Characteraction of Ag-doped ZnO thin film synthesized by sol–gel method and its using in thin film solar cells

Pure 2% and 4% Ag-doped ZnO thin films have been synthesized on glass substrates by sol–gel method. The structure, morphology and optical properties of the samples have been studied by X-ray diffractometer (XRD), scanning probe microscope, UV–vis spectrophotometer, respectively. The XRD result shows that the pure ZnO has a wurtzite hexagonal structure, no phase segregation is observed. The surface morphology of pure ZnO thin film shows that the grains are growing preferentially along the c-axis orientation perpendicular to the substrates. The transmittance spectra reveal that all samples have high transmittance above 90% in visible region. With Ag doping content increase, a red shift is observed. The performance of Ag-doped ZnO films using in thin film solar cells are simulated. The results show that 4% Ag-doped ZnO thin film can greatly improve the absorption of the cells. Compare to pure ZnO, solar cell's energy conversion efficiency improvement of 2.47% is obtained with 4% Ag doped ZnO thin film.     

Comparison of the optical properties of undoped and Ga-doped ZnO thin films deposited using RF magnetron sputtering at room temperature

The optical properties of undoped zinc oxide (ZnO) thin films of various thicknesses were compared with those of Ga-doped (GZO) thin films. Transparent, high-quality undoped ZnO and GZO films were deposited successfully using radio-frequency (RF) sputtering at room temperature. The films were polycrystalline with a hexagonal structure and a strongly preferred orientation along the c-axis. The films had an average optical transmission >85% in the visible part of the electromagnetic spectrum. The undoped ZnO thin films were more transparent than the GZO thin films. In the photoluminescence (PL) spectrum, ZnO film has higher quality than GZO as a result of decrease in the green emission intensity.     

Electrical conductivity and optical properties of ZnO nanostructured thin film

The electrical conductivity, structural and optical properties of ZnO nanostructured semiconductor thin film prepared by sol-gel spin coating method have been investigated. The X-ray diffraction result indicates that the ZnO film has the polycrystalline nature with average grain size of 28 nm. The optical transmittance spectrum indicates the average transmittance higher than 90% in visible region. The optical band gap, Urbach energy and optical constants (refractive index, extinction coefficient, real and imaginary parts of the dielectric constant) of the film were determined. The electrical conductivity of the film dependence of temperature was measured to identify the dominant conductivity mechanism. The conductivity mechanism of the film is the thermally activated band conduction. The electrical conductivity and optical results revealed that the ZnO film is an n-type nanostructured semiconductor with a direct band gap of about 3.30 eV at room temperature.     

Effect of aging time of ZnO sol on the structural and optical properties of ZnO thin films prepared by sol-gel method

In this work, ZnO thin films were prepared by sol-gel method and the effect of aging time of ZnO sol on the structural and optical properties of the films was studied. The structural characteristics of the samples were analyzed by an atomic force microscope and an X-ray diffractometer. The optical properties were studied by a UV-vis spectrophotometer and a fluorophotometer. The results show that the ZnO thin film prepared by the as-synthesized ZnO sol had relatively poor crystalline quality, low optical transmittance in the visible range and relatively weak ultraviolet emission performance. After the as-synthesized ZnO sol was aged for 24 h, the degree of the preferred crystal orientation along the c-axis of the ZnO thin film prepared by this aged sol was improved. At the same time, this film had a very smooth surface with uniform grains and both its visible range transmittance and ultraviolet emission intensity were obviously increased. These results suggest that appropriate aging of ZnO sol is very important for the improvement of structural and optical quality of ZnO thin films derived from sol-gel method.     

Photochemical synthesis of ZnO/Ag nanocomposites

Composite ZnO/Ag nanoparticles have been formed via the photocatalytic reduction of silver nitrate over the ZnO nanocrystals, their optical, electrophysical and photochemical properties have been investigated. Mie theory has been applied to analyze the structure of the absorption spectra of ZnO/Ag nanocomposite. The irradiation effects upon the optical properties of ZnO/Ag nanostructure have been investigated. It has been found that the irradiation of ZnO/Ag nanoparticles results in electrons accumulation by both the semiconductor and the metallic components of the nanocomposite. It has been found that silver nitrate can be photochemically deposited onto the surface of ZnO nanoparticles under the illumination with the visible light in the presence of the sensitizer – methylene blue. Kinetics of the sensitized Ag(I) photoredution has been studied. It has been concluded that the key stage of this process is the electron injection from singlet-excited methylene blue molecule into ZnO nanoparticle.     

Comparative study on structural and optical properties of ZnO thin films prepared by PLD using ZnO powder target and ceramic target

Zinc oxide thin films have been obtained in O₂ ambient at a pressure of 1.3 Pa by pulsed laser deposition (PLD) using ZnO powder target and ceramic target. The effect of temperature on structural and optical properties of ZnO thin films was investigated systematically by XRD, SEM, FTIR and PL spectra. The results show that the best structural and optical properties can be achieved for ZnO thin film fabricated at 700 °C using powder target and at 400 °C using ceramic target, respectively. The PL spectrum reveals that the efficiency of UV emission of ZnO thin film fabricated by using powder target is low, and the defect emission of ZnO thin film derived from Zn_i and O_i is high.     

Influence of substrate temperature on the optical and piezoelectric properties of ZnO thin films deposited by rf magnetron sputtering

In this study, ZnO thin films were fabricated using the rf magnetron sputtering method and their piezoelectrical and optical characteristics were investigated for various substrate temperatures. The ZnO thin film has the largest crystallization orientation for the (0 0 2) peak and the smallest FWHM value of 0.56° at a substrate temperature of 200 °C. The surface morphology shows a relatively dense surface structure at 200 °C compared to the other substrate temperatures. The surface roughness shows the smallest of 1.6 nm at a substrate temperature of 200 °C. The piezoelectric constant of the ZnO thin film measured using the pneumatic loading method (PLM) has a maximum value of 11.9 pC/N at a substrate temperature of 200 °C. The transmittance of the ZnO thin film measured using spectrophotometry with various substrate temperatures ranged from 75 to 93% in the visible light region. By fitting the refractive index from the transmittance to the Sellmeir dispersion relation, we can predict the refractive index of the ZnO thin film according to the wavelength. In the visible light range, the refraction index of the ZnO thin film deposited at a substrate temperature of 200 °C is the range of 1.88-2.08.     

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.     

ZnO/Ag/ZnO multilayer films for the application of a very low resistance transparent electrode

Transparent conductive ZnO/Ag/ZnO multilayer electrodes having much lower electrical resistance than the widely used transparent electrodes were prepared by simultaneous RF magnetron sputtering of ZnO and DC magnetron sputtering of Ag. An Ag film with different thickness was used as intermediate metallic layers. The optimum thickness of Ag thin films was determined to be 6 nm for high optical transmittance and good electrical conductivity. With about 20-25 nm thick ZnO films, the multilayer showed high optical transmittance in the visible range of the spectrum and had color neutrality. The electrical and optical properties of the multilayers were changed mainly by Ag film properties. A high quality transparent electrode, having sheet resistance as low as 3 ohm/sq and high transmittance of 90% at 580 nm, was obtained and could be reproduced by controlling the preparation parameter properly. The above property is suitable as transparent electrode for dye sensitized solar cells (DSSC).     

ZnO可见区发光机理研究进展

近年来,科研工作者对ZnO纳米材料研究产生了浓厚的兴趣。ZnO是一种具有宽带隙(3.37 eV)和较大的激子束缚能(60 meV)的六方纤锌矿结构半导体材料。它具有优异的光电、压电、压敏及发光等特性,在发光(激光)二极管、传感器、发光器件、紫外探测器等领域都有非常好的应用前景。至今,有很多非常成熟的实验方法(包括静电纺丝、水热法、溶胶-水热法、化学气相沉积法、旋涂法及电化学沉积法等)用来合成ZnO纳米材料,如纳米线、纳米棒、纳米盘及量子点等。氧化锌纳米结构的制备和性质已得到了广泛的研究,ZnO的可见发光机理一直是研究的热点,但很少有人对可见光范围内的光致发光进行总结。光致发光光谱能反映一些重要信息,如表面缺陷和氧空位、半导体材料的表面状态、光诱导电荷转移过程等。有学者认为ZnO的发光机理与其晶体缺陷有关,还有研究者认为其发光机理与氧空位有关等。通过量子限域效应、带边调制、表面修饰方法、缺陷调控方法等方面综述了ZnO可见区发光机理。     

The growth of ZnO:Ga:Cu as new TCO film of advanced electrical,optical and structural quality

Because of having similarities in many physical as well as chemical properties to those of Zn, Cu has been strategically used as an effective dopant e.g., Al, Ga, F, etc., to change the optical, electrical and the micro-structural properties of ZnO thin films for obtaining its favorable opto-electronic performance as a transparent conducting oxide suitable for devices. Present study demonstrates the growth of transparent conducting ZnO:Ga:Cu thin films, by low power RF magnetron sputtering at a low substrate temperature (100 °C). Highly crystalline ZnO:Ga:Cu film with preferred c-axis orientation has been obtained demonstrating a high magnitude of transmission ~85% in the visible range and a high electrical conductivity ~40 S cm^–1, facilitated by large crystallite size (~29 nm), introducing reduced grain boundary scattering. XPS O 1S spectrum reveals the presence of a significant fraction of oxygen atoms effectively increasing the optical transparency. Incorporation of Ga and Cu ions into the ZnO matrix promotes violation of the local translational symmetry as suggested by the relaxation of Raman selection rules for the network, evident by the presence of strong (B₁^high–B₁^low) modes which are typically Raman inactive. The consequences of Cu doping has been compared with identically prepared ZnO and ZnO:Ga films.     

Effects of the ion-beam voltage on the properties of the diamond-like carbon thin film prepared by ion-beam sputtering deposition

Diamond-like carbon(DLC) thin film is one of the most widely used optical thin films.The fraction of chemical bondings has a great influence on the properties of the DLC film.In this work,DLC thin films are prepared by ion-beam sputtering deposition in Ar and CH4 mixtures with graphite as the target.The influences of the ion-beam voltage on the surface morphology,chemical structure,mechanical and infrared optical properties of the DLC films are investigated by atomic force microscopy(AFM),Raman spectroscopy,nanoindentation,and Fourier transform infrared(FTIR) spectroscopy,respectively.The results show that the surface of the film is uniform and smooth.The film contains sp2 and sp3hybridized carbon bondings.The film prepared by lower ion beam voltage has a higher sp3 bonding content.It is found that the hardness of DLC films increases with reducing ion-beam voltage,which can be attributed to an increase in the fraction of sp3 carbon bondings in the DLC film.The optical constants can be obtained by the whole infrared optical spectrum fitting with the transmittance spectrum.The refractive index increases with the decrease of the ion-beam voltage,while the extinction coefficient decreases.     

Optical parameters of epitaxial GaN thin film on Si substrate from the reflection spectrum

A method has been proposed for determining the optical properties of a thin film layer on absorbing substrates. The film optical parameters such as thickness, refractive index, absorption coefficient, extinction coefficient and the optical energy gap of an absorbing film are retrieved from the interference fringes of the reflection spectrum at normal incidence. The envelopes of the maxima of the spectrum E_M and of the minima E_m are introduced in analytical forms to find the reflectance amplitudes at the interfaces and approximate values of the thin film refractive index. Then, the interference orders and film thickness are calculated to get accurate values of the needed optical parameters. There are no complex fitting procedures or assumed theoretical refractive index dispersion relations. The method is applied to calculate the optical properties of an epitaxial gallium nitride thin film on a silicon (1 1 1) substrate. Good agreement between our results and the published data are obtained.     

生长条件对脉冲激光沉积制备ZnO：Al薄膜光电性能的影响

本文研究了脉冲激光沉积(PLD)生长过程中, 铝掺量、氧压及衬底温度等实验参数对ZnO:Al(AZO)薄膜生长的影响, 并利用扫描电子显微镜、原子力显微镜、X射线衍射、霍尔效应、光透射光谱等实验手段对其透明导电性能进行了探讨. 变温霍尔效应和光透射测量表明, 当靶材中铝掺量大于0.5 wt%时, 所制备AZO薄膜中铝施主在80 K时已完全电离, 因Bernstein-Moss (BM) 效应其带隙变大, 均为重掺杂简并半导体. 进一步系统研究了氧压和衬底温度对AZO薄膜透明导电性能的影响, 实验发现当氧压为1 Pa, 衬底温度为200 ℃时, AZO 导电性能最好, 其霍尔迁移率为28.8 cm²/V·s, 薄膜电阻率最小可达2.7×10^-4 Ω·cm, 且在可见光范围内光透过率超过了85%. 氧压和温度的增加, 都会导致薄膜电阻率变大. 关键词： 脉冲激光沉积法 ZnO：Al薄膜 透光性 导电性     

钼掺杂氧化锌薄膜的结构、光学和表面等离子体特性研究

室温下,通过直流磁控反应溅射在石英衬底上制备一系列钼掺杂氧化锌薄膜。分别采用X射线衍射(XRD)、原子力显微镜(AFM)、分光光度计及拉曼光谱仪研究了钼掺杂浓度对氧化锌薄膜结构、表面形貌、光学性能和表面等离子体特性的影响。XRD测试结果表明,零掺杂氧化锌薄膜结晶良好,呈c轴择优取向,掺杂后薄膜缺陷增多,结晶质量下降,当掺杂浓度达到3.93 Wt%时,薄膜由c轴择优取向的晶态转变为非晶态。AFM测试结果表明非晶态掺钼氧化锌薄膜表面光滑,粗糙度最低可达489 pm。透射光谱表明所有薄膜样品在可见光范围(400～760 nm)平均透过率均达到80%,禁带宽度随着掺杂浓度的提高从3.28 eV单调增加至3.60 eV。吸收光谱表明氧化锌薄膜表面等离子体共振吸收峰随钼掺杂量的增大发生蓝移,而拉曼光谱表明Mo重掺杂时ZnO薄膜表面拉曼散射信号强度显著降低。通过Mo掺杂获得非晶态氧化锌薄膜,拓宽了氧化锌薄膜材料的应用领域,同时研究了Mo掺杂浓度对氧化锌薄膜表面等离子体的调控作用,这对制备氧化锌基光子器件具有重要参考价值。     

替位和间隙原子N对ZnO电子结构和光学性质的影响

本文采用密度泛函理论,深入研究了N作为替位和间隙原子对ZnO电子结构和光学性质的影响,结果表明：由于N在八面体间隙位置的形成能小所以更倾向于占据八面体间隙位置;N掺杂ZnO会形成p型半导体;N在间隙位置能够明显的缩小带隙宽度,可以有效的促进ZnO对光的吸收;在可见光区,处于间隙位置的N具有良好的光学吸收谱并且产生明显的红移,这与带隙的变化规律一致。     

在不同衬底上制备的ZnO薄膜透射率的研究

采用反应磁控溅射在不同结构衬底上生长ZnO薄膜,通过X-ray衍射(XRD)及透射光谱来分析薄膜的成膜情况,并得出在Al₂O₃/AlN复合基上溅射沉积的ZnO薄膜比单独在AlN薄膜衬底的结晶质量好且透过率也较高。而经不同的快速热退火温度验证,发现在400 ℃时,ZnO薄膜的结晶化及在(002)方向上的择优取向达到最好,并在可见光范围内的平均透过率达到88%以上。当退火温度超过450 ℃时,温度过高改变了ZnO薄膜的内部结构,使其氧原子和锌原子发生了较大距离的位移,导致薄膜内部缺陷的增多,从而存在过多的晶界,增加了其薄膜的散射机制,使光的透过性变差,退火温度为500 ℃时,薄膜的平均透过率为80%。     

厚度对未掺杂ZnO薄膜光谱性能的影响

X射线衍射光谱、拉曼光谱和紫外可见透射光谱技术是薄膜材料检测的重要技术手段。通过对薄膜材料光谱性能的分析,可以获得薄膜材料的物相、晶体结构和透光性能等信息。为了解厚度对未掺杂ZnO薄膜的X射线衍射光谱、拉曼光谱和紫外可见透射光谱性能的影响,利用溶胶-凝胶法在石英衬底上旋涂制备了不同厚度的未掺杂ZnO薄膜样品,并对薄膜样品进行了X射线衍射光谱、拉曼光谱和紫外可见透射光谱的检测。首先,通过X射线衍射光谱检测发现,薄膜样品呈现出（002）晶面的衍射峰,ZnO薄膜为六角纤锌矿结构,均沿着C轴择优取向生长,且随着薄膜厚度的增加,衍射峰明显增强,ZnO薄膜的晶粒尺寸随着膜厚的增加而长大。利用扫描电子显微镜对薄膜样品的表面形貌分析显示,薄膜表面致密均匀,具有纳米晶体的结构,其晶粒具有明显的六角形状。通过拉曼光谱检测发现,薄膜样品均出现了437 cm-1的拉曼峰,这是ZnO纤锌矿结构的特征峰,且随着薄膜厚度的增加,其特征拉曼峰强度也增加,进一步说明了随着ZnO薄膜厚度的增加,ZnO薄膜晶化得到了加强。最后,通过紫外可见透射光谱测试发现,随着膜厚的增加,薄膜的吸收边发生一定红移,薄膜样品在可见光区域内的透过率随着膜厚度增加而略有降低,但平均透过率都超过90%。通过对薄膜样品的紫外-可见透射光谱进一步分析,估算了薄膜样品的折射率,定量计算了薄膜样品的光学禁带宽度,计算结果表明：厚度的改变对薄膜样品的折射率影响不大,但其禁带宽度随着薄膜厚度的增加而变窄,且均大于未掺杂ZnO禁带宽度的理论值3.37 eV。进一步分析表明,ZnO薄膜厚度的变化与ZnO晶粒尺寸的变化呈正相关,本质上,吸收边或光学禁带宽度的变化是由于ZnO晶粒尺寸变化引起的。     

SiO2和HfO2薄膜光学性能的椭偏光谱测量

结合XRD和原子力显微镜等方法,利用椭圆偏振光谱仪测试了单层SiO2薄膜（K9基片）和单层HfO2薄膜（K9基片）的椭偏参数,并用Sellmeier模型和Cauchy模型对两种薄膜进行拟合,获得了SiO2薄膜和HfO2薄膜在300-800nm波段内的色散关系。用X射线衍射仪确定薄膜结构,并用原子力显微镜观察薄膜的微观形貌,分析表明：SiO2薄膜晶相结构呈现无定型结构,HfO2薄膜的晶相结构呈现单斜相结构;薄膜光学常数的大小和薄膜的表面形貌有关;Sellmeier和Cauchy模型较好地描述了该波段内薄膜的光学性能,并得到薄膜的折射率和消光系数等光学常数随波长的变化规律。     

Improvement in the electrical performance and bias-stress stability of dual-active-layered silicon zinc oxide/zinc oxide thin-film transistor

Si-doped zinc oxide(SZO) thin films are deposited by using a co-sputtering method,and used as the channel active layers of ZnO-based TFTs with single and dual active layer structures.The effects of silicon content on the optical transmittance of the SZO thin film and electrical properties of the SZO TFT are investigated.Moreover,the electrical performances and bias-stress stabilities of the single- and dual-active-layer TFTs are investigated and compared to reveal the effects of the Si doping and dual-active-layer structure.The average transmittances of all the SZO films are about 90% in the visible light region of 400 nm-800 nm,and the optical band gap of the SZO film gradually increases with increasing Si content.The Si-doping can effectively suppress the grain growth of ZnO,revealed by atomic force microscope analysis.Compared with that of the undoped ZnO TFT,the off-state current of the SZO TFT is reduced by more than two orders of magnitude and it is 1.5 × 10~(-12) A,and thus the on/off current ratio is increased by more than two orders of magnitude.In summary,the SZO/ZnO TFT with dual-active-layer structure exhibits a high on/off current ratio of 4.0 × 10~6 and superior stability under gate-bias and drain-bias stress.