Optical properties of hexagonal boron nitride thin films deposited by radio frequency bias magnetron sputtering

The optical properties of hexagonal boron nitride (h-BN) thin films were studied in this paper. The films were characterized by Fourier transform infrared spectroscopy, UV--visible transmittance and reflection spectra. h-BN thin films with a wide optical band gap E_g (5.86 eV for the as-deposited film and 5.97 eV for the annealed film) approaching h-BN single crystal were successfully prepared by radio frequency (RF) bias magnetron sputtering and post-deposition annealing at 970~K. The optical absorption behaviour of h-BN films accords with the typical optical absorption characteristics of amorphous materials when fitting is made by the Urbach tail model. The annealed film shows satisfactory structure stability. However, high temperature still has a significant effect on the optical absorption properties, refractive index n, and optical conductivity σ of h-BN thin films. The blue-shift of the optical absorption edge and the increase of E_g probably result from stress relaxation in the film under high temperatures. In addition, it is found that the refractive index clearly exhibits different trends in the visible and ultraviolet regions. Previous calculational results of optical conductivity of h-BN films are confirmed in our experimental results.     

Annealing effect on the structural and optical properties of a Cd1−xZnxS thin film for photovoltaic applications

Herein is a report of a study on a Cd_1−xZn_xS thin film grown on an ITO substrate using a chemical bath deposition technique. The as-deposited films were annealed in air at 400 °C for 30 min. The composition, surface morphology and structural properties of the as-deposited and annealed Cd_1−xZn_xS thin films were studied using EDX, SEM and X-ray diffraction techniques. The annealed films have been observed to possess a crystalline nature with a hexagonal structure. The optical absorption spectra were recorded within the range of 350-800 nm. The band gap of the as-deposited thin films varied from 2.46 to 2.62 eV, whereas in the annealed film these varied from 2.42 to 2.59 eV. The decreased band gap of the films after annealing was due to the improved crystalline nature of the material.     

Chemical bath-deposited ZnS thin films: Preparation and characterization

Chemical bath deposition of ZnS thin films from NH₃/SC(NH₂)₂/ZnSO₄ solutions has been studied. The effect of various process parameters on the growth and the film quality are presented. The influence on the growth rate of solution composition and the structural, optical properties of the ZnS thin films deposited by this method have been studied. The XRF analysis confirmed that volume of oxygen of the as-deposited film is very high. The XRD analysis of as-deposited films shows that the films are cubic ZnS structure. The XRD analysis of annealed films shows the annealed films are cubic ZnS and ZnO mixture structure. Those results confirmed that the as-deposited films have amorphous Zn(OH)₂. SEM studies of the ZnS thin films grown on various growth phases show that ZnS film formed in the none-film phase is discontinuous. ZnS film formed in quasi-linear phase shows a compact and a granular structure with the grain size about 100 nm. There are adsorbed particles on films formed in the saturation phase. Transmission measurement shows that an optical transmittance is about 90% when the wavelength over 500 nm. The band gap (E_g) value of the deposited film is about 3.51 eV.     

Characterization of chemically deposited ZnSe/SnO2/glass films: Influence of annealing in Ar atmosphere on physical properties

The Zinc Selenide (ZnSe) thin films have been deposited on SnO₂/glass substrates by a simple and inexpensive chemical bath deposition (CBD). The structural, optical and electrical properties of ZnSe films have been characterized by X-ray diffraction (XRD), Energy Dispersive X-ray Analysis (EDAX), optical absorption spectroscopy, and four point probe techniques, respectively. The films have been subjected to different annealing temperature in Argon (Ar) atmosphere. An increase in annealing temperature does not cause a complete phase transformation whereas it affects the crystallite size, dislocation density and strain. The optical band gap (E_g) of the as-deposited film is estimated to be 3.08 eV and decreases with increasing annealing temperature down to 2.43 eV at 773 K. The as-deposited and annealed films show typical semiconducting behaviour, dρ/dT > 0. Interestingly, the films annealed at 373 K, 473 K, and 573 K show two distinct temperature dependent regions of electrical resistivity; exponential region at high temperature, linear region at low temperature. The temperature at which the transition takes place from exponential to linear region strongly depends on the annealing temperature.     

Influence of annealing on the structure and optical properties of Zn40Se60 thin films

Thin films of Zn₄₀Se₆₀ were prepared by the vacuum thermal evaporation technique. The influence of annealed temperature on the structural and optical properties was investigated using the X-ray diffraction (XRD), scanning electron microscopy (SEM) and optical transmission. The XRD studies show that the as-deposited film is amorphous in nature, but the crystallinity improved with increasing the annealing temperature. Furthermore the particle size and crystallinity increased whereas the dislocation and strains decreased with increasing the annealing temperature. SEM studies showed that the annealing temperature induced changes in the morphology of the as-deposited sample. Various optical constant have been calculated for as-deposited and annealed films. The mechanism of the optical absorption follows the rule of direct transition. It was found that, the optical energy gap (E_g) decreased with increasing the annealing temperature. These results can be interpreted by the Davis and Motte model. On the other hand the maximum value of the refractive index (n) is shifted toward the long wavelength by increasing the annealing temperature.     

Influence of air annealing on the structural, morphological, optical and electrical properties of chemically deposited ZnSe thin films

Zinc selenide nanocrystalline thin films are grown onto amorphous glass substrate from an aqueous alkaline medium, using chemical bath deposition (CBD) method. The ZnSe thin films are annealed in air for 4 h at various temperatures and characterized by structural, morphological, optical and electrical properties. The as-deposited ZnSe film grew with nanocrystalline cubic phase alongwith some amorphous phase present in it. After annealing metastable nanocrystalline cubic phase was transformed into stable polycrystalline hexagonal phase with partial conversion of ZnSe into ZnO. The optical band gap, E_g, of as-deposited film is 2.85 eV and electrical resistivity of the order of 10⁶-10⁷ Ω cm. Depending upon annealing temperature, decrease up to 0.15 eV and 10² Ω cm were observed in the optical band gap, E_g, and electrical resistivity, respectively.     

Structural, optical properties and band gap alignments of ZrOxNy thin films on Si (1 0 0) by radio frequency sputtering at different deposition temperatures

ZrO_xN_y thin films have been prepared by radio frequency magnetron sputtering at various substrate temperatures. The effect of substrate temperature on structural, optical properties and energy-band alignments of as-deposited ZrO_xN_y thin films are investigated. Atomic force microscopy results indicate the decreased root-mean-square (rms) values with substrate temperature. Fourier transform infrared spectroscopy spectra indicate that an interfacial layer has been formed between Si substrate and ZrO_xN_y thin films during deposition. X-ray photoelectron spectroscopy and spectroscopy ellipsometry (SE) results indicate the increased nitrogen incorporation in ZrO_xN_y thin films and therefore, the decreased optical band gap (E_g) values as a result of the increased valence-band maximum and lowered conduction-band minimum.     

Optical and electrical properties of plasma-oxidation derived HfO2 gate dielectric films

High-k gate dielectric HfO₂ thin films have been deposited on Si(1 0 0) by using plasma oxidation of sputtered metallic Hf thin films. The optical and electrical properties in relation to postdeposition annealing temperatures are investigated by spectroscopic ellipsometry (SE) and capacitance-voltage (C-V) characteristics in detail. X-ray diffraction (XRD) measurement shows that the as-deposited HfO₂ films are basically amorphous. Based on a parameterized Tauc-Lorentz dispersion mode, excellent agreement has been found between the experimental and the simulated spectra, and the optical constants of the as-deposited and annealed films related to the annealing temperature are systematically extracted. Increases in the refractive index n and extinction coefficient k, with increasing annealing temperature are observed due to the formation of more closely packed thin films and the enhancement of scattering effect in the targeted HfO₂ film. Change of the complex dielectric function and reduction of optical band gap with an increase in annealing temperature are discussed. The extracted direct band gap related to the structure varies from 5.77, 5.65, and 5.56 eV for the as-deposited and annealed thin films at 700 and 800 °C, respectively. It has been found from the C-V measurement the decrease of accumulation capacitance values upon annealing, which can be contributed to the growth of the interfacial layer with lower dielectric constant upon postannealing. The flat-band voltage shifts negatively due to positive charge generated during postannealing.     

Growth, structural and optical transport properties of nanocrystal Zn1−xCdS thin films deposited by solution growth technique (SGT) for photosensor applications

Solution Growth Technique (SGT) has been used for deposition of Zn_1−xCdS nanocrystalline thin films. Various parameters such as solution pH (10.4), deposition time, concentration of ions, composition and deposition and annealing temperatures have been optimized for the development of device grade thin film. In order to achieve uniformity and adhesiveness of thin film on glass substrate, 5 ml triethanolamine (TEA) have been added in deposition solution. The as-deposited films have been annealed in Rapid Thermal Annealing (RTA) system at various temperature ranges from 100 to 500 °C in air. The changes in structural formation and optical transport phenomena have been studied with annealing temperatures and composition value (x). As-deposited films have two phases of ZnS and CdS, which were confirmed by X-ray diffraction studies; further the X-ray analysis of annealed (380 °C) films indicates that the films have nanocrystalline size (150 nm) and crystal structure depends on the films stoichiometry and annealing temperatures. The Zn_0.4CdS films annealed at 380 °C in air for 5 min have hexagonal structure where as films annealed at 500 °C have represented the oxide phase with hexagonal structure. Optical properties of the films were studied in the wavelength range 350-1000 nm. The optical band gap (E_g=2.94-2.30 eV) decreases with the composition (x) value. The effect of air rapid annealing on the photoresponse has also been observed on Zn_1−xCdS nanocrystal thin films. The Zn_1−xCdS thin film has higher photosensitivity at higher annealing temperatures (380-500 °C), and films also have mixed Zn_1−xCdS/Zn_1−xCdSO phase with larger grain size than the as-deposited and films annealed up to 380 °C. The present results are well agreed with the results of other studies.     

退火对含氮氟非晶碳膜结构及光学带隙的影响

采用射频等离子体增强化学气相沉积法,在不同条件下制备了含氮氟非晶碳膜,着重考察了退火温度对膜结构和光学带隙的影响. 研究发现：在350℃时,膜仍很稳定,当退火温度达到400℃时,其内各化学键的相对含量发生很大的改变. 膜的光学带隙随着退火温度的升高而增大,红外和拉曼光谱分析显示其原因是：退火使得膜内F的相对浓度降低,sp²相对含量升高,导致σ-σ^*带边态密度降低. 关键词： 含氮氟非晶碳膜 退火 光学带隙     

Optical and electrical properties of thermally evaporated In49Se48Sn3 films

Nearly stoichiometric thin films of In₄₉Se₄₈Sn₃ were deposited at room temperature, by conventional thermal evaporation of the presynthesized materials, onto precleaned glass substrates. The microstructural studies on the as-deposited and annealed films, using transmission electron microscopy and diffraction (TEMD), revealed that the as-deposited films are amorphous in nature, while those annealed at 498 K are crystalline. The optical properties of the investigated films were determined from the transmittance and reflectance data, in the spectral range 650-2500 nm. An analysis of the optical absorption spectra revealed a non-direct energy gap characterizing the amorphous films, while both allowed and forbidden direct energy gaps characterized the crystalline films. The electrical resistance of the deposited films was carried out during heating and cooling cycles in the temperature range 300-600 K. The results show an irreproducible behavior, while after crystallization the results become reproducible. The analysis of the temperature dependence of the resistance (ln(R) vs. 1000/T) for crystalline films shows two straight lines corresponding to both extrinsic and intrinsic conduction. The room temperature I-V characteristics of the as-deposited films sandwiched between similar Ag metal electrodes shows an ohmic behavior, while non-ohmic behavior attributed to space charge limited conduction has been observed when the films are sandwiched between dissimilar Ag/Al metal electrodes.     

Optical properties of amorphous CuInSe2

Optical absorption spectra of polycrystalline and amorphous CuInSe₂ thin films were measured at room temperature in the photon energy range from 0.8 to 2.1 eV. In amorphous CuInSe₂ the absorption coefficient follows the relation α(hv) = A(hv?E₀)/hv characteristic of optical transitions between extended states in both the valence and conduction band. The optical gap of E₀ = 1.38 ± 0.01 eV is larger than the fundamental gap energy of E_g = 1.01 ± 0.01 eV in crystalline CuInSe₂. A comparison of the results for CuInSe₂ with those for ZnSe is given.     

Effect of substrate temperature on the structural and optical properties of ZnO and Al-doped ZnO thin films prepared by dc magnetron sputtering

ZnO and Al-doped ZnO(ZAO) thin films have been prepared on glass substrates by direct current (dc) magnetron sputtering from 99.99% pure Zn metallic and ZnO:3 wt%Al₂O₃ ceramic targets, the effects of substrate temperature on the crystallization behavior and optical properties of the films have been studied. It shows that the surface morphologies of ZAO films exhibit difference from that of ZnO films, while their preferential crystalline growth orientation revealed by X-ray diffraction remains always the (0 0 2). The optical transmittance and photoluminescence (PL) spectra of both ZnO and ZAO films are obviously influenced by the substrate temperature. All films exhibit a transmittance higher than 86% in the visible region, while the optical transmittance of ZAO films is slightly smaller than that of ZnO films. More significantly, Al-doping leads to a larger optical band gap (E_g) of the films. It is found from the PL measurement that near-band-edge (NBE) emission and deep-level (DL) emission are observed in pure ZnO thin films. However, when Al was doped into thin films, the DL emission of the thin films is depressed. As the substrate temperature increases, the peak of NBE emission has a blueshift to region of higher photon energy, which shows a trend similar to the E_g in optical transmittance measurement.     

Effect of deposition parameters on structural, optical and electrical properties of nanocrystalline ZnSe thin films

This paper presents the chemical bath deposition of zinc selenide (n-ZnSe) nanocrystalline thin films on non-conducting glass substrates, in an aqueous alkaline medium using sodium selenosulphate as Se²⁻ ion source. The X-ray diffraction studies show that the deposited ZnSe material is nanocrystalline with a mixture of hexagonal and cubic phase. The direct optical band gap ‘E_g’ for the as-deposited n-ZnSe films is found to be 3.5 eV. TEM studies show that the ZnSe nanocrystals (NCs) are spherical in shape. Formation of ZnSe has been confirmed with the help of infrared (IR) spectroscopy by observing bands corresponding to the multiphonon absorption. We demonstrate the effect of the deposition temperature and reactant concentration on the structural, optical and electrical properties of ZnSe films.     

Investigation of optical properties of annealed aluminum phthalocyanine derivatives thin films

Semiconducting molecular materials based on aluminum phthalocyanine chloride (AlPcCl) and bidentate amines have been successfully used to prepare thin films by using a thermal evaporation technique. The morphology of the deposited films was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Studies of the optical properties were carried out on films deposited onto quartz and (1 0 0) monocrystalline silicon wafers and films annealed after deposition. The absorption spectra recorded in the UV–vis region for the as-deposited and annealed samples showed two absorption bands, namely the Q- and B-bands. In addition, an energy doublet in the absorption spectra of the monoclinic form at 1.81 and 1.99 eV was observed. A band-model theory was employed in order to determine the optical parameters. The fundamental energy gap (direct transitions) was determined to be within the 2.47–2.59 and 2.24–2.44 eV ranges, respectively, for the as-deposited and annealed thin films.     

Effect of composition and thermal annealing on the absorption and electrical conduction of Se85−xTe15Sbx glasses

The optical absorption of the as-prepared and thermally annealed Se_85−xTe₁₅Sb_x (0≤x≤9) thin films was measured. The mechanism of the optical absorption follows the rule of non-direct transition. The optical energy gap (E₀) decreased from 1.12 to 0.84 eV with increasing Sb content of the as-prepared films from 0 to 9 at.%. The as-prepared Se₇₆Te₁₅Sb₉ films showed an increase in (E₀) with increasing the temperature of annealing in the range above T_g (363 K). The electrical conductivity of the as-prepared and annealed films was found to be of Arrhenius type with temperature in the range 300-360 K. The activation energy for conduction was found to decrease with increasing both the Sb content and temperature of annealing. The results were discussed on the basis of the lone-pair electron effect and of amorphous crystalline transformation.     

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.     

Effect of annealing on the optical properties of In2Te3 thin films

2 Te₃ thin films of different thickness were prepared in a vacuum of 10^-5 Torr onto glass and quartz substrates held at about 300 K during the deposition process. X-ray diffraction analysis showed that the prepared samples in bulk or as-deposited thin-film forms were in an amorphous state. On annealing at 573 K, films have a β-phase polycrystalline structure. Transmittance and reflectance measurements in the spectral range of 400–2500 nm for films deposited onto quartz substrates were used to calculate the optical constants (the refractive index n, the absorption index k and the absorption coefficient α) for In₂Te₃ films, either as-deposited or annealed at different temperatures. The refractive index has anomalous behavior in the region of the fundamental absorption edge. The allowed optical transitions were found to be nondirect transitions, with an optical gap of 1.02 eV for the samples under test. The effect of annealing on the optical gap is interpreted in terms of the density of states proposed by Mott and Davis. Received: 22 June 1997/Accepted: 9 July 1997     

Optical characteristics of transparent samarium oxide thin films deposited by the radio-frequency sputtering technique

Transparent metal oxide thin films of samarium oxide (Sm₂O₃) were prepared on pre-cleaned fused optically flat quartz substrates by radio-frequency (RF) sputtering technique. The as-deposited thin films were annealed at different temperatures (873, 973 and 1073 K) for 4 h in air under normal atmospheric pressure. The topological morphology of the film surface was characterized by using atomic force microscopy (AFM). The optical properties of the as-prepared and annealed thin films were studied using their reflectance and transmittance spectra at nearly normal incident light. The estimated direct optical band gap energy (\(E_{\mathrm {g}}^{\mathrm {d}}\)) values were found to increase by increasing the annealing temperatures. The dispersion curves of the refractive index of Sm₂O₃ thin films were found to obey the single oscillator model.     

Laser-induced changes on optical band gap of amorphous and crystallized thin films of Se75S25−xAGx

Optical band gap of amorphous, crystallized, laser induced amorphous and laser induced crystallized films of Se₇₅S_25−xAg_x (x=4, 6 and 8) glassy alloys was studied from absorption spectra. The amorphous and crystallized films were induced by pulse laser for 10 min. After laser irradiation on amorphous and crystalline films, optical band gap was measured. It has been found that the mechanism of the optical absorption follows the rule of indirect transition. The amorphous thin films show an increase in the optical band gap, while the crystallized (thermally annealed) thin films show a decrease in the optical band gap by inducing laser irradiation. Crystallization and amorphization of chalcogenide films were accompanied with the change in the optical band gap. The change in optical energy gap could be determined by identification of the transformed phase. These results are interpreted in terms of concentration of localized states due to shift in Fermi level.