Optical constants of Na-doped ZnO thin films by sol-gel method

The structural and optical properties of pure and Na-doped ZnO thin films have been investigated by X-ray diffraction (XRD), atom force microscopy and UV-Vis spectrophotometer. The crystal structure of all the thin films is the hexagonal wurtzite. The average grain size and surface roughness increases with the increase of the Na/Zn ratio. The optical band gap of the thin films decreases from 3.26 to 3.12 eV by increasing the Na/Zn ratio from 0.0 to 0.10. Transmittance spectra were used to determine the optical constants of the thin films, and the effect of Na/Zn ratio on the optical constants was investigated. With the increase of Na/Zn ratio, the refractive index decreases and the extinction coefficient increases in the 380-700 nm spectral range.     

Fe掺杂对溶胶凝胶法制备的ZnO: Ni薄膜结构及发光特性的影响

采用溶胶凝胶法在玻璃基片上制备了ZnO及Ni, Fe共掺杂的Zn_0.95-xNi_0.05Fe_xO (x=0, 0.005, 0.01, 0.03, 0.05) 薄膜. 通过扫描电镜(SEM) 和X射线衍射(XRD) 研究了薄膜样品的表面形貌和晶体结构. 结果表明所有样品都具有(002) 择优取向, Fe掺杂导致ZnO: Ni薄膜的晶体质量变差, 晶粒尺寸减小, 但适当的Fe掺杂有利于获得致密、 均匀的薄膜. XPS测试结果表明样品中Ni离子的价态为+2价, Fe离子的价态为+2价和+3价.室温光致发光(PL) 测量表明, 所有样品均观察到较强的紫外发光峰, 蓝光双峰和绿光发光峰. ZnO: Ni薄膜的发光强度可以通过Fe掺杂进行有效调节. 进而我们讨论了Ni, Fe共掺杂ZnO样品的发光机理.     

Fe,Co共掺杂ZnO薄膜结构及发光特性研究

采用溶胶凝胶法在玻璃衬底上制备了Fe,Co共掺Zn0.9FexCo0.1-xO(x=0,0.03,0.05,0.07)系列薄膜.通过扫描电镜(SEM)、X射线衍射(XRD)、X射线光电子谱(XPS)和光致发光(PL)谱对薄膜样品的表面形貌、晶体结构、成分和光学性能进行了研究.XRD结果表明所有ZnO薄膜样品都呈六方纤锌矿结构,在样品中没有观察到与Fe和Co相关的团簇,氧化物及其他杂相的衍射峰,表明共掺杂改善了Fe或Co在ZnO的分散性.XPS测试结果揭示样品中Co离子的价态为+2价;Fe离子的价态为+2价和+3价共存,但Fe相对浓度的增大导致Fe3+含量增加.所有样品的室温光致发光谱(PL)均观察到紫外发光峰和蓝光双峰,其中Fe,Co共掺ZnO薄膜的紫外发光峰较本征ZnO出现蓝移,蓝光双峰峰位没有变化,但发光强度有所减弱;而掺杂ZnO薄膜的绿光发光峰几乎消失.最后,结合微结构和成分分析对薄膜样品的发光机理进行了讨论.     

Co,Sn共掺ZnO薄膜结构与光致发光的研究

采用溶胶-凝胶旋涂法在玻璃衬底上制备了Co,Sn掺杂ZnO系列薄膜.通过金相显微镜和X射线衍射(XRD)研究了Co与Sn掺杂对薄膜的表面形貌和微结构的影响.XRD结果表明,所有ZnO薄膜样品都存在(002)择优取向,特别Sn单掺ZnO薄膜的c轴择优取向最为显著,而且晶粒尺寸最大.XPS测试表明样品中Co和Sn的价态分别为2+和4+,证实Co²⁺,Sn⁴⁺进入了ZnO的晶格.室温光致发光谱(PL)显示在所有的样品中都有较强的蓝光双峰发射和较弱的绿光发 关键词： ZnO薄膜 溶胶-凝胶 掺杂 光致发光     

Engineering of electronic and optical properties of ZnO thin films via Cu doping

ZnO thin films doped with different Cu concentrations are fabricated by reactive magnetron sputtering technique. XRD analysis indicates that the crystal quality of the ZnO:Cu film can be enhanced by a moderate level of Cu-doping in the sputtering process. The results of XPS spectra of zinc, oxygen, and copper elements show that Cu-doping has an evident and complicated effect on the chemical state of oxygen, but little effect on those of zinc and copper. Interestingly, further investigation of the optical properties of ZnO:Cu samples shows that the transmittance spectra exhibit both red shift and blue shift with the increase of Cu doping, in contrast to the simple monotonic behavior of the Burstein–Moss effect. Analysis reveals that this is due to the competition between oxygen vacancies and intrinsic and surface states of oxygen in the sample. Our result may suggest an effective way of tuning the bandgap of ZnO samples.     

Co与Cu掺杂ZnO薄膜的制备与光致发光研究

采用溶胶-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.用金相显微镜观察了Co与Cu掺杂对ZnO薄膜形貌的影响.X射线衍射（XRD）研究揭示所有ZnO薄膜样品都存在（002）择优取向,在Cu单掺的ZnO薄膜中晶粒尺寸最大.对所有样品的室温光致发光测量都观察到较强的蓝光双峰发射和较弱的绿光发射,其中长波长的蓝光峰和绿光峰都能够通过掺杂进行控制.对不同掺杂源的ZnO薄膜发光性能进行了分析,认为蓝光峰来源于电子由导带底到锌空位能级的跃迁及锌填隙到价带顶的跃迁,绿光峰是由于掺杂造成的 关键词： ZnO薄膜 溶胶-凝胶 Co Cu掺杂 光致发光     

微量Mg掺杂ZnO薄膜的光致发光光谱和带隙变化机理研究

利用射频磁控溅射(RF-MS)法在450℃玻璃基底上制备了Mg掺杂量分别为0.81at%,2.43at%和4.05at%的ZnO薄膜,对其微观结构、室温光致发光光谱(PL)、光学和电学性质进行了研究.结果发现,微量Mg掺杂ZnO薄膜晶体具有六方纤锌矿结构并保持高结晶质量;掺杂0.81at%和2.43at%Mg的ZnO薄膜室温PL谱中近带边发射(NBE)峰的短波方向出现了高能发射带与NBE峰同时存在;随着Mg掺杂量增加至4.05at%,这个高能发射带逐步将NBE峰掩盖.推测在Mg掺杂ZnO薄膜中,Mg2+替代Zn2+附近核外电子的能量增大并产生了一个高能级.而未被Mg2+替代的Zn2+周围的核外电子能量状态不变,带间能级依然存在,随着Mg掺杂量的增加处于高能级的电子数目逐步增加并占绝对优势.因此,ZnO薄膜随着Mg掺杂量增加薄膜禁带宽度增大,这是由于Mg掺杂后周围电子能量增大与Burstein-Moss效应共同作用的结果.另外,薄膜在可见光区域的平均透射率均大于85%,随着Mg掺杂量的增加,薄膜禁带宽度增大并在3.36—3.52eV内变化;Mg掺杂量为0.81at%,2.43at%和4.05at%时,薄膜电阻率分别为2.2×10-3,3.4×10-3和8.1×10-3Ω.cm.     

Thermal conductivity of thermoelectric Al‐substituted ZnO thin films

ZnO:Al thin films with a low electrical resistivity were grown by magnetron sputtering on sapphire substrates. The cross‐plane thermal conductivity (κ = 4.5 ± 1.3 W/mK) at room temperature is almost one order of magnitude lower than for bulk materials. The thermoelectric figure of merit ZT at elevated temperatures was estimated from in‐plane power factor and the cross‐plane thermal conductivity at room temperature. It is expected that the thermal conductivity drops with increasing temperature and is lower in‐plane than cross‐plane. Consequently, the thin film ZT is at least three times higher than for bulk samples at intermediate temperatures. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural characterization of supported nanocrystalline ZnO thin films prepared by dip-coating

Nanocrystalline ZnO thin films prepared by the sol-gel dip-coating technique were characterized by grazing incidence X-ray diffraction (GIXD), atomic force microscopy (AFM), X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS). The structures of several thin films subjected to (i) isochronous annealing at 350, 450 and 550 °C, and (ii) isothermal annealing at 450 °C during different time periods, were characterized. The studied thin films are composed of ZnO nanocrystals as revealed by analysing several GIXD patterns, from which their average sizes were determined. Thin film thickness and roughness were determined from quantitative analyses of AFM images and XR patterns. The analysis of XR patterns also yielded the average density of the studied films. Our GISAXS study indicates that the studied ZnO thin films contain nanopores with an ellipsoidal shape, and flattened along the direction normal to the substrate surface. The thin film annealed at the highest temperature, T = 550 °C, exhibits higher density and lower thickness and nanoporosity volume fraction, than those annealed at 350 and 450 °C. These results indicate that thermal annealing at the highest temperature (550 °C) induces a noticeable compaction effect on the structure of the studied thin films.     

The transparence comparison of Ga- and Al-doped ZnO thin films

The Ga-doped ZnO (GZO) and Al-doped ZnO (AZO) thin films were grown on quartz glass substrates by pulsed laser deposition under different oxygen partial pressures (PO₂). The transparent performances of films versus properties of structure and conductivity were discussed. With the increase of PO₂, the transmittance of both GZO films and AZO films increased to maximum and then decreased which were in according with the change of crystallization quality. The transmittance of GZO films was higher than that of AZO films, which were not dominated by the impurity ions induced by doping. AFM images and surface roughness mean square coefficients showed that the surfaces of GZO films were smoother than that of AZO films, which were due to the dopant Ga acting as the surfactant and smoothed the GZO films surface.     

Ordered ultra thin ZnO films on metal substrate

Ultra thin ZnO films were prepared on metal Mo(1 1 0) substrate under ultrahigh vacuum conditions either by depositing Zn in 10⁻⁵ Pa oxygen or by oxidizing pre-deposited Zn films. The films were characterized in situ by various surface analytical techniques, including Auger electron spectroscopy, X-ray and ultraviolet photoelectron spectroscopies, low energy electron diffraction and high resolution electron energy loss spectroscopy. The results indicate that a long-range ordered and stoichiometric ZnO films are formed along its [0 0 0 1] direction. The annealing experiments show that as-prepared ZnO films are thermal stable until 800 K. This study provides constructive information to further understand the growth mechanism of ZnO films on different substrates.     

Platinum role in hydrophilicity enhancement of Cr-doped TiO2 thin films

In this paper, we have investigated the hydrophilic properties of the titania films doped with increasing chromium percentages (from 2.1 at.% till 4.0 at.%). Cr-doping induces an increase in the rutile weight %, a more compact structure, and a significant red shift of the TiO₂ absorption edge, the last property being very important in the self cleaning applications. For the chosen Cr concentrations, the films did not show promising hydrophilic properties. To improve them, we have applied a novel surface modification method, reported in literature mainly for powders, namely, surface metallisation. We have observed that, by depositing Pt islands on the film with the highest Cr content, its hydrophilic properties improve for a certain metal coverage area. The explanation was based on FT-IR and X-ray photoelectron spectroscopy analysis, performed on the UV irradiated and non-irradiated films, which gives information on the relationship between hydrophilicity and the amount of the adsorbed hydroxyl groups.     

An investigation on the variations in properties of Ni+ irradiated ZnO thin films

ZnO thin films, irradiated by 80 MeV Ni⁺ ions, were analysed with the help of different characterization techniques like X-ray diffraction, optical absorption, transmission, photoluminescence (PL), electrical resistivity, photosensitivity (PS) and thermally stimulated current (TSC) measurements. Crystallinity and absorption edge were hardly affected by irradiation. PL spectrum of pristine sample showed a broad peak at 517 nm, whereas irradiated film had two emissions at 517 and 590 nm. Intensity ratio between these two emissions (I₅₁₇/I₅₉₀) decreased with the fluence, and finally at a fluence of 3×10¹³ ions/cm², the emission at 517 nm completely disappeared. Electrical resistivity of the sample irradiated with a fluence of 1×10¹³ ions/cm² drastically increased. However, on increasing the fluence to 3×10¹³ ions/cm², resistivity decreased, probably due the onset of hopping conduction through defects. PS also decreased due to irradiation. TSC measurements on pristine sample could reveal only one defect level at 0.6 eV, due to interstitia1 zinc (Zn_I). But, irradiation at a fluence of 1×10¹² ions/cm², resulted in three different defect levels as per TSC studies. Interestingly, the sample irradiated at a fluence of 3×10¹³ ions/cm² had only one defect level corresponding to a deep donor. The possible origin of these defect levels is also discussed in the paper.     

Physical properties of ZnO thin films deposited by spray pyrolysis technique

Thin films of ZnO have been prepared on glass substrates at different thicknesses by spray pyrolysis technique using 0.2 M aqueous solution of zinc acetate. X-ray diffraction reveals that the films are polycrystalline in nature having hexagonal wurtzite type crystal structure. The resistivity at room temperature is of the order 10⁻² Ω cm and decreased as the temperature increased. Films are highly transparent in the visible region. The dependence of the refractive index, n, and extinction coefficient, k, on the wavelength for a sprayed film is also reported. Optical bandgap, E_g, has been reported for the films. A shift from E_g = 3.21 eV to 3.31 eV has been observed for deposited films.     

Effect of Mn doping on the nanostructure and optical properties of ZnO films synthesized by magnetron sputtering

We investigated the microstructure and optical properties of Zn_1−xMn_xO films synthesized by the magnetron sputtering technique. Structural analyses suggest that Mn occupied the Zn sites successfully and did not change the wurtzite structure of ZnO. In addition, nanoscale columnar grain arrays were found in the Mn-doped ZnO films. The experimental results indicate that moderate Mn doping could enhance the photoluminescence emission of ZnO. The possible origin of the emissions from our samples was also explored.     

The modification of the characteristics of nanocrystalline ZnO thin films by variation of Ta doping content

Thin films of Ta-doped ZnO were synthesised via sol–gel spin coating route. The structural and optical properties of the films were evaluated to find out the effect of Ta dopant content. X-ray diffraction results indicated that all samples have hexagonal wurtzite crystal structure with polycrystalline nature. (0 0 2) peak is the most intense peak observed in all samples as well as the highest textured coefficient. Standard deviation results have shown that the kind of nucleation varies from heterogeneous to homogenous with Ta doping content. Additionally, Ta-incorporated ZnO films revealed not only a decreased surface roughness, but also an increased optical transmittance. Direct optical band gap values increased from 3.14 to 3.28 eV, and Urbach energy values decreased from 217 to 147 meV with increasing Ta doping. Refractive index and dielectric constant values were determined by means of two different functions and a significant consistency was found among them. Moreover, the correlation between the optical and structural properties showed that there is a relationship between refractive index and lattice constants of Ta-doped ZnO films.     

Effects of sapphire substrates surface treatment on the ZnO thin films grown by magnetron sputtering

The surface treatment effects of sapphire substrate on the ZnO thin films grown by magnetron sputtering were studied. The sapphire substrates properties have been investigated by means of atomic force microscopy (AFM) and X-ray diffraction rocking curves (XRCs). The results show that sapphire substrate surfaces have the best quality by CMP with subsequent chemical etching. The surface treatment effects of sapphire substrate on the ZnO thin films were examined by X-ray diffraction (XRD) and photoluminescence (PL) measurements. Results show that the intensity of (0 0 2) diffraction peak of ZnO thin films on sapphire substrates treated by CMP with subsequent chemical etching was strongest, FWHM of (0 0 2) diffraction peak is the narrowest and the intensity of UV peak of PL spectrum is strongest, indicating surface treatment on sapphire substrate preparation may improve ZnO thin films crystal quality and photoluminescent property.     

Induced growth of high quality ZnO thin filmsby crystallized amorphous ZnO

This paper reports the induced growth of high quality ZnO thin film by crystallized amorphous ZnO. Firstly amorphous ZnO was prepared by solid-state pyrolytic reaction, then by taking crystallized amorphous ZnO as seeds (buffer layer), ZnO thin films have been grown in diethyene glycol solution of zinc acetate at 80℃. X-ray Diffraction curve indicates that the films were preferentially oriented [001] out-of-plane direction of the ZnO. Atomic force microscopy and scanning electron microscopy were used to evaluate the surface morphology of the ZnO thin film. Photoluminescence spectrum exhibits a strong ultraviolet emission while the visible emission is very weak. The results indicate that high quality ZnO thin film was obtained.     

Characteristics of ZnO:In thin films prepared by RF magnetron sputtering

In-doped ZnO (ZnO:In) transparent conductive thin films were deposited on glass substrates by RF magnetron sputtering. The effect of substrate temperature on the structural, electrical and optical properties of the ZnO:In thin films was investigated. It was found that higher temperature improves the crystallinity of the films and promotes In substitution easily. ZnO:In thin films with the best crystal quality were fabricated at 300 °C, which exhibit a larger grain size of 29 nm and small tensile strain of 0.9%. The transmittance of all the films was revealed to be over 85% in the visible range independence of the substrate temperatures and the lowest resistivity of ZnO:In thin films is 2.4×10⁻³ Ω cm.     

Influence of polarity inversion on the electrical properties of Ga‐doped ZnO thin films

This study investigates how polarity inversion influences the relationship between the electrical properties of heavily Ga‐doped ZnO (GZO) films deposited by RF magnetron sputtering and their thickness. The electrical properties observed in very thin films are correlated with a change of polarity from O‐polar to Zn‐polar face upon increasing the film thickness based on results of valence band spectra measured by X‐ray photoelectron spectroscopy. It is found that the electrical properties of very thin GZO films deposited on Zn‐polar ZnO templates are significantly improved compared to those deposited on O‐polar face. A low resistivity of 2.62 × 10^–4 Ω cm, high Hall mobility of 26.9 cm²/V s, and high carrier concentration of 8.87 × 10²⁰ cm^–3 being achieved with 30 nm‐thick GZO films using Zn‐polar ZnO templates on a glass substrate. In contrast, the resistivity of 30 nm‐thick GZO films on bare glass that shows more likely O‐polar is very poor about 1.44 × 10^–3 Ω cm with mobility and carrier concentration are only 11.9 cm²/V s and 3.64 × 10²⁰ cm^–3, respectively. It is therefore proposed that polarity inversion plays an important role in determining the electrical properties of extremely thin GZO films. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)