Fine pattern fabrication on SnO2:Sb thin films formed by the sol–gel process

The effects of UV irradiation on the properties of Sb⁵⁺ doped gel films were studied, which were prepared from stannic chloride (SnCl₄·5H₂O) and sodium alkoxide (NaOR) modified with benzytone (BzAcH). It was found that the absorption peak at around 335 nm due to the π → π* transition showed the formation of a chelate ring to Sn. The intensity of the absorption band decreased with UV light irradiation at 365 nm from a high‐pressure mercury lamp (250W). This finding showed that the SnO₂:Sb gel films modified with BzAcH were photosensitive to UV light. Additionally, this finding was applied to the fabrication of patterns on the SnO₂:Sb thin films. A gel film was irradiated through a mask and leached in water. Then a positive pattern was formed on the SnO₂:Sb thin films attached to the substrate. After heat treatment, the SnO₂:Sb gel films changed into transparent conductive films with an average conductivity of 1.20 × 10^?2Ω cm and with a transmission of 97.1%. Copyright © 2006 John Wiley & Sons, Ltd.     

Electrical,optical, and structural characterization of p‐type N‐doped SnO thin films prepared by thermal oxidation of sputtered SnNx thin films

We present a study of electrical and optical properties of nitrogen‐doped tin oxide thin films deposited on glass by the DC Magnetron Sputtering method. The deposition conditions to obtain p‐type thin films were a relative partial pressure between 7% and 11% (N₂ and/or O₂), a total working pressure of 1.8 mTorr and a plasma power of 30 W. The deposited thin films were oxidized after annealing at 250°C for 30 minutes. X‐ray diffraction results showed that the as‐deposited thin films exhibit a Sn tetragonal structure, and after annealing, they showed SnO tetragonal structure. X‐ray photoelectron spectroscopy results showed the presence of nitrogen in the samples before and after annealing. The measured physical parameters of the thin films were optical band gap between 1.92 and 2.68 eV, resistivity between 0.52 and 5.46 Ωcm, a concentration of p‐type carriers between 10¹⁸ and 10¹⁹ cm^?3, and a Hall mobility between 0.1 and 1.94 cm²V^?1s^?1. These thin films were used to fabricate p‐type thin film transistors.     

Influence of substrate temperature on the structural and optical properties of crystalline ZnO films obtained by pulsed spray pyrolysis

In this work, we report on the structural and optical properties of ZnO films deposited by pulsed spray pyrolysis at relatively low temperatures, compatible with a large variety of substrates and processing technologies. Crystalline ZnO films were deposited onto glass substrates using zinc acetate dihydrate dissolved in distilled water with concentration of 0.2 M. The temperature of the substrate was varied in the range T_s = 473–673 K with ΔТ = 50 K. Effect of T_s were investigated by scanning electron microscopy, x‐ray diffraction and energy dispersive x‐ray, and optical spectroscopies. Also, the influence of T_s on the grain size, phase composition, texture quality, coherent scattering domain size, crystal lattice parameters, chemical composition, transmission coefficient, and the bang gap of the ZnO films were studied. X‐ray diffraction analysis revealed that films were polycrystalline with hexagonal phase and showed as preferential orientation (101) at T_s < 573 K and (100) and (002) at T_s > 573 K. Scanning electron microscopy (SEM) measurements showed that the substrate temperature has a strong effect on morphology of the films. Energy dispersive analysis revealed that ZnO films consisted of the non‐stoichiometric compounds. Optical measurements showed ZnO films to be highly transparent in the visible region, and optical band gap is shifting from 3.18 eV to 3.30 eV. Copyright © 2015 John Wiley & Sons, Ltd.     

Structural and nanomechanical properties of sol–gel prepared (K,Na)NbO3 thin films

Perovskite (K, Na)NbO₃ (KNN) thin films (~100 nm) were prepared by sol–gel/spin coating process on Pt/SiO₂/Si substrates and annealed at 650 °C. The structural properties of KNN films were confirmed by X‐ray diffraction analysis (XRD), Raman spectroscopy and scanning electron, transmission electron and atomic force microscopy (SEM, TEM and AFM) analysis. Pure perovskite phase of K_0.65Na_0.35NbO₃ in nonstoichiometric composition with monoclinic symmetry in film was revealed. Uniform homogeneous microstructure of KNN film with the roughness (~6.9 nm) contained spherical particles (~50–90 nm). Nanoindentation technique was used to characterize the mechanical properties of KNN films. Elastic modulus and hardness of Pt, SiO₂ and KNN thin films were calculated from their composite values of KNN/Pt/SiO₂/Si film/substrate system. The modulus and hardness of KNN film (71 and 4.5 GPa) were lower in comparison with SiO₂ (100 and 7.5 GPa). Pt film (~30 nm) did not influence the composite modulus, but had effect on hardness of KNN film. Copyright © 2015 John Wiley & Sons, Ltd.     

Investigation of molar concentration effect on structural,optical, electrical,and photovoltaic properties of spray‐coated Cu2O thin films

High quality copper oxide thin films were prepared by nebulizer spray pyrolysis technique using different concentrations of copper precursor solution. Concentration‐dependent structural, morphological, optical, and electrical properties of the prepared films are discussed. X‐ray diffraction studies done for the samples confirmed that the deposited films are in Cu₂O phase with polycrystalline cubic structure. Atomic force microscopy analysis revealed that all the films are composed of nano sheet shaped grains covering the substrate surface. Optical studies done on the samples showed band gap values 2.42, 2.31, and 2.02 eV for the solution concentration 0.01, 0.05, and 0.1 M, respectively. Photoluminescence spectral analysis showed the emission band at 620 nm confirming the formation of cuprous oxide. Electrical analysis of the films showed p‐type conductivity with a low resistivity 2.19 × 10² Ω.cm and high carrier concentration 16.76 × 10 ¹⁵ cm⁻³ for the molar concentration 0.1 M. In this work, Cu₂O/ZnO heterojunctions were also prepared, and solar cell properties were studied; they were found to show increased open circuit voltage and short circuit current for higher copper concentration.     

Preparation and characterization of mesoporous silica thin films from polyethoxysiloxanes

Tetraethoxysilane (TEOS) and polyethoxysiloxanes (PEOSs; prepared by the acid‐catalyzed hydrolytic polycondensation of TEOS) were subjected to the sol–gel process in the presence of cetyltrimethylammonium bromide (CTAB), respectively. The PEOSs with M_w 700–26,000, as prepared by sol–gel coating of TEOS and PEOS under various conditions, were used. Uniform and crack‐free thin films of thickness 276–613 nm were prepared by spin‐coating of a PEOS solution containing CTAB. When the coating films were sintered at 400 °C, the combustion of ethoxy groups and CTAB took place to provide porous silica thin films. The structure of the thin films was found to be dependent on the molecular weight of PEOS and the molar ratio of CTAB/Si: lamellar or hexagonal phase was observed for M_w less than 15,000 and for CTAB/Si molar ratios greater than 0.10. Honeycomb structures were observed for M_w less than 5000 and for CTAB/Si molar ratios of 0.15. The honeycomb structure was also observed by atomic force microscopy and transmission electron microscope. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2542–2550, 2006     

Investigation of IrO2/SnO2 thin film evolution by thermoanalytical and spectroscopic methods

The formation mechanism of thermally prepared IrO₂/SnO₂ thin films has been investigated under in situ conditions by thermogravimetry combined with mass spectrometry (TG-MS) and infrared emission spectroscopy (IRES). Mixtures of varying composition of the precursor salts (SnCl₂·2H₂O dissolved in ethanol and IrCl₃·3H₂O dissolved in isopropanol) were prepared onto titanium metal supports. Then the solvent was evaporated and the gel-like films were heated in an atmosphere containing 20% O₂ and 80% Ar to 600°C. The thermogravimetric curves showed that the evolution of the oxide phases take place in several decomposition stages and the final mixed oxide film is formed between 490 and 550°C, depending on the noble metal content. Mass spectrometric ion intensity curves revealed that below 200°C crystallization water, residual solvent, and hydrogen-chloride (formed as a result of an intramolecular hydrolysis) are liberated. The decomposition of surface species (surface carbonates, carbonyls and carboxylates) formed via the interaction of the residual solvent with the precursor salts takes place up to 450°C as evidenced by emission Fourier transform infrared spectrometry. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study of zinc thiocarbamide chloride,a single-source precursor for zinc sulfide thin films by spray pyrolysis

Thermal decomposition of the title compound, Zn(tu)₂Cl₂ (tu=thiourea), was studied up to 1200°C in dynamic inert (N₂) and oxidative (air) atmospheres using simultaneous TG/DTA techniques. In addition, XRD and IR were employed ex situ to resolve the reaction mechanism and products. Cubic ZnS (sphalerite) is formed below 300°C in both atmospheres and is observed until 760°C, whereafter it transforms in nitrogen to the hexagonal ZnS (wurtzite). EGA by FTIR revealed the complexity of the decomposition reactions involving also the evolution of H₂NCN, which reacts to form hexagonal ZnCN₂ as revealed by an XRD analysis. This revised version was published online in July 2006 with corrections to the Cover Date.     

CdS和CdSe薄膜的制备及其光电化学性质

本文采用简易的化学水浴沉积法和自牺牲模板法制备CdS、CdSe薄膜,对两种薄膜进行了XRD表征,比较了两种薄膜的紫外吸收光谱并研究了CdS、CdSe薄膜作为太阳能电池中的光阳极时所产生的光电流和光电压,对两种薄膜的电化学性能进行了比较.     

自组装成膜法制TiO2薄膜

采用有机分子自组装(Self-Assembly)成膜技术将硅烷偶联剂[(CH3O)3Si(CH2)3SH]组装在普通的玻片表面, 得到二维有的单层有机膜, 并将膜端基(SH)原位氧化为磺酸基(SO3H)。利用该功能基(SO3H)的吸附性, 从四氯化钛的水溶液中淀积制得了TiO2薄膜。X射线光电子能谱(XPS)和原子力显微镜(AFM)等研究显示, TiO2薄膜是均匀和连续的, 具有良好的透明性。     

Fe-doped SnO2 transparent semi-conducting thin films deposited by spray pyrolysis technique: Thermoelectric and p-type conductivity properties

In this paper, we report structural, electrical, optical, and especially thermoelectrical characterization of iron (Fe) doped tin oxide films, which have been deposited by spray pyrolysis technique. The doping level has changed from 0 to 10 wt% in solution ([Fe]/[Sn] = 0–40 at% in solution). The thermoelectric response versus temperature difference has exhibited a nonlinear behavior, and the Seebeck coefficient has been calculated from its slope in temperature range of 300–500 K. The Hall effect and thermoelectric measurements have shown p-type conductivity in SnO₂:Fe films with [Fe]/[Sn] ≥ 7.8 at%. In doping levels lower than 7.8 at%, SnO₂:Fe films have been n-type with a negative thermoelectric coefficient. The Seebeck coefficient for SnO₂:Fe films with 7.8 at% doping level has been obtained to be as high as +1850 μV/K. The analysis of as-deposited samples with thicknesses ～350 nm by X-ray diffraction (XRD) and scanning electron microscopy (SEM) has shown polycrystalline structure with clear characteristic peak of SnO₂ cassiterite phase in all films. The optical transparency (T%) of SnO₂:Fe films in visible spectra decreases from 90% to 75% and electrical resistivity (ρ) increases from 1.2 × 10^?2 to 3 × 10³ Ω cm for Fe-doping in the range 0–40 at%.     

The role of thermal analysis in optimization of the electrochromic effect of nickel oxide thin films, prepared by the sol–gel method: Part II

Thin films and the corresponding xerogels were prepared from nickel acetate precursor using the sol–gel dip-coating technique. The differences in thermal stability of the two forms of samples were studied by dynamic and isothermal thermogravimetry. For thin films, the onset decomposition temperature of acetate groups was 230 °C and for the xerogel 250 °C. During thermal decomposition, the formation of nanosized nickel oxide took place. Carbonate ions, which were formed during thermal decompostion of acetate groups, remained either free or bidentately coordinated to nickel. In situ monochromatic optical transmittance changes showed that an optical stability up to the 100th cycle was already achieved for films heated for 15 min at the isothermal temperature (thermal decompositon 25%). Comparison of the results obtained for nickel sulfate (Part I) and nickel acetate precursors shows that at least two parameters, the precursor used and the degree of thermal treatment, have considerable influence on the thermal stability of the thin film and also on its electrochromic response during the cycling process.     

Surface roughness and electrical conductivity of the SnO2 ultra‐thin layers investigated by X‐ray reflectivity

Spray pyrolysis technique was applied to deposit two sets of ultra‐thin layers of tin dioxide (SnO₂). For the first and second sets, 0.01 and 0.05 molar precursor solutions were prepared, respectively. In both sets, utilizing the X‐ray reflectivity (XRR) technique, the effect of precursor concentration (PC) and precursor volume (PV) on the layer structure are investigated. The layer thickness of the samples, in each set, is a PV‐dependent parameter. For the same PV, samples with higher PC have a larger thickness and higher density. The electron density profiles deduced from XRR data analyses establish a link between measured values of sheet resistance and electron densities. The samples with higher PV and PC show less sheet resistance. The quantum size effect was utilized to show that the surface roughness for layers of more than almost 200 Å of samples in set two plays no role in the layer conductivity. Meanwhile, the same effect explains, adequately, the role of the surface roughness in the resistivity of the ultra‐thin layers in Set 1.     

Solar photocatalytic activities of porous Nb-doped TiO2 microspheres prepared by ultrasonic spray pyrolysis

Ultrasonic spray pyrolysis method was used to prepare Nb-doped TiO₂ porous microspheres with an average diameter of 500 nm for solar photocatalytic applications. The effect of Nb-doping on morphology, structure, surface area, as well as spectral absorption properties of TiO₂ microspheres was investigated with SEM, TEM, XRD, Raman spectra, BET, and UV-Vis absorption spectra. The Nb-doping decreased the grain size of TiO₂ porous microsphere, and influenced its surface area and pore size distribution dependent on the doping concentration, but changed negligibly the morphology and size of TiO₂ microspheres. Moreover, the Nb-doping was observed to extend the spectral absorption of TiO₂ into visible spectrum, and the absorption onset was red-shifted for about 88 nm at a doping level of 5% compared to pristine TiO₂ microspheres. Under solar or visible irradiation, Nb-doped TiO₂ microspheres showed higher photocatalytic activity for methylene blue degradation compared with TiO₂ microspheres, which could be ascribed to the extended light absorption range and the suppression of electron-hole pair recombination.     

Mesoporous hybrid thin films: the physics and chemistry beneath

Mesoporous films containing organic or biological functions within an organised array of cavities are produced by combining sol-gel, self-assembly of supramolecular templates and surface chemistry. This paper reviews the essential physics and chemical concepts behind the synthesis of these complex multifunctional materials.     

乙醇-盐酸-水体系中溶胶-凝胶法制备纳米TiO2薄膜的研究

以Ti (OBu)4为前驱体,设计单因素优选实验,通过溶胶凝胶-浸渍提拉法在玻璃基片上制备TiO2纳米薄膜,研究了无水乙醇、浓盐酸、超纯水对其结构和性能的影响,获得了纳米TiO2薄膜的最佳制备条件.     

Thin films of Ln1−xSrxCoO3 (Ln=La, Nd and Gd) and SrRuO3 by nebulized spray pyrolysis

Thin films of La_1−xSr_xCoO₃, Nd_0.5Sr_0.5CoO₃, Gd_0.5Sr_0.5CoO₃ and SrRuO₃ have been deposited on Si(100), LaAlO₃(100) and SrTiO₃(100) single crystal substrates by nebulized spray pyrolysis. The films deposited on Si are generally polycrystalline, but they are highly oriented on the oxide substrates. The cobaltate films are generally not metallic, but exhibit low resistivity specially when x=0.3 and 0.5, the latter also exhibiting ferromagnetic characteristics. Films of La_0.7Sr_0.3CoO₃ show negative magnetoresistance of 35% around 180 K. Films of SrRuO₃ are metallic on Si and LaAlO₃ substrates but show an insulator–metal transition on SrTiO₃ around 130 K, around which temperature negative magnetoresistance is observed.     

CO-sensing properties of undoped and doped tin oxide thin films prepared by electron beam evaporation

Undoped thin films of tin oxide and those doped with indium oxide and nickel oxides were deposited by electron beam evaporation. The effects of the film thickness and preparation conditions (films prepared with or without the presence of oxygen environment during deposition) on the optical and carbon monoxide sensing properties of the films were studied. The films were characterized using X-ray diffraction and X-ray photoelectron spectroscopy and optical spectroscopy techniques. All the films were found to be amorphous. It was found that the sensitivity of the films to CO increased with the thickness and the porosity of the films. It was found that their selectivity to CO gas relative to CO₂ and SO₂ gases could be improved upon doping the films with indium (or nickel) oxide.     

Synthesis and photoluminescence of titania nanoparticle arrays templated by block-copolymer thin films.

High-density arrays of titania nanoparticles were prepared using a polystyrene-b-poly(ethylene oxide) block copolymer (PS-b-PEO) as a template and a titanium tetraisopropoxide based sol-gel precursor as titania source via a spin-coating method. The hydrophilic titania sol-gel precursor was selectively incorporated into hydrophilic PEO domains of PS-b-PEO and form titania nanoparticle arrays, due to a microphase separation between the PS block and the sol-gel/PEO phase. Field emission scanning electron microscopy (FESEM) and scanning probe microscopy (SPM) images showed that the uniformity and long-range order of the titania/PEO domains improved with increasing sol-gel precursor amount. Grazing incidence small-angle X-ray scattering (GISAXS) results indicate that the ordered structures exist over large length scales. Titania nanocrystal arrays of anatase modification were obtained by calcination at 600 degrees C for 4 h. After calcination, separated particles were observed for low and medium amounts of sol-gel precursors. Films with higher precursor amounts showed wormlike structures due to the aggregation between neighboring particles. Removal of the polymer matrix via UV treatment leads to highly ordered arrays of amorphous titania while retaining the domain size and interparticle distance initially present in the hybrid films. Photoluminescence (PL) properties were investigated for samples before and after calcination. The PL intensity increases with the increasing amount of sol-gel precursor. Bands at 412 nm were ascribed to self-trapped exitons and bands at 461 and 502 nm to oxygen vacancies, respectively. Uncalcined or UV-treated samples also showed PL properties similar to calcined samples, indicating that the local environment of the titanium atoms is similar to the environment of the crystalline anatase modification.     

Preparation of ZnO:CeO2-x thin films by AP-MOCVD: Structural and optical properties

The growth of columnar CeO₂, ZnO and ZnO:CeO_2−x films on quartz and AA6066 aluminum alloy substrates by economic atmospheric pressure metal-organic chemical vapor deposition (AP-MOCVD) is reported. A novel and efficient combination of metal acetylacetonate precursors as well as mild operating conditions were used in the deposition process. The correlation among crystallinity, surface morphology and optical properties of the as-prepared films was analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM) and UV-vis spectroscopy. The synthesized films showed different crystallographic orientations depending on the ZnO and CeO₂ lattice mismatch, cerium content and growth rate. The CeO₂ films synthesized in this work showed plate-like compact structures as a result of the growth process typical of CVD. Both pure and ZnO:CeO_2−x films were obtained with a hexagonal structure and highly preferred orientation with the c-axis perpendicular to both substrates under the optimal deposition conditions. The microstructure was modified from dense, short round columns to round structures with cavities (“rose-flower-like” structures) and the typical ZnO morphology by controlling the cerium doping the film and substrate nature. High optical transmittance (>87%) was observed in the pure ZnO films. As for the ZnO:CeO_2−x films, the optical transmission was decreased and the UV absorption increased, which subsequently was affected by an increase in cerium content. This paper assesses the feasibility of using ZnO:CeO_2−x thin films as UV-absorbers in industrial applications.