电化学沉积高c轴取向ZnO薄膜及其光学性能分析

采用阴极还原方法,在透明导电玻璃(ITO)上制备了高c轴择优取向的ZnO薄膜.通过X射线衍射、扫描电子显微镜等表征技术,研究了沉积电流对ZnO薄膜的结构、应力状态及表面形貌的影响;利用光致荧光光谱及透射光谱等分析方法,探讨了沉积电流变化对ZnO薄膜的光学性能的影响.研究结果显示:各沉积电流下均可制得高c轴取向的ZnO薄膜;薄膜表面形貌受电流的影响较大;从透射谱可以看出,薄膜在可见光波段有较高透射率,且薄膜厚度随沉积电流的增大而增大.光致荧光测量表明,电化学沉积的ZnO薄膜具有明显的带隙展宽.而且,随着沉积电流的增加,带隙发光强度逐渐减弱,缺陷发光逐渐增强.     

阴极电沉积ZnO薄膜的取向控制生长

采用阴极电沉积法,在Zn(NO3)2水溶液中,以304不锈钢为衬底制备了ZnO薄膜,研究了Zn2+浓度和电流密度对ZnO薄膜择优取向的影响规律。XRD结果表明:随着Zn2+浓度和电流密度增大,ZnO薄膜逐渐由(002)面择优取向生长转变为(101)面择优取向生长;当Zn2+浓度为0.005mol.L-1、电流密度为2.0mA.cm-2或Zn2+浓度为0.05mol.L-1、电流密度为0.5mA.cm-2时,可以得到(002)面择优取向生长的ZnO薄膜;当Zn2+浓度为0.05mol.L-1、电流密度为2.0mA.cm-2时,可以得到(101)面择优取向生长的ZnO薄膜。根据二维晶核理论,通过分析不同生长条件下的过饱和度及其对ZnO的(002)型和(101)型二维晶核形核活化能的影响,对这一规律进行了解释。可见,通过改变Zn2+浓度和电流密度能够实现阴极电沉积ZnO薄膜的取向可控生长。     

低温电化学沉积ZnO薄膜及光学性质

利用阴极还原沉积原理,在水浴65℃的Zn(NO3)2水溶液中,以金属锌片为衬底电沉积制备了ZnO薄膜。采用拉曼光谱和低温光致发光谱(LTPL)对ZnO膜的光学性质进行了表征。实验表明,较小电沉积过电位制备的样品没有明显的与富锌缺氧有关的580cm-1附近的拉曼峰,呈现373nm的紫外光致发光峰,说明较小的电沉积过电位有利于高晶体质量的ZnO膜生长。     

基于SSCVD方法的a-b轴取向ZnO薄膜制备

以Zn₄(OH)₂(O₂CCH₃)₆·2H₂O为单一固相有机源,采用单源化学气相沉积法(Single sour cechem icalvapor deposition,SSCVD)在Si(100)衬底上制备ZnO薄膜,用X射线衍射(XRD)、原子力显微镜(AFM)分析ZnO薄膜样品的晶体结构和微观形貌,并用X射线光电子能谱(XPS)对薄膜的锌氧化学计量比进行了分析。研究结果表明:在非平衡条件下所得到的ZnO薄膜沿a-b轴取向生长,基片温度对ZnO薄膜生长过程影响较大,随着基片温度的升高,薄膜呈现c轴生长趋势;晶粒成柱状、尺寸均匀、膜层结构致密;薄膜样品中n_Zn:n_O=0.985。     

生长温度对磁控溅射ZnO薄膜的结晶特性和光学性能的影响

采用反应射频磁控溅射方法，在Si (100) 基片上制备了具有高c轴择优取向的ZnO薄膜.利用 原子力显微镜、透射电子显微镜、X射线衍射分析、拉曼光谱等表征技术，研究了沉积温度 对ZnO薄膜的表面形貌、晶粒尺度、应力状态等结晶性能的影响；通过沉积温度对透射光谱 和光致荧光光谱的影响，探讨了ZnO薄膜的结晶特性与光学性能之间的关系.研究结果显示， 在室温至500℃的范围内，ZnO薄膜的晶粒尺寸随沉积温度的增加而增加，在沉积温度为500 ℃时达到最大；当沉积温度为750℃时，ZnO薄膜的晶粒尺度有所减小；在室温至750℃的范 围内，薄膜中ZnO晶粒与Si基体之间均存在着相对固定的外延关系；在沉积温度低于500℃时 ，制备的ZnO薄膜处于压应变状态，而750℃时沉积的薄膜表现为张应变状态.沉积温度的不 同导致ZnO薄膜的折射率、消光系数、光学禁带宽度以及光致荧光特性的变化，沉积温度对 紫外光致荧光特性起着决定性的作用.此外，探讨了影响薄膜近紫外光致荧光发射的可能因 素. 关键词： ZnO薄膜 表面形貌 微观结构 光学常数     

ZnO纳米薄膜的电化学制备及其AFM形貌表征

利用恒电位电化学沉积方法在ITO导电玻璃基底上制备了纳米ZnO薄膜,并利用原子力显微镜进行了形貌表征。结果显示,当沉积电压为-0．8V时,经过30min的沉积在基底上形成了由规则排列的三角形ZnO晶粒构成的纳米薄膜。对晶粒的形成机理进行了初步的讨论。     

磁约束电感耦合等离子体增强溅射沉积Co掺杂ZnO薄膜及其光学特性

采用磁约束电感耦合等离子体增强溅射法(ICP-PVD)在Si(100)和石英玻璃衬底上沉积了Zn_0.95Co_0.05O薄膜。XRD谱显示薄膜具有较强的(002)衍射峰,表明Zn_0.95Co_0.05O薄膜为c轴择优取向生长;透过光谱显示Zn_0.95Co_0.05O薄膜具有良好的透过性,其在可见光和红外波段的平均透过率大于80%,吸收光谱表明Co²⁺取代了Zn²⁺处于四配位晶体场中;喇曼光谱证明Zn_0.95Co_0.05O薄膜具有良好的六方纤锌矿结构;室温PL谱测量发现在可见光的蓝光波段和绿光波段存在较宽的发光带,却没有发现本征的近紫外光发射,这是由于Co掺杂后引入较多的缺陷导致的。     

ZnO·TiO2双层复合薄膜的制备及其光学性能的研究

采用溶胶-凝胶法(Sol-Gel),分别以乙酸锌(Zn(CH₃COO)₂H₂O)、钛酸酊酯(Ti(OC₄H₉)₄)为锌源和钛源,在玻璃衬底以及硅衬底上制备了不同浓度的、均匀的、结晶质量良好的单层ZnO、TiO₂薄膜及双层的ZnO·TiO₂复合薄膜。结果表明,所制备的单层本征ZnO、TiO₂薄膜分别沿(002)、(101)晶面生长,且当本征ZnO、TiO₂的浓度分别为0.45 mol/L、0.65 mol/L时,择优取向生长最明显。ZnO·TiO₂复合薄膜的(101)、(004)特征峰明显,且0.45 mol/L/0.55 mol/L的双层ZnO·TiO₂复合薄膜结晶质量最好;薄膜表面最为平整,粒子分布均匀,粘连现象最少;对紫外光的吸收最强,禁带宽度为3.39 eV。     

工作气压对磁控溅射ZnO薄膜结晶特性及生长行为的影响

采用射频反应磁控溅射方法，在Si(001)基片上制备了具有高c轴择优取向的ZnO薄膜.利用原子力显微镜、X射线衍射、透射电子显微镜和透射光谱分析技术，对不同工作气压下合成的ZnO薄膜的表面形貌、微观结构和光学性能进行表征，研究了工作气压对ZnO薄膜的结晶性能以及生长行为的影响.研究结果显示：对于Ar/O₂流量比例接近1∶1的固定比值下，ZnO薄膜的生长行为主要取决于成膜空间中氧的密度，临界工作气压介于0.5—1.0 Pa之间.当工作气压小于临界值时，ZnO薄膜的成核密度较高，且随工作气压的变化明显，ZnO的生长行为受控于氧的密度，属于氧支配的薄膜生长；当工作气压大于临界值以后，ZnO薄膜的成核密度基本保持不变，Zn原子的数量决定薄膜的生长速率；在0.1—5.0 Pa的工作气压范围内，均可获得高度c轴取向的ZnO薄膜，但工作气压的变化改变着ZnO晶粒之间的界面特征和取向关系.随着工作气压的增加，ZnO晶粒之间的界面失配缺陷减少，但平面织构特征逐渐消失，三叉晶界的空洞逐渐扩大，薄膜的密度下降，折射率减小. 关键词： ZnO薄膜 磁控溅射 表面形貌 微观结构 光学性能     

沉积温度对硫化锌(ZnS)薄膜的结晶和光学特性影响研究

对不同温度下沉积的ZnS薄膜的结晶情况和光学特性进行了研究, 结果表明：沉积温度对ZnS薄膜的物理和光学特性有较大影响, 不同的温度沉积的ZnS薄膜具有不同的择优取向, 牢固度也大不相同; 不同沉积温度下, ZnS薄膜的光学常数也不尽相同. 温度为115 ℃和155 ℃时, ZnS薄膜的物理性能和光学性能较差, 不适合空间用光学薄膜的研制使用. 而190 ℃和230 ℃沉积温度下所得薄膜具有较好的物理和光学性能, 适合于不同要求的空间用薄膜器件的研制使用. 关键词： 硫化锌薄膜 沉积温度 表面形貌 光学常数     

Optical and electrical properties of aluminum-doped ZnO thin films grown by pulsed laser deposition

Transparent aluminum-doped zinc oxide (AZO) thin films were deposited on quartz glass substrates by pulsed laser deposition (PLD) from ablating Zn-Al metallic targets. The structural, electrical and optical properties of these films were characterized as a function of Al concentration (0-8 wt.%) in the target. Films were deposited at a low substrate temperature of 150 °C under 11 Pa of oxygen pressure. It was observed that 2 wt.% of Al in the target (or 1.37 wt.% of Al doped in the AZO film) is the optimum concentration to achieve the minimum film resistivity and strong ultraviolet emission. The presence of Al in the ZnO film changes the carrier concentration and the intrinsic defects.     

Correlation between electrical and optical properties of Cr:ZnO thin films grown by pulsed laser deposition

Highly transparent and conducting Chromium doped ZnO (Cr:ZnO) thin films with preferential c-axis orientation were grown on (0 0 0 1) sapphire substrates using buffer assisted pulsed laser deposition. The resistivity of Cr:ZnO thin films was found to decrease to a minimum value of ∼1.13×10⁻³Ω cm with the increasing Cr concentration up to ∼1.9 at.% and then increase with further increase of Cr concentration. On the contrary, the band gap and carrier concentration of Cr:ZnO thin films increased up to ∼3.37 eV and ∼2×10²⁰ cm⁻³, respectively, with the increase of Cr concentration up to ∼1.9 at.%, then decreased with further increase of Cr concentration. The increase of carrier concentration and conductivity with Cr doping at low Cr concentrations (<1.9 at.%) could be attributed to the presence of Cr in +3 valence state in ZnO thus acting as donor while decrease of carrier concentration beyond ∼1.9 at.% of Cr concentration could be attributed to the charge compensating effect due to the presence of acceptor like point defects such as oxygen interstitials. This was experimentally confirmed using x-ray photoelectron spectroscopy. The observed variation in the band gap of Cr:ZnO thin films with increasing Cr doping was attributed to the competing effects of the high free carrier concentration induced Burstein-Moss blue shift and band gap narrowing.     

Electrical and optical properties of Sb-doped ZnO thin films synthesized by sol–gel method

Sb-doped ZnO thin films with different values of Sb content （from 0 to 1.1 at.%） are deposited by the sol-gel dip- coating method under different sol concentrations. The effects of Sb-doping content, sol concentration, and annealing ambient on the structural, optical, and electrical properties of ZnO films are investigated. The results of the X-ray diffraction and ultraviolet-visible spectroscopy （UV-VIS） spectrophotometer indicate that each of all the films retains the wurtzite ZnO structure and possesses a preferred orientation along the c axis, with high transmittance （〉 90%） in the visible range. The Hall effect measurements show that the vacuum annealed thin films synthesized in the sol concentration of 0.75 mol/L each have an adjustable n-type electrical conductivity by varying Sb-doping density, and the photoluminescence （PL） spectra revealed that the defect emission （around 450 nm） is predominant. However, the thin films prepared by the sol with a concentration of 0.25 mol/L, despite their poor conductivity, have priority in ultraviolet emission, and the PL peak position shows first a blue-shift and then a red-shift with the increase of the Sb doping content.     

Effect of intrinsic stress on the optical properties of nanostructured ZnO thin films grown by rf magnetron sputtering

In this paper we report the effect of deposition temperature on the structural and optical properties of ZnO thin films prepared by rf magnetron sputtering. The films grown at lower deposition temperatures were in a state of large compressive stress, whereas the films grown at higher temperature (450 °C) were almost stress free. In the absorption spectra, the ZnO excitonic and the Zn surface plasmon resonance (SPR) peaks have been observed. A redshift in the optical band gap of ZnO films has also been observed with the increase in the deposition temperature. The shift in the band gap calculated from the size effect did not match with the observed shift values and the observed shift has been attributed to the compressive stress present in the films.     

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.     

Near-field study of optical modes in randomly textured ZnO thin films

We report on near-field scanning optical microscopy measurements on randomly textured ZnO thin films. These films are commonly used as transparent conducting oxide in thin-film solar cells. Textured interfaces are used to increase the scattering of light, which leads to a better light trapping in the solar cell. Here, both the topography and the local transmission are measured with a tapered fiber tip with very high spatial resolution. By varying the distance of the tip and the wavelength of the incident light, the optical profile is visualized and reveals a strong confinement of light on a subwavelength scale which corresponds to ridges in the surface structure. The confinement of light results from guided optical modes in the ZnO which are accompanied by a modulated evanescent field in air. No corresponding structure to this modulation is found in the topography. These results give new insight for further improvement of light trapping in solar cells.     

Annealing effects on electrical and optical properties of ZnO thin films synthesized by the electrochemical method

Microstructural and electrical properties of potentiostatically electrodeposited ZnO thin films from an aqueous bath were investigated after annealing at different temperatures in Ar and 5% H₂/Ar atmospheres. It is confirmed that the bandgap energy of ZnO thin films decreased with annealing from 3.42 to 3.27-3.29 eV by calculating the wavelength of the absorption region. The annealing at temperatures as low as 200 °C decreased the sheet resistance of ZnO thin films because of the extinction of Zn(OH)₂ in the atmosphere. In addition, the sheet resistance of ZnO thin films decreased by annealing in a 5% H₂ atmosphere, which caused an increase of carrier concentration by hydrogen reduction.     

Microstructure and optical properties of nitrogen-doped ZnO film

The nitrogen doping of ZnO film deposited by the magnetron sputtering method is subsequently realized by the hydrothermal synthesis method.The nitrogen-doped ZnO film is preferably(002) oriented.With the increase of hexamethylenetetramine(HMT) solution concentration,the average grain size of the film along the 002 direction almost immediately decreases and then monotonously increases,conversely,the lattice strain first increases and then decreases.The structural evolution of the film surface from compact and even to sparse and rough is attributed to the enhanced nitrogen doping content in the hydrothermal process.The transmission and photoluminescence properties of the film are closely related to grain size,lattice strain,and nitrogen-related defect arising from the enhanced nitrogen doping content with HMT concentration increasing.     

Electrical characterisation of phosphorus-doped ZnO thin films grown by pulsed laser deposition

Phosphorus-doped ZnO films were grown by pulsed laser deposition using a ZnO:P₂O₅-doped target as the phosphorus source with the aim of producing p-type ZnO material. ZnO:P layers (with phosphorus concentrations of between 0.01 to 1 wt%) were grown on a pure ZnO buffer layer. The electrical properties of the films were characterised from temperature dependent Hall-effect measurements. The samples typically showed weak n-type conduction in the dark, with a resistivity of 70 Ω cm, a Hall mobility of μ_n0.5 cm² V ⁻¹ s⁻¹ and a carrier concentration of n3×10¹⁷ cm⁻³ at room temperature. After exposure to an incandescent light source, the samples underwent a change in conduction from n- to p-type, with an increase in mobility and decrease in concentration for temperatures below 300 K.