Surface characterization and microstructure of ITO thin films at different annealing temperatures

In this study, the electron beam evaporation method is used to generate an indium tin oxide (ITO) thin film on a glass substrate at room temperature. The surface characteristics of this ITO thin film are then investigated by means of an AFM (atomic force microscopy) method. The influence of postgrowth thermal annealing on the microstructure and surface morphology of ITO thin films are also examined. The results demonstrate that the film annealed at higher annealing temperature (300 °C) has higher surface roughness, which is due to the aggregation of the native grains into larger clusters upon annealing. The fractal analysis reveals that the value of fractal dimension D_f falls within the range 2.16-2.20 depending upon the annealing temperatures and is calculated by the height-height correlation function.     

In_2O_3:Sn中间层改善B掺杂ZnO薄膜的性能及其应用研究

金属有机化学气相沉积(MOCVD)法生长的掺硼氧化锌(BZO)薄膜,具有天然的"类金字塔"绒面结构,作为硅基薄膜太阳电池的前电极具有良好的陷光效果.但直接获得的BZO薄膜表面形貌过于尖锐,影响后续硅基薄膜材料生长质量及太阳电池的光电转换效率.本文设计了以一层超薄In2O3:Sn(ITO)薄膜(～4 nm厚度)作为中间层的多层膜,并通过对顶层BZO薄膜的厚度调制,改善BZO薄膜的表面特性,薄膜结构为:glass/底层BZO/ITO/顶层BZO.合适厚度的顶层BZO薄膜有助于获得类似"菜花状"形貌特征,尖锐的表面趋于"柔和",而较厚的顶层BZO薄膜仍然保持"类金字塔状"结构."柔和"的BZO薄膜表面结构有助于提高后续生长薄膜电池的结晶质量.将获得的新型"三明治"结构多层膜应用于p-i-n型氢化微晶硅(μc-Si:H)薄膜太阳电池,相比传统的BZO薄膜,电池的量子效率QE在500—800 nm波长范围提高了～10%,并且电池的Jsc和Voc均有所提高.     

Equilibrium and kinetic surface segregation in binary alloy thin films

A general theoretical analysis of the effect of film thickness on equilibrium and kinetic surface segregation in binary alloy thin films is presented. In this analysis, a constrained condition that represents the finite size of thin film system has been introduced to the modified Darken model, which has been used to describe both equilibrium and kinetic surface segregation in bulk materials. Simulation of surface segregation for alloy thin films can be carried out for all composition ranges and all film thicknesses if only knowing the surface segregation parameters for bulk materials. Simulations of equilibrium and kinetic surface segregation in Cu(1 1 1)Ag binary alloy thin film are presented.     

Near-Field Birefringence Response of Liquid Crystal Molecules in Thickness Direction of Liquid Crystal Thin Film Orientated by Shear Force

Information of molecular orientation in nematic liquid crystal （LC） is attractive and important for applications in the field of display devices. We demonstrate a novel method using a birefringence scanning near-field optical microscope （Bi-SNOM） with a probe which is inserted into the LC thin film to detect the molecular orientation from its birefringence responses in the thickness direction of the LC thin film. The probe is laterally vibrated when going forward into the LC thin film, and the retardation and azimuth angle are recorded as the probe going down. Firstly, the thickness of the LC thin film is measured by the shear force detection. Since the shear force acts as a stimulation to reorientate the LC molecules above the substrate surface, we can detect the molecular orientation caused by a polyimide alignment substrate and the effect to molecular orientation caused by vibration of fibre probe. As a result, the orientation profiling of the LC film in depth direction is obtained in both the cases that the direction of probe vibrating is vertical/parallel to the rubbing direction of the alignment film. Furthermore, the thickness of completely orientated layers just above the substrate surface can also be obtained by either vibrating probe or no-vibrating probe. Ultimately, the LC thin film can be modelled in thickness direction from all the results using this method.     

Langmuir-Blodgett film and nematic interface

The orientation induced by a Langmuir-Blodgett film on a Nematic Liquid Crystal (NLC) is theoretically analyzed. We show that the effective surface energy is due to different contributions connected with steric and van der Waals interactions between the nematic and the solid substrate. The analysis shows that the Langmuir-Blodgett film orientation depends on the surface density of the molecules. The initial homeotropic orientation may become unstable giving rise to a tilted film. The average orientation of the nematic molecules is also analyzed. We show that, in the event in which the steric interaction Nematic-Langmuir-Blodgett film is very large with respect to the dispersion interaction Nematic-Substrate, the nematic orientation coincides with the one of the film. On the contrary, when the two interactions are comparable, the orientation of the two media may differ. In particular, we analyze how the stable orientation depends on the surface molecular density of the film.     

Influence of surface ordering on the wetting of structured liquids

The substrate is shown to induce substantial ordering in diblock copolymer thin films above the bulk order-disorder transition (ODT) where, thermodynamically, a phase mixed state is favored. Initially, uniform films reorganize to form a hierarchy of transient surface patterns and stable film thicknesses that depend on the initial film thickness and on the substrate. Self-consistent field calculations of the free energy of the system for different situations, depending on the relative tendency for the different block components to be attracted to the substrate and/or free surface, provide an explanation of the formation of the stable film thicknesses. A continuum picture proposed earlier by Brochard et al.rovides an explanation of the wetting characteristics of this system. In some cases the ordering destabilizes the film so that dewetting occurs (wetting autophobicity), whereas in other cases the surface ordering results in a kinetic stabilization of a film that would otherwise dewet. Received 3 August 2001 and Received in final form 1 November 2001     

Preparation and photocatalytic activity of CeO2/TiO2 interface composite film

The CeO₂/TiO₂ and TiO₂/CeO₂ interface composite films were prepared on glass substrates by the sol-gel process via dip-coating and calcining technique. The scanning electron microscopy (SEM) revealed that the TiO₂ layer has a compact and uniformity glasslike surface with 200 nm in thickness, and the CeO₂ layer has a coarse surface with 240 nm in thickness. The X-ray diffractometer (XRD) analysis showed that the TiO₂ layer is made up of anatase phase, and the CeO₂ layer is structured by cubic fluorite phase. Through a series of photo-degradation experiments, the relationship of the photocatalytic activity with the constituents of the films was studied. In virtue of the efficient interfacial charge separation via the process of electron transfer from TiO₂ to CeO₂, the photocatalytic activity of the CeO₂/TiO₂ composite film is high. Contrarily, the photocatalytic activity of the TiO₂/CeO₂ composite film is low, due to its inert surface made up of CeO₂ with broad bandwidth. Apart from the effect of the film structure, the effect of film thickness on photocatalytic activity was also discussed.     

A comparative study of the physical properties of Sb2S3 thin films treated with N2 AC plasma and thermal annealing in N2

As-deposited antimony sulfide thin films prepared by chemical bath deposition were treated with nitrogen AC plasma and thermal annealing in nitrogen atmosphere. The as-deposited, plasma treated, and thermally annealed antimony sulfide thin films have been characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy, scanning electron microscopy, atomic force microscopy, UV-vis spectroscopy, and electrical measurements. The results have shown that post-deposition treatments modify the crystalline structure, the morphology, and the optoelectronic properties of Sb₂S₃ thin films. X-ray diffraction studies showed that the crystallinity of the films was improved in both cases. Atomic force microscopy studies showed that the change in the film morphology depends on the post-deposition treatment used. Optical emission spectroscopy (OES) analysis revealed the plasma etching on the surface of the film, this fact was corroborated by the energy dispersive X-ray spectroscopy analysis. The optical band gap of the films (E_g) decreased after post-deposition treatments (from 2.36 to 1.75 eV) due to the improvement in the grain sizes. The electrical resistivity of the Sb₂S₃ thin films decreased from 10⁸ to 10⁶ Ω-cm after plasma treatments.     

Effects of annealing in nitrogen atmosphere and HCl-etching on the photoluminescence spectra of spray-deposited CdS:In thin films

The aim of this work is to find the effect of processing on the photoluminescence (PL) of spray-deposited CdS:In thin films. So the PL spectra of the as-deposited, annealed and HCl-etched CdS:In thin films prepared by the spray pyrolysis (SP) technique were recorded at T = 23 K. The yellow and red bands were observed in the spectrum of the as-deposited film beside bands with weaker intensity in the infrared region. The PL signal was weakened by annealing in nitrogen atmosphere at T = 400 °C and HCl-etching. A deconvolution peak fit was established to find the effects of these treatments on the different bands. The spectrum of the as-deposited film was deconvoluted to 12 peaks, which were reduced to 6 peaks after both treatments. It was found that both treatments have approximately the same effects on the PL spectra; that is they removed most of the peaks and shoulders in the red and infrared regions and attenuated most of the peaks in the yellow region. Some peaks were blue-shifted after annealing which was explained by the growth of nanocrystallites due to the thermal stress that results from the different expansion coefficients of the film and the substrate. These changes were accompanied by a phase change from the mixed (cubic and hexagonal) phase to the hexagonal phase as shown in the X-ray diffractograms.     

The timescale of spinodal dewetting at a polymer/polymer interface

We investigate the dynamics of spinodal dewetting in liquid-liquid polymer systems. Dewetting of poly(methyl-methacrylate) (PMMA) thin films on polystyrene (PS) “substrates” is followed in situ using neutron reflectivity. By following the development of roughness at the PS/PMMA interface and the PMMA surface we extract characteristic growth times for the dewetting process. These characteristic growth times are measured as a function of the molecular weight of the two polymers. By also carrying out experiments in the regime where the dynamics are independent of the PS molecular weight, we are able to use dewetting to probe the scaling of the PMMA thin film viscosity with temperature and molecular weight. We find that this scaling reflects bulk behaviour. However, absolute values are low compared to bulk viscosities, which we suggest may be due in part to slippage at the polymer/polymer interface. Received 25 June 2001 and Received in final form 5 December 2001     

Thickness dependence of structural, electrical and optical properties of indium tin oxide (ITO) films deposited on PET substrates

Without intentionally heating the substrates, indium tin oxide (ITO) thin films of thicknesses from 72 nm to 447 nm were prepared on polyethylene terephthalate (PET) substrates by DC reactively magnetron sputtering with pre-deposition substrate surfaces plasma cleaning. The dependence of structural, electrical, and optical properties on the films thickness were systematically investigated. It was found that the crystal grain size increases, while the transmittance, the resistivity, and the sheet resistance decreases as the film thickness was increasing. The thickest film (∼447 nm) was found of the lowest sheet resistance 12.6 Ω/square, and its average optical transmittance (400-800 nm) and the 550 nm transmittance was 85.2% and 90.4%, respectively. The results indicate clearly that dependence of the structural, electrical, and optical properties of the films on the film thickness reflected the improvement of the film crystallinity with the film thickness.     

The microstructure investigation of GeTi thin film used for non-volatile memory

GeTi thin film has been found to have the reversible resistance switching property in our previous work. In this paper, the microstructure of this material with a given composition was investigated. The film was synthesized by magnetron sputtering and treated by the rapid temperature process. The results indicate a coexist status of amorphous and polycrystalline states in the as-deposited GeTi film, and the grains in the film are extremely fine. Furthermore, not until the film annealed at 600 °C, can the polycrystalline state be detected by X-ray diffraction. Based on the morphological analysis, the sputtered GeTi has the column growth tendency, and the column structure vanishes with the temperature increasing. The microstructure and thermal property analysis indicate that GeTi does not undergo evident phase change process during the annealing process, which makes the switching mechanism of GeTi different from that of chalcogenide memory material, the most widely used phase change memory material.     

Surface chemical states of barium zirconate titanate thin films prepared by chemical solution deposition

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin films grown on Pt/Ti/SiO₂/Si(1 0 0) substrates were prepared by chemical solution deposition. The structural and surface morphology of BZT thin films has been studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the random oriented BZT thin film grown on Pt/Ti/SiO₂/Si(1 0 0) substrate with a perovskite phase. The SEM surface image showed that the BZT thin film was crack-free. And the average grain size and thickness of the BZT film are 35 and 400 nm, respectively. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Ti, and Zr exist mainly in the forms of BZT perovskite structure.     

Novel type of indium oxide thin films sputtering for opto-electronic applications

Transparent conductive oxide (TCO) thin films play a significant role in recent optical technologies. Displays of various types, photovoltaic systems, and opto-electronic devices use these films as transparent signal electrodes. They are used as heating surfaces and active control layers. Oxides of TCO materials such as: tin, indium, zinc, cadmium, titanium and the like, exhibit their properties. However, indium oxide and indium oxide doped with tin (ITO) coatings are the most used in this technology.In this work, we present conductive transparent indium oxide thin films which were prepared using a novel triode sputtering method. A pure In₂O₃ target of 2 in. in diameter was used in a laboratory triode sputtering system. This system provided plane plasma discharge at a relatively low pressure 0.5-5 mTorr of pure argon. The substrate temperature was varied during the experiments from room temperature up to 200 °C. The films were deposited on glass, silicon, and flexible polyimide substrates. The films were characterized for optical and electrical properties and compared with the indium oxide films deposited by magnetron sputtering.     

Structure and frustration in liquid crystalline polyacrylates II. Thin-film properties

We report on the thin-film behaviour of a polyacrylate with phenyl benzoate mesogenic side groups and a narrow polydispersity. Depending on the degree of polymerisation, these polymers show a nematic, a smectic-A _d, a re-entrant nematic and a C phase with a two-dimensional monoclinic lattice. X-ray reflectivity and atomic-force microscopy have been used to characterize the structure and surface morphology. The system exhibits two stable side-chain packing configurations with incommensurate spacings that can be both stabilized at a free surface. Thin films in the nematic phase show a structural dewetting induced by the growth of surface domains of the C phase. Additionally, surface-induced ripples with a nanoscale lateral period form at the air-film interface. We attribute these patterns to a coupling between the local liquid crystalline ordering of the mesogenic side groups and the surface curvature energy. Received 28 February 2001 and Received in final form 6 August 2001     

In situ measurement of the surface stress evolution during magnetron sputter-deposition of Ag thin film

We measured the evolution of in situ surface stress of Ag thin film during the magnetron sputter deposition. The measurement of force per width of Ag thin film showed that both the surface state and surface stress of Ag layer can be controlled through the variation of the deposition conditions such as the deposition temperature and rate. At room temperature, the force per width curve of Ag film deposited to 1 Å/s showed a typical curve consisting of three stages of surface stress. A brief presence of initial compressive stage and broad tensile maximum resulting in a compressive state had a tendency to disappear with increasing the deposition temperature. Meanwhile, a development of final compressive stage was more at higher temperature. Similar effect was observed but less obvious on increasing the deposition rate.     

Cascade of shocks in inertial liquid-liquid dewetting

We study the inertial dewetting of water films (A) (thickness e) deposited on highly hydrophobic liquid substrates (B). On these ideal surfaces, thin films can be made which dewet at large velocities obeying under those conditions the Culick law for the bursting of soap films. The rim collecting the water film can become coupled to the surface waves characterized by a surface tension gamma(B) upstream of the rim (coated substrate) and gamma = gamma(B) downstream, where the water film has dried. Upon decreasing the thickness, we observe a sequence of two hydraulic shocks during the dewetting inducing gravity waves behind the rim, and capillary waves ahead.     

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.     

Improvement of organic solar cells by flexible substrate and ITO surface treatments

In this paper, surface treatments on polyethylene terephthalate with polymeric hard coating (PET-HC) substrates are described. The effect of the contact angle on the treatment is first investigated. It has been observed that detergent is quite effective in removing organic contamination on the flexible PET-HC substrates. Next, using a DC-reactive magnetron sputter, indium tin oxide (ITO) thin films of 90 nm are grown on a substrate treated by detergent. Then, various ITO surface treatments are made for improving the performance of the finally developed organic solar cells with structure Al/P3HT:PCBM/PEDOT:PSS/ITO/PET. It is found that the parameters of the ITO including resistivity, carrier concentration, transmittance, surface morphology, and work function depended on the surface treatments and significantly influence the solar cell performance. With the optimal conditions for detergent treatment on flexible PET substrates, the ITO film with a resistivity of 5.6 × 10⁻⁴ Ω cm and average optical transmittance of 84.1% in the visible region are obtained. The optimal ITO surface treated by detergent for 5 min and then by UV ozone for 20 min exhibits the best WF value of 5.22 eV. This improves about 8.30% in the WF compared with that of the untreated ITO film. In the case of optimal treatment with the organic photovoltaic device, meanwhile, 36.6% enhancement in short circuit current density (J_sc) and 92.7% enhancement in conversion efficiency (η) over the untreated solar cell are obtained.