Effect of annealing temperature on photocatalytic activity of ZnO thin films prepared by sol-gel method

Zinc oxide thin films are deposited on Si and quartz substrates using the sol-gel method. The thin films, annealed at 400, 600 and 800 °C respectively, are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), ultraviolet-visible spectrophotometer (UV-Vis), fluorescence spectrometer (FL) and the photocatalytic activity is tested by the decomposition of methyl orange dye under UV illumination. The results show that the mean grain size, surface-to-volume ratio, rms roughness and degradation efficiency of the thin films increases with increasing annealing temperature. In particular, ZnO thin film annealed at 800 °C exhibits the highest photocatalytic activity, degrading methyl orange by almost 88% in 180 min. Photocatalytic reaction mechanism of the ZnO thin films is discussed in detail, and the oxygen defects are proposed to be the active sites of the ZnO photocatalyst.     

Al掺杂原子分数及退火温度对ZnO薄膜光学特性的影响

 采用溶胶凝胶法在（0001）Al₂O₃衬底上制备了不同掺杂原子分数的ZnO:Al薄膜,在Ar气氛中进行了600～950 ℃不同温度的退火处理,研究了掺杂原子分数和退火温度对薄膜光致发光、光吸收和透射的影响。结果显示,薄膜的紫外峰强度随掺杂原子分数和退火温度的提高而增强,与缺陷相关的绿光强度却随着掺杂原子分数和退火温度的提高而降低;薄膜光学带隙随掺杂原子分数的提高从3.21 eV增大到3.25 eV;光吸收在可见光区随着退火温度的升高而增大,在紫外区却随着退火温度的升高而减小,透射与吸收的变化规律相反;薄膜吸收边随退火温度的升高出现轻微的红移。     

Effect of hydrogen doping in ZnO thin films by pulsed DC magnetron sputtering

This study examined the role of hydrogen impurities in highly oriented ZnO thin films. Hydrogen intentionally incorporated was found to play an important role as a donor in n-type conduction, improving the free carrier concentration. The increase in the conductivity of ZnO thin films was attributed to the two centers assigned to isolated hydrogen atoms in the anti-bonding sites as well as bond-centered interstitial hydrogen located between the Zn–O bonds and Zn vacancy passivated by one or two hydrogen atoms. Micro Raman spectroscopy showed two additional modes at approximately 501 and 573 cm⁻¹. These two peaks were attributed to damage to the crystal lattice, which could be explained by the optical-phonon branch at the zone boundary and host lattice defects, such as vacancy clusters, respectively.     

Influence of glucose 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 on glass substrates followed by calcinations at 500 °C for an hour. The effect of glucose on the structure and optical properties of the films was studied. The structural characteristics of the samples were analyzed by X-ray diffractometer (XRD) and atomic force microscope (AFM). The optical properties were studied by a UV-visible spectrophotometer. The results show that some of the prepared ZnO thin films have a high preferential oriented c-axis orientation with compact hexagonal wurtzite structure due to a proper amount of glucose introducing. After introducing the glucose additive in ZnO colloids, the intensity of (002) peak, the transmittance, and the optical band gap of the ZnO thin films increases because of the enhanced ZnO crystallization. On the contrary, the absorbance, the film thickness, and the surface root-mean-square (RMS) roughness of the ZnO thin films decreases. The glucose additive could not only improve the surface RMS roughness and microstructure of ZnO thin films, but also enhance the transmittance and the energy band gap more easily.     

Synthesis and characterization of the Pd/InVO4-TiO2 co-doped thin films with visible light photocatalytic activities

Novel Pd/InVO₄-TiO₂ thin films with visible light photocatalytic activity were synthesized from the Pd and InVO₂ co-doped TiO₂ sol via sol-gel method. The photocatalytic activities of Pd/InVO₄-TiO₂ thin films were investigated based on the oxidative decomposition of methyl orange in aqueous solution. The as-prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectroscopy (UV-vis). The results indicate that the Pd/InVO₄-TiO₂ thin films are compact, uniform and consist of sphere nanoparticles with diameters about 80-100 nm. The UV-vis spectra show that the Pd/InVO₄-TiO₂ thin films extend the light absorption spectrum toward the visible region. XPS results reveal that doped Pd exist in the form of metallic palladium. The photocatalytic experiments demonstrate that Pd doping can effectively enhance the photocatalytic activities of InVO₄-TiO₂ thin films in decomposition of aqueous methyl orange under visible light irradiation. It has been confirmed that Pd/InVO₄-TiO₂ thin films could be excited by visible light (E < 3.2 eV) due to the existence of the Pd and InVO₄ doped in the films.     

Photocatalytic reduction of chromium(VI) in aqueous solution using dye-sensitized nanoscale ZnO under visible light irradiation

Photocatalytic removal of Cr⁶⁺ from aqueous solution using dye-sensitized nanoscale ZnO under visible light irradiation was studied in this work. First, nanoscale ZnO was prepared by the co-precipitation method. Then, sensitization of nanoscale ZnO by Alizarin Red S dye followed. Further, nanoscale ZnO and dye-sensitized nanoscale ZnO (designated nanoZnO and nanoZnO*, respectively) were both characterized by various photospectrometry methods, such as scanning electron microscopy (SEM), scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDS), EDS-mapping, transmission electron microscopy (TEM), and X-ray diffractometry (XRD). It was found that both types of prepared particles are spherical in shape with a size range of 20 to 50 nm. XRD patterns showed that both nanoZnO and nanoZnO* had the same crystalline structure of zincite. In the photocatalytic reduction aspect, effects of different light sources and dosage of nanoZnO* on Cr⁶⁺ reduction ([Cr⁶⁺]_initial = 20 mg/L) were evaluated in this work. Treatment of chromium(VI)-bearing wastewater under the conditions of using 1.0 g/L of nanoZnO*, neutral pH, irradiation of household fluorescence lamps for 6 h and 17 h would yield Cr⁶⁺ removal efficiencies of about 68% and 90%, respectively. When the household fluorescence lamps were replaced by visible-light lamps of 400–500 nm in wavelength, the corresponding removal efficiencies dropped to about 50% and 75%, respectively. When nanoZnO* was irradiated by sunlight under almost the same experimental conditions, the Cr⁶⁺ reduction efficiency increased up to 90%. In summary, sensitizing nanoscale ZnO with Alizarin Red S dye for photocatalytic applications using visible light is feasible. The relevant reaction mechanism and pathways were also proposed in this work.     

不同退火温度下氧化锌薄膜可见发光与n型导电研究

采用脉冲激光沉积法在蓝宝石衬底上制备出可见光发光良好的氧化锌薄膜, 在不同的温度下进行了后退火处理. 随着退火温度的升高, 薄膜的可见光发光发生了显著改变, 载流子浓度、迁移率、电阻率也呈现出一定的变化规律. 结合 X射线衍射、扫描电子显微镜、光致发光谱及霍尔测量, 探讨了本征氧化锌薄膜可见光发光的发射机理, 并分析了其 n型导电的原因. 关键词： 氧化锌薄膜 可见光发光 n型导电     

Photoluminescence study of pure and Li-doped ZnO thin films grown by sol-gel technique

The effect of annealing atmosphere, temperature and aging on the photoluminescence of pure and Li-doped ZnO thin films has been investigated. Annealing the pure ZnO in N₂ and He above 800 °C results in green emission centered at ca. 500 nm; however annealing in air red-shifts the green emission to 527 nm. The visible emission of the Li-doped ZnO is found to be largely dependent on the annealing atmosphere. Warm-white photoluminescence with a broad emission band covering nearly the whole visible spectrum is obtained for the Li-doped ZnO films annealed in helium. The substitutional and interstitial extrinsic point defects created by lithium doping may mediate the relative concentration of the intrinsic defects and thereby tune the intrinsic-defect-related visible emission. The enhanced intensity ratio of near-band-edge ultraviolet emission to deep-level visible emission with aging time may be ascribed to both in-diffusion of oxygen from air and self-diffusion of oxygen interstitials to heal the oxygen vacancies during the aging process.     

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,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     

A novel Ce, C-codoped TiO2 nanoparticles and its photocatalytic activity under visible light

A novel photocatalyst (Ce, C-codoped titania) was synthesized through a modified sol-gel method under mild condition. The as-prepared sample was investigated by XRD, SEM, DRS and XPS. It was found that the as-prepared photocatalyst was composed of spheroidal particles, which were smaller than undoped ones. The absorbance spectrum of Ce, C-codoped TiO₂ exhibited significant red-shift to visible region. It can be ascribed to appearance of a new electronic state in the middle of the TiO₂ band-gap. Furthermore, cerium doping could slow the radiative recombination process of photogenerated electrons and holes in TiO₂. Accordingly, for degradation of dye Reactive Brillint Red X-3B (C.I. reactive red 2) under visible light, the photocatalytic activity of Ce, C-codoped TiO₂ improved much compared to other samples (C-doped TiO₂, undoped TiO₂ and P25).     

Effect of K-doping on structural and optical properties of ZnO thin films

In this work, K-doped ZnO thin films were prepared by a sol–gel method on Si(111) and glass substrates. The effect of different K-doping concentrations on structural and optical properties of the ZnO thin films was studied. The results showed that the 1 at.% K-doped ZnO thin film had the best crystallization quality and the strongest ultraviolet emission ability. When the concentration of K was above 1 at.%, the crystallization quality and ultraviolet emission ability dropped. For the K-doped ZnO thin films, there was not only ultraviolet emission, but also a blue emission signal in their photoluminescent spectra. The blue emission might be connected with K impurity or/and the intrinsic defects (Zn interstitial and Zn vacancy) of the ZnO thin films.     

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.     

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.     

Copper NPs decorated titania: A novel synthesis by high energy US with a study of the photocatalytic activity under visible light

The most important drawback of the use of TiO₂ as photocatalyst is its lack of activity under visible light. To overcome this problem, the surface modification of commercial micro-sized TiO₂ by means of high-energy ultrasound (US), employing CuCl₂ as precursor molecule to obtain both metallic copper as well as copper oxides species at the TiO₂ surface, is here. We have prepared samples with different copper content, in order to evaluate its impact on the photocatalytic performances of the semiconductor, and studied in particular the photodegradation in the gas phase of some volatile organic molecules (VOCs), namely acetone and acetaldehyde. We used a LED lamp in order to have only the contribution of the visible wavelengths to the TiO₂ activation (typical LED lights have no emission in the UV region). We employed several techniques (i.e., HR-TEM, XRD, FT-IR and UV–Vis) in order to characterize the prepared samples, thus evidencing different sample morphologies as a function of the various copper content, with a coherent correlation between them and the photocatalytic results. Firstly, we demonstrated the possibility to use US to modify the TiO₂, even when it is commercial and micro-sized as well; secondly, by avoiding completely the UV irradiation, we confirmed that pure TiO₂ is not activated by visible light. On the other hand, we showed that copper metal and metal oxides nanoparticles strongly and positively affect its photocatalytic activity.     

Effect of precursors on structure, optical and electrical properties of chemically deposited nanocrystalline ZnO thin films

Nanocrystalline ZnO thin films were chemically deposited on glass substrates using two different precursors namely, zinc sulphate and zinc nitrate. XRD studies confirm that the films are polycrystalline zinc oxide having hexagonal wurtzite structure with crystallite size in the range 25-33 nm. The surface morphology of film prepared using zinc sulphate exhibits agglomeration of small grains throughout the surface with no visible holes or faulty zones, while the film prepared using zinc nitrate shows a porous structure consisting of grains with different sizes separated by empty spaces. The film prepared using zinc sulphate shows higher reflectance due to its larger refractive index which is related to the packing density of grains in the film. Further, the film prepared using zinc sulphate is found to have normal dispersion for the wavelength range 550-750 nm, whereas the film prepared using zinc nitrate has normal dispersion for the wavelength range 450-750 nm. The direct optical band gaps in the two films are estimated to be 3.01 eV and 3.00 eV, respectively. The change in film resistance with temperature has been explained on the basis of two competing processes, viz. thermal excitation of electrons and atmospheric oxygen adsorption, occurring simultaneously. The activation energies of the films in two different regions indicate the presence of two energy levels - one deep and one shallow near the bottom of the conduction band in the bandgap.     

Photoluminescence and photoelectrochemical properties of nanocrystalline ZnO thin films synthesized by spray pyrolysis technique

A simple and inexpensive spray pyrolysis technique (SPT) was employed for the synthesis of nanocrystalline zinc oxide (ZnO) thin films onto soda lime glass and tin doped indium oxide (ITO) coated glass substrates at different substrate temperatures ranging from 300 °C to 500 °C. The synthesized films were polycrystalline, with a (0 0 2) preferential growth along c-axis. SEM micrographs revealed the uniform distribution of spherical grains of about 80-90 nm size. The films were transparent with average visible transmittance of 85% having band gap energy 3.25 eV. All the samples exhibit room temperature photoluminescence (PL). A strong ultraviolet (UV) emission at 398 nm with weak green emission centered at 520 nm confirmed the less defect density in the samples. Moreover, the samples are photoelectrochemically active and exhibit the highest photocurrent of 60 μA, a photovoltage of 280 mV and 0.23 fill factor (FF) for the Zn₄₅₀ films in 0.5 M Na₂SO₄ electrolyte, when illuminated under UV light.     

Influence of MoS2 deposition time on the photocatalytic activity of MoS2/ V,N co-doped TiO2 heterostructure thin film in the visible light region

Electron-hole separation and a narrow band-gap are essential steps to obtain efficient photocatalysis, towards which the use of co-catalysts or co-doped-TiO₂ photocatalysts has become a widely used strategy. In this article, the combination of MoS₂ and co-doping of V, N is the goal to achieve high performance photocatalysts. We synthesized MoS₂/V, N co-doped TiO₂ heterostructure thin film by sol-gel and chemical bath deposition methods. Herein, we investigated the influence of deposition time of MoS₂ layer on visible-photocatalytic activity of the obtained samples. The thin films were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV–vis spectroscopy techniques. Visible-photocatalytic activity of these samples were evaluated on the removal of methylene blue (MB) under visible light irradiation. The results show that the aforementioned heterostructure thin films have better photocatalytic activities than those of TiO₂, MoS₂ and V, N co-doped TiO₂ counterparts in visible light region. The mechanism for increasing visible-photocatalytic property of the heterostructure thin films is discussed in detail. We find that MoS₂/V, N co-doped TiO₂ heterostructure thin film at MoS₂ deposition time of 45-min shows the highest photocatalytic performance in the visible light region with MB photodegradation rate about 99% for 150 min and the degradation rate constant is 2.06 times higher than that of V and N co-doped TiO₂ counterpart.