZnO films

The n-ZnO films doped with Ga to the content 2.5 at % are produced by pulse laser deposition onto the (0001) oriented single crystal sapphire substrates. The transmittance spectra of the ZnO films in the range from 200 to 3200 nm are studied in relation to the Ga dopant content. It is established that an increase in the Ga content shifts the fundamental absorption edge to the blue region, but reduces the transparency of the ZnO films in the infrared spectral region. The dependence of the band gap on the level of doping with Ga is determined. The photoluminescence spectra of the ZnO films doped to different levels are recorded. It is established that the PL intensity and peak position vary unsteadily with the level of doping. X-ray diffraction studies of the structure of the films are carried out. It is found that the crystallographic parameters (the lattice constant c) of the ZnO film depend on the Ga dopant content and the conditions of deposition of the films.     

Study on the adhesive mechanism between the Ga doped ZnO thin film and the polycarbonate substrate

The Ga doped ZnO (GZO) film was deposited on the polymer substrate at room temperature by magnetron sputtering. The resistivity is 8.9×10⁻⁴ Ω cm. The average transmittance in the visible region is over 85%. According to the resistivity and transmittance in the visible light, it is obtained that the film exhibits excellent electrical and optical properties, which satisfies the application for optoelectronic devices. However, the adhesion between the film and the polymer substrate is very weak. In order to figure out the reason of the weak adhesion, we study the adhesive mechanism between the GZO film and the polymer substrate through using depth profiling XPS method, residual stress test, and SIMS method for the first time. The residual stress of the film is a compressive stress. According to the SIMS results, an element diffusion exists at the interface. However, according to the depth profiling XPS results, there is no chemical bonding between the GZO film and the polymer substrate.     

Enhanced Performance of GaN-Based Green Light-Emitting Diodes with Gallium-Doped ZnO Transparent Conducting Oxide

Ga-doped ZnO (GZO) transparent conducting oxide was grown by oxygen plasma-enhanced pulsed laser deposition. GZO grown in the presence of oxygen radicals had resistivity of 1 × 10^?3 Ω cm and average visible (500–700 nm) transmittance of 92.5%. A low specific contact resistance of 6.5 × 10^?4 Ω cm² of GZO on p-GaN was achieved by excimer laser annealing (ELA) treatment of p-GaN before GZO electrode deposition. The ELA-treated light emitting diode (LED) fabricated with the GZO electrode as a current-spreading layer resulted in light-output power enhanced by 56.2% at 100 mA compared with that fabricated with a conventional Ni/Au metal electrode. The high-light output and low degradation of light-output power were attributed to the decrease in contact resistance between the p-GaN layer and the GZO electrode and uniform current spreading over the p-GaN layer. In addition, low contact resistance results in a decrease of self-heat generation during current drive.     

A Ga-doped ZnO transparent conduct layer for GaN-based LEDs

An 8 μm thick Ga-doped ZnO (GZO) film grown by metal-source vapor phase epitaxy was deposited on a GaN-based light-emitting diode (LED) to substitute for the conventional ITO as a transparent conduct layer (TCL). Electroluminescence spectra exhibited that the intensity value of LED emission with a GZO TCL is markedly improved by 23.6% as compared to an LED with an ITO TCL at 20 mA. In addition, the forward voltage of the LED with a GZO TCL at 20 mA is higher than that of the conventional LED. To investigate the reason for the increase of the forward voltage, X-ray photoelectron spectroscopy was performed to analyze the interface properties of the GZO/p-GaN heterojunction. The large valence band offset (2.24±0.21 eV) resulting from the formation of Ga2O3 in the GZO/p-GaN interface was attributed to the increase of the forward voltage.     

Study on the thermal stability of Ga-doped ZnO thin film: A transparent conductive layer for dye-sensitized TiO2 nanoparticles based solar cells

Generally, optoelectronic devices are fabricated at a high temperature. So the stability of properties for transparent conductive oxide (TCO) films at such a high temperature must be excellent. In the paper, we investigated the thermal stability of Ga-doped ZnO (GZO) transparent conductive films which were heated in air at a high temperature up to 500 °C for 30 min. After heating in air at 500 °C for 30 min, the lowest sheet resistance value for the GZO film grown at 300 °C increased from 5.5 Ω/sq to 8.3 Ω/sq, which is lower than 10 Ω/sq. The average transmittance in the visible light of all the GZO films is over 90%, and the highest transmittance is as high as 96%, which is not influenced by heating. However, the transmittance in the near-infrared (NIR) region for the GZO film grown at 350 °C increases significantly after heating. And the grain size of the GZO film grown at 350 °C after annealing at 500 °C for 30 min is the biggest. Then dye-sensitized TiO2 NPs based solar cells were fabricated on the GZO film grown at 350 °C (which exhibits the highest transmittance in NIR region after heating at 500 °C for 30 min) and 300 °C (which exhibits the lowest sheet resistance after heating at 500 °C for 30 min). The dye-sensitized solar cell (DSSC) fabricated on the GZO film grown at 350 °C exhibits superior conversion efficiency. Therefore, transparent conductive glass applying in DSSCs must have a low sheet resistance, a high transmittance in the ultraviolet–visible–infrared region and an excellent surface microstructure.     

梯度掺杂生长绒面结构ZnO:B-TCO薄膜及其特性研究

采用新的金属有机化学气相淀积(MOCVD)-ZnO镀膜工艺技术-梯度掺杂技术生长绒面结构。研究ZnO:B-TCO薄膜。结果表明,梯度掺杂技术可有效增加薄膜晶粒尺寸和提高光散射作用。并且,梯度掺杂技术有效地提高了薄膜在近红外区域的光学透过率,有利于应用于宽谱域薄膜太阳电池。生长获得的MOCVD-ZnO薄膜,其薄膜电子迁移率为24 cm2/V,电阻率为2.17×10-3Ω.cm,载流子浓度为1.20×1020cm-3,且在小于1 000 nm波长范围内的平均透过率大于85%。     

酞菁染料ZnPc和Q-PbS复合敏化纳米晶ZnO薄膜电极的研究

利用溶胶-凝胶旋涂镀膜法结合热处理工艺在FTO玻璃上制备了ZnO薄膜,并通过X射线衍射(XRD)、扫描电子镜(SEM)对其晶相及表面形貌进行了表征;以酞菁染料ZnPc和窄禁带半导体PbS量子点(Q-PbS)为敏化剂,分别制备了FTO/ZnO/ZnPc电极、FTO/ZnO/Q-PbS电极和FTOZnO/Q-PbS/ZnPc电极,结果表明,ZnPc和Q-PbS对ZnO纳米颗粒膜产生了良好的敏化作用,且两者的复合敏化效果最好;制备了FTO/ZnO/Q-PbS/ZnPc为光阳极的染料敏化太阳能电池(DSSC),在模拟太阳光下,电池的开路电压为304mV,短路电流为1.42mA,光电转换效率为0.696%,填充因子为0.348。     

Effects of deposition pressure on the properties of transparent conductive ZnO:Ga films prepared by DC reactive magnetron sputtering

Gallium (Ga)-doped zinc oxide (ZnO:Ga) transparent conductive films were deposited on glass substrates by DC reactive magnetron sputtering. Effects of deposition pressure on the structural, electrical and optical properties of ZnO:Ga films were investigated. X-ray diffraction (XRD) studies show that the films are highly oriented with their crystallographic c-axis perpendicular to the substrate almost independent of the deposition pressure. The morphology of the film is sensitive to the deposition pressure. The transmittance of the ZnO:Ga thin films is over 90% in the visible range and the lowest resistivity of ZnO:Ga films is 4.48×10⁻⁴ Ω cm.     

Enhancement of the hydrogen gas sensitivity by large distribution of c-axis preferred orientation in highly Ga-doped ZnO polycrystalline thin films

The hydrogen gas sensing properties of highly Ga-doped ZnO (GZO) polycrystalline thin films deposited by radio-frequency magnetron sputtering have been studied. The relationship between the microstructural properties of preferred c-axis oriented thin films and the hydrogen gas sensing properties is described. The crystallite size and the preferred orientation distribution were characterized by X-ray diffraction. The crystallite size increased and the preferred orientation distribution decreased with increasing film thickness. In order to control the crystallite size and the c-axis orientation separately, a highly oriented ZnO template layer with different thickness was employed for deposition of 30-nm-thick GZO films. The c-axis orientation of these films were nearly comparable each other, while the crystallite size increased significantly with increasing thickness of the ZnO templates. The hydrogen gas sensitivity at an operating temperature of 330 °C increased slightly with decreasing crystallite size, while the sensitivity was dramatically enhanced by increasing the preferred orientation distribution. It is therefore proposed that the c-axis orientation plays an important role in determining the sensitivity of the hydrogen gas sensor.     

Influence of Ti dopant on the properties and dye sensitized solar cell performance of ZnO chunk-shaped nanostructures

This paper presents the results of photoanode constructed with undoped and Ti-doped ZnO chunk shaped nanostructures for dye sensitized solar cells (DSSC). Nanostructures are prepared by simple chemical method and moreover the structural, morphological, optical and photovoltaic performances are investigated by XRD, SEM, UV–Vis, PL, and I–V measurements, respectively. The experimental observations demonstrate that the Ti is effectively doped into Zn site, which increases free electron concentration, hereby expected an enhancement in the DSSC performance. Fabricated DSSCs are tested and the results reveal that undoped ZnO shows conversion efficiency of 0.42% with better photocurrent density and photovoltage but the fill factor gets enhance up to 0.447 with 3 mole% (dilute) of Ti doping. Comparably, PEO/KI/LiI/I₂ electrolyte matches well for Ti doped ZnO DSSC due to the easier diffusion path offered by KI salt rather than TiO₂ and PEG additives.     

Co与Cu掺杂ZnO磁性薄膜的溶胶-凝胶旋涂法制备

用溶胶-凝胶旋涂法在玻璃衬底上制备了Co,Cu单掺杂及(Co,Cu)共掺杂ZnO薄膜.磁性测量表明,无论是单掺还是共掺的ZnO薄膜都具有室温铁磁性,且Co掺杂和共掺杂ZnO薄膜的磁性相近,而Cu单掺ZnO薄膜磁性稍弱一点.用原子力显微镜和X射线衍射研究了Co,Cu掺杂对ZnO薄膜表面形貌和晶体结构的影响,在薄膜中没有发现第二相和磁性团簇的存在,且所有ZnO薄膜样品都存在(002)择优取向.室温光致发光测量在所有的样品中都观察到447和482 nm附近的蓝光发射,认为是由于氧空位浅施主能级上的电子到价带上的跃迁所导致的.     

A study of the design of ZnO thin film pressure sensors

This study takes the first step in designing ZnO thin film pressure sensors with high operating temperatures. To fabricate the pressure sensors, ZnO thin films are deposited on SiO₂/(100)Si substrates to obtain structures similar to those of silicon-on-insulator. The optimal deposition parameters used to deposit the thin films are a full width at half maximum (FWHM) of 0.269, a c-axis-oriented structure near 100% and an average grain size of 321 Å. Here, to simplify the ZnO thin film pressure sensor system, a new parameter, the ZnO resistance, which changes with the change of pressure, is analysed. ZnO thin film fabricated under the optimal conditions can work as a pressure sensor and its response value, which is proportional to pressure, is greater than 8mΩ/psi. The relative pressure can be obtained from the difference between the response value before applying pressure and after. Further, a special characteristic of these ZnO pressure sensors is that the pressure can be read even during gas inlet.     

Effect of the formation conditions on the properties of ZnO:Ga thin films deposited by magnetron-assisted sputtering onto a cold substrate

The results of studying ZnO:Ga thin films produced by magnetron-assisted sputtering of the corresponding target in argon and in argon with a 5% hydrogen content without heating of the substrate are reported. It is shown that the resistivity and temporal stability of the ZnO:Ga films substantially depend on their thickness, exposure to solar radiation, and influence of the environment. It is found that doping the ZnO:Ga thin films with hydrogen provides a means for greatly decreasing their resistivity, whereas the degree of temporal stability of the films can be improved using a coating protecting them from the influence of the gas environment.     

Investigation of characteristics of ZnO:Ga nanocrystalline thin films with varying dopant content

In this study, undoped and Ga doped ZnO thin films were synthesized by the sol–gel spin coating technique. The effect of Ga contribution on the structural, morphological and optical properties of the ZnO thin films was examined. XRD results showed that all films had a hexagonal wurtzite crystal structure with polycrystalline nature. The intensity of the (002) peak changed with the variable Ga content. The scanning electron microscopy (SEM) results revealed that the surface morphology of the ZnO thin films was affected by Ga content. Moreover, it consisted of nanorods as a result of the increased function of the Ga content. Additionally, the presence of Ga contributions was evaluated by energy dispersive x-ray (EDX) measurements. Although the transparency and the optical band gap of the ZnO thin films increased with Ga contribution, Urbach energy values decreased from 221 meV to 98 meV. In addition, these steepness parameters increased with the increased Ga content from 0% to 6%. The correlation between structural and optical properties was investigated and significant consistency was found.     

N-doped ZnO based fast response ultraviolet photoconductive detector

We report a study on the fabrication and characterization of ultraviolet photodetectors based on N-doped ZnO films. Highly oriented N-doped ZnO films with 10 at.% N doping are deposited using spray pyrolysis technique onto glass substrates. The photoconductive UV detector based on N-doped ZnO thin films, having a metal–semiconductor–metal (MSM) configuration are fabricated by using Al as a contact metal. I–V characteristic under dark and UV illumination, spectral and transient response of ZnO and N-doped ZnO photodetector are studied. The photocurrent increases linearly with incident power density by more than two orders of magnitude. The photoresponsivity (580 A/W at 365 nm with 5 V bias, light power density 2 μW/cm²) is much higher in the ultraviolet region than in the visible.     

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.