Structural, electrical, and optical properties of copper indium diselenide thin film prepared by thermal evaporation method

Stoichiometric compound of copper indium diselenide (CuInSe₂) was synthesized by direct reaction of high-purity elemental copper, indium and selenium in an evacuated quartz ampoule. The phase structure and composition of the synthesized pulverized material analyzed by X-ray diffraction (XRD) and energy dispersive analysis of X-rays (EDAX) revealed the chalcopyrite structure and stoichiometry of elements. Thin films of CuInSe₂ were deposited onto organically cleaned soda lime glass substrates held at different temperatures (i.e. 300 K to 573 K) using thermal evaporation technique. CuInSe₂ thin films were then thermally annealed in a vacuum chamber at 573 K at a base pressure of 10^− 2 mbar for 1 h. The effect of substrate temperature (T_s) and thermal annealing (T_a) on structural, compositional, morphological, optical and electrical properties of films were investigated using XRD, transmission electron microscopy, EDAX, atomic force microscopy (AFM), optical transmission measurements and Hall effect techniques. XRD and EDAX studies of CuInSe₂ thin films revealed that the films deposited in the substrate temperature range of 423-573 K have preferred orientation of grains along the (112) plane and near stoichiometric composition. AFM analysis indicates that the grain size increases with increase of T_s and T_a. Optical and electrical characterizations of films suggest that CuInSe₂ thin films have high absorption coefficient (10⁴ cm^− 1) and resistivity value in the interval 10^− 2-10¹ Ω cm influenced by T_s and T_a.     

Characterisation of SiOxCyHz thin films deposited by low-temperature PECVD

SiO_xC_yH_z thin films were deposited from hexamethyldisiloxane (HMDSO)/O₂ mixtures in a parallel plate, capacitively coupled, RF plasma reactor. Polyethylene terephthalate (PET), Si(1 0 0) wafers and KBr tablets were chosen as substrates. Effect of HMDSO/O₂ ratio, total treatment pressure and power input on the properties of the deposited films were investigated. The structure and bondings were studied by means of Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Wettability characteristics of the deposited thin films were investigated by means of water droplet contact angle measurements. Surface morphology was investigated with atomic force microscopy. Barrier properties of the SiO_xC_yH_z thin films were investigated by measuring the water vapour transmission rate of the coated PET substrates. Correlations between the characteristics of the deposited film and their barrier properties were discussed.     

Preparation and characterization of APTES films on modification titanium by SAMs

In this study, the titanium plates, which were modified by NaOH alkali solution, were associated with 3-Aminopropyltriethoxysilane (APTES) films using self-assembled monolayers (SAMs). The surfaces of titanium before and after modification were characterized by scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and attenuated total refraction-Fourier transform infrared spectroscopy (ATR-FTIR). After bonding the APTES films on the modification titanium, the new peaks located around 1095 cm⁻¹ attributes to siloxane groups indicating that silane agent had been grafted onto the surface of the modification titanium substrate by SAMs. Following the deposition of APTES films on titanium, significant change were seen in the amounts of oxygen, silicon and carbon present on the titanium surface, which were consistent with the anticipated reaction steps.     

Microstructure-Property relationships in thin film ITO

Polycrystalline tin-doped indium oxide (ITO) thin films were prepared by pulsed laser deposition (PLD) with an ITO (In₂O₃-10 wt.% SnO₂) target and deposited on borosilicate glass substrates. By changing independently the deposition temperature and the oxygen pressure, a variety of microstructures were deposited. These different microstructures were mainly investigated not only by transmission electron microscopy (TEM) with cross-section and plan-view electron micrographs, but also by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction. Composition changes in ITO thin films grown under different deposition conditions were characterized by energy dispersive X-ray spectroscopy (EDX). The optical and electrical properties were studied respectively by UV-visible spectrophotometry and a four-point probe. The best compromise in terms of high transmittance (T) in the visible range and low resistivity (ρ) was obtained for films deposited between 0.66 and 2 Pa oxygen pressure (P_O2) at 200 °C substrate temperature (T_s). The influence of P_O2 and T_s on the microstructure and ITO film properties is discussed.     

Effect of some growth parameters on vacuum-deposited CulnSe2 films

P-type copper indoselenide (CulnSe₂) thin films were vacuum-deposited on glass substrates by a single-source thermal evaporation technique under different conditions of preparation. The structural properties of the films were investigated by X-ray diffraction and transmission electron microscopy and diffraction techniques. The dark resistivity of the deposited films was investigated as a function of film thickness, deposition rate and substrate temperature. The conductivity activation energy ranges from 0.851 to 1.01 eV depending on the deposition rate. Single-phase and stoichiometric CulnSe₂ films could be deposited at low deposition rates (less than 4 nms^–1). Higher deposition rates led to multiphase films containing InSe, ln₂Se₃, CuSe and Cu₃Se₂ in addition to CulnSe₂.     

Fabrication and electrical properties of metal-oxide semiconductor capacitors based on polycrystalline p-CuxO and HfO2/SiO2 high-κ stack gate dielectrics

Polycrystalline p-type Cu_xO films were deposited after the growth of HfO₂ dielectric on Si substrate by pulsed laser deposition, and Cu_xO metal-oxide-semiconductor (MOS) capacitors with HfO₂/SiO₂ stack gate dielectric were primarily fabricated and investigated. X-ray diffraction and X-ray photoelectron spectroscopy were applied to analyze crystalline structure and Cu⁺/Cu²⁺ ratios of Cu_xO films respectively. SiO₂ interlayer formed between the high-κ dielectric and substrate was estimated by the transmission electron microscope. Results of electrical characteristic measurement indicate that the permittivity of HfO₂ is about 22, and the gate leakage current density of MOS capacitor with 11.3 nm HfO₂/SiO₂ stack dielectrics is ∼ 10⁻⁴ A/cm². Results also show that the annealing in N₂ can improve the quality of Cu_xO/HfO₂ interface and thus reduce the gate leakage density.     

Influence of oxidant source on the property of atomic layer deposited Al2O3 on hydrogen-terminated Si substrate

Al₂O₃ thin films were deposited on hydrogen-terminated Si substrate using atomic layer deposition (ALD) technique with tri-methylaluminum (TMA) and an oxidant source of H₂O vapor, O₂ plasma, or O₃. Substrate temperature was maintained at 350 °C when the Al₂O₃ films were grown with the oxidant sources of H₂O vapor and O₃, and with the oxidant source of O₂ plasma, Al₂O₃ films were deposited at the substrate temperature of 200 °C. Growth rates of Al₂O₃ films on HF-cleaned Si surface were saturated at 0.08, 0.14, and 0.06 nm/cycle for H₂O vapor, O₂ plasma, and O₃, respectively. Equivalent oxide thickness (EOT) and leakage current vs. physical thickness of atomic layer deposited Al₂O₃ films grown with various oxidant sources were also measured in this study. To investigate the main cause of different EOT with oxidant sources, interfacial properties were examined by using transmission electron microscopy (TEM) and X-ray photoelectron microscopy (XPS). In the TEM analysis, interfacial layers with the thickness of about 1.7 and 1.3 nm were observed in as-deposited Al₂O₃ films grown using O₂ plasma and O₃. We confirmed that the interfacial layers were mainly composed of SiO_x in the XPS depth analysis. Using angle resolved X-ray photoelectron spectroscopy, effect of annealing on the interfacial structure of Al₂O₃ films grown with O₃ and O₂ plasma was also studied, and we found that after annealing, the peak corresponding to silicon suboxide and Al-silicate disappeared and fully oxidized Si⁴⁺ increased.     

Optical and structural properties of SiOx films from ion-assisted deposition

This study investigates the optical and structural properties of SiO_x (x ∼ 1) films prepared by an ion-assisted deposition (IAD) process. The films were prepared by evaporating silicon monoxide, with and without simultaneous Ar⁺ bombardment. The stoichiometry of each film was determined as measured by the infrared spectrometry and X-ray photoelectron spectrometry. The variation in the stoichiometry revealed that the oxygen content of the SiO_x thin films varied slightly under the different conditions of the Ar⁺ bombardment. The results of the X-ray diffraction and transmission electron microscopy (TEM) measurements illustrated that all of the films had amorphous structures. However, a different interfacial appearance between the film and the substrate was observed from the TEM image. The optical constants of the SiO_x thin films were determined by a spectroscopic ellipsometry. The extinction coefficient of all of the films approached zero in the infrared wavelength range from 2 to 7 μm, but the refractive index was varied by the IAD process. The variation of these refractive indices is mainly related to the packing density of the films.     

Effects of cetyltrimethylammonium bromide on redox deposition and rectification properties of silicon oxide thin film

Silicon oxide (SiO_x) thin film was deposited onto fluorine-doped tin oxide (FTO) and silicon wafer substrate by the reduction of an aqueous solution containing ammonium hexafluorosilicate, dimethylamine borane and cetyltrimethylammonium bromide (CTAB). Characterization of the films by X-ray photoelectron spectroscopic depth profile and infrared spectroscopy proved that the addition of CTAB into the film enhanced the aggregation of silica particles and the growth rate. The SiO_x films (resistivity: 3.2 × 10⁸ Ω cm) remarkably improved the rectification properties of FTO/SiO_x/poly(3,4-ethylenedioxythiophene) derivative diodes. A rectification mechanism based on conduction of electron and ions was investigated.     

A hexane solution deposition of SnS2 films from tetrabutyltin via a solvothermal route at moderate temperature

SnS₂ films have been deposited on glass and alumina plate substrates by the reactions between an organotin precursor [tetrabuyltin, (CH₂CH₂CH₂CH₃)₄Sn] and carbon disulfide in n-hexane at the temperature range 180-200 °C for 10-40 h. The reaction system was oxygen free and applied at a moderate temperature. The films so prepared were characterized by techniques of X-ray diffraction, Scanning electron microscopy, Raman and Mössbauer spectroscopies. The films deposited on glass as well as on alumina plate have an average thickness of 30 μm, but have different rose-like morphologies, which are influenced by both the anisotropic growths of crystals and the different substrate structures. Photoluminescence measurements show that the films have an emission peak at approximately 590 nm.     

Nanostructured Er3+-doped SiO2–TiO2 and SiO2–TiO2–Al2O3 sol–gel thin films for integrated optics

The nanostructured multilayer silica–titania or silica–titania–alumina films doped with Er³⁺ were prepared by sol–gel method. The sol–gel method is a flexible and convenient way to prepare oxide films on several types of substrates, and for this reason it was extensively investigated for optical waveguides fabrication. The selected molar composition was 90%SiO₂–10%TiO₂ or 85%SiO₂–10%TiO₂–5% Al₂O₃ and 0.5% Er₂O₃.The films were characterized by Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Spectroellipsometry (SE), as well as by Atomic Force Microscopy (AFM) and photoluminescence (PL). The films deposited on Si/SiO₂ substrate by dip-coating or spin-coating, followed by annealing at 900 °C, presented homogenous and continuous surface and good adherence to the substrate. Differences were noticed in the structure and properties of the prepared films, depending on the composition and the number of deposited layers.Channel optical waveguides were obtained by patterning Er³⁺-doped SiO₂–TiO₂ and SiO₂–TiO₂–Al₂O₃ sol–gel layers deposited on oxidized silicon wafers.     

Effects of physical growth conditions on the structural and optical properties of sputtered grown thin HfO2 films

HfO₂ thin films were prepared by reactive DC magnetron sputtering technique on (100) p-Si substrate. The effects of O₂/Ar ratio, substrate temperature, sputtering power on the structural properties of HfO₂ grown films were studied by Spectroscopic Ellipsometer (SE), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectrum, and X-ray photoelectron spectroscopy (XPS) depth profiling techniques. The results show that the formation of a SiO_x suboxide layer at the HfO₂/Si interface is unavoidable. The HfO₂ thickness and suboxide formation are highly affected by the growth parameters such as sputtering power, O₂/Ar gas ratio during sputtering, and substrate temperature. XRD spectra show that the deposited films have (111) monoclinic phase of HfO₂, which is also supported by FTIR spectra. XPS depth profiling spectra shows that highly reactive sputtered Hf atoms consume some of the oxygen atoms from the underlying SiO₂ to form HfO₂, leaving Si-Si bonds behind.     

Properties of indium tin oxide films deposited on unheated polymer substrates by ion beam assisted deposition

The optical, electrical and mechanical properties of indium tin oxide (ITO) films prepared on polyethylene terephthalate (PET) substrates by ion beam assisted deposition at room temperature were investigated. The properties of ITO films can be improved by introducing a buffer layer of silicon dioxide (SiO₂) between the ITO film and the PET substrate. ITO films deposited on SiO₂-coated PET have better crystallinity, lower electrical resistivity, and improved resistance stability under bending than those deposited on bare PET. The average transmittance and the resistivity of ITO films deposited on SiO₂-coated PET are 85% and 0.90 × 10^− 3 Ω cm, respectively, and when the films are bent, the resistance remains almost constant until a bending radius of 1 cm and it increases slowly under a given bending radius with an increase of the bending cycles. The improved resistance stability of ITO films deposited on SiO₂-coated PET is mainly attributed to the perfect adhesion of ITO films induced by the SiO₂ buffer layer.     

Synthesis and characterization of carbon/silica superhydrophobic multi-layer films

C/SiO₂ multi-layer films (3-layer films and 5-layer films) were obtained by sol-gel method and physical deposition on glass plates, and then heated at 500 °C for 1 h under a nitrogen atmosphere. The mechanical adhesive force with the substrate of the multi-layer films was sharply enhanced compared to the as-deposited amorphous carbon film. An absorption layer was formed on heat treated C/SiO₂ multi-layer films by modification of the surface with trimethylchlorosilane, and the wettability of the films changed from hydrophilic to super-hydrophobic. The structures of the physically deposited carbon and the multi-layer films were analyzed by X-ray diffraction, transmission electron microscopy and scanning electron microscopy. The experimental results showed that the 5-layer films had a concentric ring structure that caused the film to be superhydrophobic.     

Self-organized patterned arrays of Au and Ag nanoparticles by thickness-dependent dewetting of template-confined films

In this work we report on the formation of self-organized and multimodal sized patterned arrays of Au and Ag nanoparticles on SiO₂ surface exploiting the thickness-dependent solid-state dewetting properties of template-confined deposited nanoscale films. In this approach, the Au and Ag surface pattern order, on the SiO₂ substrate, is established by the template confined deposition on a micrometric scale, while the solid-state dewetting phenomenon is induced by thermal processes (below the Au and Ag melting temperature). The deposited films have not an uniform thickness. They, instead, present a controlled thickness due to shadowing mask effects during depositions. Such an inhomogeneity can be further controlled by changing the deposition angle. After the dewetting process, scanning electron microscopy analyses allowed us to correlate the mean diameter 〈D〉 and spacing 〈s〉 of the formed nanoparticles by the thickness h of the deposited films. Despite the dewetting process of the Au and Ag films occurs in the solid state, relations describing the evolution of 〈D〉 and 〈s〉 with 〈h〉 typical of the linear hydrodynamic spinodal dewetting process of liquid films, 〈D〉 ∝ h ^5/3 and 〈s〉 ∝ h ², were verified within a 20 % experimental error. As a consequence we call this process “pseudo-spinodal dewetting”.     

Annealing effect on the structural and optical properties of embedded Au nanoparticles in silicon suboxide films

Au/SiO_x nanocomposite films have been fabricated by co-sputtering Au wires and SiO₂ target using an RF magnetron co-sputtering system before the thermal annealing process at different temperatures. The structural and optical properties of the samples were characterized using X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), optical transmission, and reflection spectroscopy. XPS analysis confirms that the as-prepared SiO_x films are silicon-rich suboxide films. FESEM images reveal that with an increase in annealing temperature, the embedded Au NPs tend to diffuse toward the surface of the SiO_x films. In IR spectra, the intensity of the Si-O-Si absorption band increases with the annealing temperature. Optical spectra reveal that the position and intensity of the surface plasmon resonance (SPR) peak are dominated by the effect of the inter-particle distance and size of the Au NPs embedded in the SiO_x films, respectively. The SPR absorption peak shows the blue-shift from 672 to 600 nm with an increase in annealing temperature. The growth of silica nanowires (SiO_x NWs) is observed in the film prepared on a c-Si substrate instead of a quartz substrate and annealed at temperatures of 1000 °C.     

Effect of substrate temperature on the structural,morphological and optical properties of copper bismuth sulfide thin films deposited by electron beam evaporation method

Copper bismuth sulfide thin films were deposited at 200 °C, 300 °C, 400 °C and 500 °C on the glass substrates by electron beam evaporation method. X-ray diffraction study revealed that the copper bismuth sulfide films of single and mixed phases were formed as a function of substrate temperatures. Substrate temperature of 300 °C and 400 °C formed single phase Cu₄Bi₄S₉ and Cu₄Bi₅S₁₀ films respectively whereas substrate temperature of 500 °C formed mixed phases of Cu₄Bi₄S₉ and Cu₄Bi₅S₁₀ film. Crystallite size, dislocation density and microstrain of the films were modified by the various substrate temperatures. Surface morphology of the film Cu₄Bi₅S₁₀ deposited at 400 °C examined by scanning electron microscopy showed the distribution of spherical shaped particles on the film surface. The presence of copper, bismuth and sulfur elements in the deposited films was confirmed using energy dispersive spectral studies. The calculated direct optical band gap energy of the films deposited at different substrate temperature varied from 1.47 to 1.64 eV and the absorption coefficient is in the order of 10⁶ cm^?1.     

One step room temperature photodeposition of Cu/TiO2 composite films and its conversion to CuO/TiO2

Cu/TiO₂ composite films were prepared at low temperature on glass substrates by a photodeposition method. Films were deposited by irradiating the substrate while in contact with an aqueous TiO₂ suspension containing copper(II) nitrate and ethanol. Cu/TiO₂ composite films of 500 nm in thickness were deposited at room temperature after a short irradiation time (15 min) with a 125 W mercury vapour lamp. According to scanning electron microscopy observations, the obtained films were homogeneous and porous. Energy dispersive X-ray spectroscopy analysis revealed a 3:1 Cu:Ti atomic ratio. Grazing angle X-ray diffraction analysis showed that the films contained Cu and TiO₂ as major components and Cu₂O as a minor component. Heat treatment at 400 °C in air for a period of 3 h transformed the initial material into a CuO/TiO₂ composite, improved the adhesion to the substrate and favoured a more regular distribution of copper oxide according to backscattering micrographs.     

Nano-particle thin films of tin oxides

Nano-particle thin films of tin oxides were deposited on SiO₂ substrates by using radio frequency (RF) magnetron sputtering with various substrate temperatures, sputtering powers and oxygen partial pressures. The tin oxides thin films were then investigated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). XPS data suggested that the deposited tin oxides thin films are almost made up of half of SnO₂ and half of SnO. The oxygen partial pressure nearly does not affect the chemical stoichiometry of the thin films in our deposition conditions. SEM results showed that the tin oxides thin films were formed by nano-particles with size of about 60 nm. Sputtering power has a strong influence on the particle size of the thin films. Increase of sputtering power will enlarge the size of the particles.     

Structure of diamond and diamond like carbon thin films grown by hot-filament chemical vapour deposition technique

Micro-crystalline diamond (MCD) and diamond like carbon (DLC) thin films were deposited on silicon (100) substrates by hot-filament CVD process using a mixture of CH₄ and H₂ gases at substrate temperature between 400–800°C. The microstructure of the films were studied by X-ray diffraction and scanning electron microscopy. The low temperature deposited films were found to have a mixture of amorphous and crystalline phases. At high temperatures (> 750°C) only crystalline diamond phase was obtained. Scanning electron micrographs showed faceted microcrystals of sizes up to 2μm with fairly uniform size distribution. The structure of DLC films was studied by spectroscopic ellipsometry technique. An estimate of the amount of carbon bonds existing insp ² andsp ³ form was obtained by a specially developed modelling technique. The typical values ofsp ³/sp ² ratio in our films are between 1·88–8·02. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995