ZnO/Ag复合膜的制备及其润湿性转换研究

利用溶胶-凝胶技术制备了ZnO/Ag复合膜. 采用X射线粉末衍射和扫描电子显微镜对其物相组成、 晶型结构以及表面形貌进行了表征, 采用接触角测试仪对其润湿性进行了表征, 并研究了紫外光照射下Ag的掺杂量对ZnO薄膜润湿性的影响. 结果表明, 当Ag掺杂量(摩尔分数)为5%时, 所得膜的润湿性转换速率最快, 紫外光照3 h后, 其润湿性由超疏水性转换为亲水性, 黑暗中放置5 d后, 亲水性再次转换为超疏水, 实现了润湿性的可逆转换.     

Enhancement of optical conductivity in the ultra-violet region of Cs doped ZnO sol gel thin films

Nano crystalline cesium (Cs) doped ZnO thin films were deposited on glass substrate by sol gel spin coating method with 1–3 mol.% doping concentration and different annealing temperatures. The deposited films were characterized by X-ray diffraction (XRD), Hall Effect, Photoluminescence (PL) and UV–Visible studies. XRD measurements reveal that all the samples abound in the wurtzite structure with polycrystalline nature. An increase in crystalline size from 19.60 to 44.54 nm is observed with the increase of doping concentration. Electrical conductivity of Cs doped ZnO films were observed from Hall effect measurements and the maximum carrier concentration obtained is 7.35 × 10¹⁸ cm^?3. The near band emission (384 nm) peak intensity increases with the increase of Cs doping concentration and a maximum intensity 55,280 was observed for CZ3 film from PL spectrum. Also a low energy near infrared (NIR) emission peak centered at 1.62 eV appears for the Cs doped ZnO films. The average transmission of CZ film is 88 % and the absorption edge is red shifted with the increase of Cs doping concentration and also the optical conductivity increases in the UV region.     

介孔TiO2-ZnO复合薄膜的制备与表征

以三嵌段聚合物P123为模板剂, 以钛酸异丙酯和二水乙酸锌为无机前驱体, 利用溶胶-凝胶法和旋涂法成功地制备了不同ZnO含量的介孔TiO2-ZnO复合薄膜. 在ZnO前驱体摩尔分数为0~50％范围内获得薄膜质量较高的介孔TiO2-ZnO复合薄膜. 用小角XRD、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、能谱仪(EDS)、紫外-可见吸收光谱(UV-Vis)及X射线光电子能谱(XPS)对所得的复合薄膜进行了表征和分析. EDS和XPS等研究证明介孔薄膜为TiO2和ZnO的复合体系, 且ZnO前驱体含量的增加仍能保持TiO2-ZnO复合薄膜的均匀性. UV-Vis研究结果表明, 介孔复合薄膜的光学带隙宽度为3.45-3.58 eV, 随着ZnO含量的增加, 复合薄膜的紫外吸收蓝移.     

Structural and electrical properties of Li doped ZnO under Ar/H2 atmosphere

Thin films of ZnO were grown by the sol–gel method using spin-coating technique on (0001) sapphire substrates. The effect of doping under Ar/H₂ atmosphere on the structural and electrical properties of ZnO was investigated by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), I–V characterization, Hall effect and micro-photoluminescence. The films that were annealed at 600 °C in Ar/H₂ (95/5) % atmosphere showed (002) a predominant orientation. The crystalline nature of 2 mol.  % of Li doped films were better when compared to 1 mol.  % of Li doped films. The incorporation of Li in ZnO lattice was confirmed by X-ray photoelectron spectroscopy, and micro-photoluminescence. Hall effect measurements and I–V characterization of the Li doped ZnO thin films exhibited a better p-type behavior.     

Dual Manipulation of Ferromagnetism in Co-Doped ZnO Thin Films by Surfactant and n-Type Carriers

We present a conceptually-new approach “dual manipulation effect” using the surfactant passivation and the electron carrier doping for mediating intrinsic ferromagnetism in Codoped ZnO dilute magnetic semiconductor (DMS) thin films. The first-principles calculations show that the surface passivation by hydrogen serves as a magnetism switch for the Co-O-Co magnetic coupling at the surface of the thin film, and thus can control the spin polarization of the doped Co atoms. Meanwhile, the electron carrier doping can further function as an effective layerlike ferromagnetism mediator for the underneath layer. The dual manipulation effect sheds light on the essential magnetism origin of n-type Co:ZnO DMS thin films, and may be used as an alternative strategy for enhancing the ferromagnetism in other n-type DMS oxides thin films.     

Influence on electrochemical impedance and photovoltaic performance of natural DSSC using Terminalia catappa based on Mg-doped ZnO photoanode

In this paper, we report the successful fabrication of a novel dye-sensitized solar cell (DSSCs) using Mg doped ZnO as photoanode and natural dye Terminalia catappa as sensitizer. We synthesized Mg doped ZnO nanoparticles at different Mg concentrations (2%, 4%, 6%, and 8%) by employing a simple solvothermal route. The structural, morphology, composition and optical investigations of synthesized Mg doped ZnO nanoparticles are carried out using XRD, FE-SEM, EDAX, TEM, SAED, FTIR and UV–visible measurements. The XRD results confirmed the formation of hexagonal-wurtzite structure for the Mg doped ZnO nanoparticles and increase of crystalline size with increasing dopant concentration up to 6% is observed. FESEM analysis indicated a gradual change in the surface morphology with increasing Mg concentration and the size of the nanoparticles are slightly reduced at higher Mg concentration. The HRTEM images and SAED pattern also confirmed the formation of wurtzite hexagonal phase of ZnO. The band gap energies calculated from the UV–visible spectra using Tauc's plots indicated decrease of band gap energy with dopant concentration. The DSSCs fabricated using Mg doped ZnO photo-anodes and Terminalia catappa sensitizer showed higher efficiency at higher Mg concentration and observed increase in efficiency is discussed based on slower charge carrier recombination and higher carrier life time as evidenced from the electrochemical impedance analysis.     

Luminescence properties of Cu‐ion‐implanted and annealed ZnO thin films deposited by chemical vapor deposition and pulsed laser deposition

Ion implantation techniques were used to study the effect of an MgO additive on the luminescence properties induced by Cu in ZnO thin films. Cu ions (accelerating voltage of 75 keV, dose of 4.5 × 10¹⁴ ions/cm²) were implanted at room temperature in nondoped and Mg‐doped ZnO thin films. After annealing, emissions in the visible region originating from Cu phosphor were observed at 510 nm in CVD‐ZnO and at 450 nm in Mg‐doped ZnO (MZO) thin films. The Cu depth profile shows distortion in the low‐concentration region of CVD‐ZnO. After the annealing, the Cu implant was homogenized in thin films, and then the Cu concentration was determined to be 1.5 × 10¹⁹ ions/cm³ in CVD‐ZnO and 5.6 × 10¹⁸ ions/cm³ in MZO thin films. Copyright © 2005 John Wiley & Sons, Ltd.     

Improved optical and electrical properties of sol–gel-derived boron-doped zinc oxide thin films

Sol–gel spin-coating was used to grow zinc oxide (ZnO) thin films doped with 0–2.5 at.% B on quartz substrates. The structural, optical, and electrical properties of the thin films were investigated using field-emission scanning electron microscopy, X-ray diffraction (XRD), photoluminescence (PL), ultraviolet–visible spectroscopy, and van der Pauw Hall-effect measurements. All the thin films had deposited well onto the quartz substrates and exhibited granular morphology. The average crystallite size, lattice constants, residual stress, and lengths of the bonds in the crystal lattice of the thin films were calculated from the XRD data. The PL spectra showed near-band-edge (NBE) and deep-level emissions, and B doping varied the PL properties and increased the efficiency of the NBE emission. The optical transmittance spectra for the undoped ZnO and boron-doped zinc oxide (BZO) thin films show that the optical transmittance of the BZO thin films was significantly higher than that of the undoped ZnO thin films in the visible region of the spectra and that the absorption edge of the BZO thin films was blue-shifted. In addition, doping the ZnO thin films with B significantly varied the absorption coefficient, optical band gap, Urbach energy, refractive index, extinction coefficient, single-oscillator energy, dispersion energy, average oscillator strength, average oscillator wavelength, dielectric constant, and optical conductivity of the BZO thin films. The Hall-effect data suggested that B doping also improved the electrical properties such as the carrier concentration, mobility, and resistivity of the thin films.     

Influence of Ga dopant on photoelectrochemical characteristic of Ga‐doped ZnO thin films deposited by sol–gel spin‐coating technique

In this study, Ga‐doped ZnO thin films were prepared using sol–gel technique via spin‐coating method. The effect of Ga‐doping dopant (0, 1, 2 and 3 at.%) on microstructural, optical, electrical and photoelectrochemical (PEC) characteristics have been investigated. The spin‐coating was repeated six times, and as‐obtained thin films were then annealed at 500 °C for 1 h in vacuum. After annealing, all samples revealed single phase of hexagonal ZnO polycrystalline structure with a main peak of (002) in X‐ray diffraction (XRD) pattern. Raman spectra show that the vibration strength of E₂ is highly decreased by Ga doping. Thicknesses of all samples were ~300 nm measured via scanning electron microscopy (SEM) cross‐section images and alpha‐step. The optical band gap and resistivity of samples were in the range of 3.24 to 3.28 eV and 102 to 9 Ohm cm, respectively. Resulting from PEC response, the 2 at.% Ga‐doped ZnO thin film has a better PEC performance with photocurrent density of ~0.14 mA/cm² at 0.5 V versus saturated calomel electrode (SCE) under illumination with the intensity of 100 mW/cm². This value was about seven times higher than the un‐doped film (reference sample). Observed higher photocurrent density was likely because of a suitable Ga‐doping concentration causing a lower resistivity. Copyright © 2016 John Wiley & Sons, Ltd.     

金属有机化学气相沉积法制备ZnO和ZnO∶Ni薄膜及其特性分析

采用金属有机化学气相沉积法制备了ZnO和ZnO∶Ni薄膜,并对它们的结构、光学和电学特性进行了对比研究.通过扫描电子显微镜( SEM)和X射线衍射(XRD)对薄膜的表面形貌和晶体结构进行了分析,结果表明,Ni元素的掺杂虽然降低了薄膜的晶体质量,但并未改变ZnO的纤锌矿结构.通过紫外-可见分光光度计对薄膜的光学特性进行了...     

Ga-F共掺杂ZnO导电性和透射率的第一性原理计算

用基于密度泛函理论的第一性原理平面波超软赝势方法,对本征ZnO,Ga、F单掺ZnO和Ga-F共掺ZnO的几何结构进行优化后计算了各体系的相关性质.结果表明各掺杂体系有各自的优缺点,在制作透明导电薄膜时可根据具体要求采取不同的掺杂方案.Ga掺杂ZnO比F掺杂ZnO的晶格畸变小.相同环境下Ga原子比F原子更容易进入ZnO晶格,因此掺杂后结构更加稳定.Ga、F掺杂都改善了ZnO的导电性,掺杂ZnO的载流子浓度比本征ZnO增加了3个数量级,相同浓度的F掺杂比Ga掺杂能产生更多的载流子.Ga-F共掺杂ZnO折中了上述Ga、F单掺杂ZnO的优缺点.另外,掺杂后ZnO的吸收边蓝移,以Ga-F共掺杂ZnO在紫外区域的透射率最大,在280~380 nm范围内其透射率在90%以上.     

Open air annealing effect on the electrical and optical properties of tin doped ZnO nanostructure

Transparent conducting undoped and tin doped ZnO multilayer films were deposited by sol-gel method. Effect of open air annealing on different parameters like grain size, carrier density, band gap, resistivity, refractive index and extinction coefficient were investigated. Films were deposited on glass and silicon substrate by keeping doping concentration 4 at%. It was observed that tin doping reduces resistivity from 194.6 Ω cm to 3.11 Ω cm. Optical transmission spectra exhibit transmittance above 88% in visible range. Maximum carrier density of 11.9 × 10¹⁸ cm⁻³ and band gap of 3.24 eV was estimated at 375 °C. Scanning Electron Microscopy showed homogenous worm like morphology. Atomic force microscopy revealed pyramid shaped nanostructure of tin doped ZnO.     

Ga-F共掺杂ZnO导电性和透射率的第一性原理计算

采用基于密度泛函理论的第一性原理平面波超软赝势方法,对本征ZnO,Ga、F单掺ZnO和Ga-F共掺ZnO的几何结构进行优化后计算了各体系的相关性质。结果表明各掺杂体系有各自的优缺点,在制作透明导电薄膜时可根据具体要求采取不同的掺杂方案。Ga掺杂ZnO比F掺杂ZnO的晶格畸变小。相同环境下Ga原子比F原子更容易进入ZnO晶格,因此掺杂后结构更加稳定。Ga、F掺杂都改善了ZnO的导电性,掺杂ZnO的载流子浓度比本征ZnO增加了3个数量级,相同浓度的F掺杂比Ga掺杂能产生更多的载流子。Ga-F共掺杂ZnO折中了上述Ga、F单掺杂ZnO的优缺点。另外,掺杂后ZnO的吸收边蓝移,以GaF共掺杂ZnO在紫外区域的透射率最大,在280~380 nm范围内其透射率在90%以上。     

Mechanistic study of the electrodeposition of nanoporous self-assembled ZnO/Eosin Y hybrid thin films: effect of eosin concentration

ZnO films prepared by one-step electrodeposition in the presence of dissolved eosin molecules present an internal nanoporous hybrid structure resulting from self-assembling processes occurring in solution between ZnO and eosin components. This study aims to better understand the underlying growth mechanism, which is still unexplained. The films were deposited by cathodic electrodeposition from an oxygen-saturated aqueous zinc chloride solution. The effects of the addition of 10 to 100 micromol.L(-1) eosin Y, as a sodium salt, on the growth rate and film properties, were systematically studied while all other parameters remained constant (concentrations of zinc salt and supporting electrolyte, applied potential of -1.4 V versus the mercurous sulfate electrode (MSE), temperature of 70 degrees C, rotating disk electrode at 300 rotations per min, and a glass-coated tin oxide electrode). It is shown that the addition of eosin provokes the formation of a nanoporous "cauliflower" structure whose nodule size and composition depend on the eosin concentration in the bath. The growth rate of the hybrid films increases markedly with the eosin concentration. The ZnO and eosin contents of the films are determined for each concentration by chemical analysis. Comparing with thickness determinations, it is shown that the total porosity increases up to 60-65% in volume fraction toward an eosin concentration of 100 micromol.L(-1). The empty pore volume fraction increases up to about 30% at an eosin concentration of about 20 micromol.L(-1) and then decreases. These correlations have been precisely established for the first time. It is shown that the global composition is fixed by the relative rate of deposition for zinc oxide, which is constant, and for the relative rate of eosin inclusion, which is proportional to the concentration in solution. This is explained on the basis of different steps in the growth mechanism, in particular, a diffusion effect limitation for both oxygen and eosin. This variation explains part of the increase in the growth rate. Another contribution is related by the structural effect on the nanoscale leading to the formation of the interpenetrated porous network. Competition between empty and eosin-filled parts of the pore network is evidenced. The formation of the porous network structure could be governed by a diffusion-limited aggregation mechanism. The system may represent a reference case of competing reactions in the electrochemical self-assembly of hybrid nanostructures.     

Improvement of electrical properties of sol–gel derived ZnO:Ga films by infrared heating method

In this study, we investigated the influences of gallium concentration and a rapid thermal annealing process on the electrical and optical properties of ZnO:Ga (GZO) films prepared by sol–gel method. Experimental data indicated that the preferential growth directions of ZnO crystallites were the (002) and (103) axes. This phenomenon implied that the nucleation and growth behaviors of ZnO crystallites were changed by the infrared heating procedure and monoethanolamine. Furthermore, since the deposited sol films were heated simultaneously, evenly, and rapidly, dopant material Ga got the opportunity to replace Zn instead of forming oxides embedded in grain boundary areas. Thus, carrier concentration of the GZO films can be considerably enhanced while the mobility of the GZO films was not apparently affected in our experiments. It was also found that the carrier concentration was not sensitive to Ga/Zn ratio even though higher Ga concentration led to lower mobility. The best sample with a resistivity of 2.20 × 10⁻³ Ω cm and a transmittance of over 80% in visible region was achieved with 1.0 at.% Ga.     

Free-standing boron doped CVD diamond films grown on partially stabilized zirconia substrates

Boron doped diamond films have been grown adhered to silicon substrates by chemical vapor deposition using boron containing gases. In this work it was shown that it is possible to grow free-standing boron doped CVD diamond films on partially stabilized zirconia substrates using boron powder as the source for doping. Results from Raman spectroscopy confirmed the boron incorporation with concentration up to ∼10²⁰ cm⁻³. X-ray diffraction and scanning electron microscopy showed that the effect of boron incorporation in the microstructure of the diamond film is negligible. The measurement of the resistivity as a function of temperature confirmed the semiconductor behavior, as expected for p-type diamond.     

磁控溅射中靶-基底距离与Si共掺对ZnO:Al薄膜性质的影响

使用射频磁控溅射, 在正方形石英衬底上沉积透明导电掺Al的ZnO(AZO)和Si共掺AZO(AZO:Si)薄膜. 系统研究了靶-基底距离(D_st)和Si共掺对AZO薄膜电学、光学性质的影响. 电阻率、载流子浓度和迁移率都强烈地依赖于靶-基底距离, 随着靶-基底距离的减少, 载流子浓度和迁移率都有显著的增加, 电导率也随之提高. 在靶-基底距离为4.5 cm处, 得到最低电阻率4.94×10^-4 Ω·cm, 此时的载流子浓度和迁移率分别是3.75×10²⁰ cm^-3和33.7 cm²·V^-1·s^-1. X射线光电子能谱(XPS)、X射线衍射(XRD)和边界散射模型被用于分析载流子浓度、迁移率和靶-基底距离的关系. 透射谱显示, 在可见-近红外范围内所有样品均有大于93%的平均透射率, 同时随着靶基距离的减少, 吸收边蓝移. AZO:Si表现出可与AZO相比拟的高电导和高透射光学特性, 但在热湿环境中却有着更好的电阻稳定性, 这在实际使用中很有意义.     

The Effect of Lithium Doping in Solution-Processed Nickel Oxide Films for Perovskite Solar Cells

The effect of substitutional Li doping into NiO_x hole transporting layer (HTL) for use in inverted perovskite solar cells was systematically studied. Li doped NiO_x thin films with preferential crystal growth along the (111) plane were deposited using a simple solution-based process. Mott-Schottky analysis showed that hole carrier concentration (N_A) is doubled by Li doping. Utilizing 4 % Li in NiO_x improved the power conversion efficiency (PCE) of solar devices from 9.0 % to 12.6 %. Photoluminescence quenching investigations demonstrate better hole capturing properties of Li:NiO_x compared to that of NiO_x, leading to higher current densities by Li doping. The electrical conductivity of NiO_x is improved by Li doping. Further improvements of the device were made by using an additional ZnO layer onto PCBM, to remove shunt paths, leading to a PCE of 14.2 % and a fill factor of 0.72.     

Preparation of nitrogen doped zinc oxide nanoparticles and thin films by colloidal route and low temperature nitridation process

Nitrogen doped zinc oxide (ZnO) nanoparticles have been synthesized using a colloidal route and low temperature nitridation process. Based on these results, 200 nm thick transparent ZnO thin films have been prepared by dip-coating on SiO₂ substrate from a ZnO colloidal solution. Zinc peroxide (ZnO₂) thin film was then obtained after the chemical conversion of a ZnO colloidal thin film by H₂O₂ solution. Finally, a nitrogen doped ZnO nanocrystalline thin film (ZnO:N) was obtained by ammonolysis at 250 °C. All the films have been characterized by scanning electron microscopy, X-ray diffraction, X-Ray photoelectron spectroscopy and UV–Visible transmittance spectroscopy.     

Realizing luminescent downshifting in ZnO thin films by Ce doping with enhancement of photocatalytic activity

ZnO thin films doped with Ce at different concentration were deposited on glass substrates by spray pyrolysis technique. XRD analysis revealed the phase purity and polycrystalline nature of the films with hexagonal wurtzite geometry and the composition analysis confirmed the incorporation of Ce in the ZnO lattice in the case of doped films. Crystalline quality and optical transmittance diminished while electrical conductivity enhanced with Ce doping. Ce doping resulted in a red-shift of optical energy gap due to the downshift of the conduction band minimum after merging with Ce related impurity bands formed below the conduction band in the forbidden gap. In the room temperature photoluminescence spectra, UV emission intensity of the doped films decreased while the intensity of the visible emission band increased drastically implying the degradation in crystallinity as well as the incorporation of defect levels capable of luminescence downshifting. Ce doping showed improvement in photocatalytic efficiency by effectively trapping the free carriers and then transferring for dye degradation. Thus Ce doped ZnO thin films are capable of acting as luminescent downshifters as well as efficient photocatalysts.