Synthesis and properties of In2(Se1-xTex)3 thin films: a new semiconductor compound

In₂(Se_1-xTe_x)₃ polycrystalline films were prepared by a dual-source thermal evaporation technique. The depositions onto glass and SnO₂-coated glass substrates were carried out in a vacuum chamber and followed by an annealing in neutral ambient (Ar or N₂). The structural, morphological and compositional studies of the films were made by X-ray diffraction, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, Raman scattering and optical transmission. Optimum conditions are investigated for the formation of the ternary compound In₂(Se_1-xTe_x)₃ in order to tune the band gap by changing the Te concentration. The film properties as a function of Te amount are discussed. It is shown that single-phase, textured and homogeneous layers of In₂(Se_1-xTe_x)₃ can be grown with x≤0.2 at optimal deposition and heat treatment conditions. For x≅0.17 these films showed an energy band gap of about 1.45 eV and an electrical conductivity at room temperature six orders of magnitude higher than that of the binary γ-In₂Se₃ thin films. Received: 9 July 1999 / Accepted: 25 November 1999 / Published online: 13 July 2000     

Structural and optical properties of Ge20SbxSe80-x films

20 Sb_xSe_80-x (where 10≤x≤40 at.%) thin films. The optical absorption results indicate that the absorption mechanism is due to non-direct transition. The optical gap of the as-deposited films was found to decrease monotonically with increasing antimony content, a result which was interpreted on the basis of the chemical-bond approach proposed by Bicerno and Ovshinsky. Annealing of the Ge₂₀Sb₄₀Se₄₀ films at temperatures higher than 450 K was found to decrease the optical gap and increase the refractive index of the investigated film. Increasing the amount of crystalline GeSe₂ and Sb₂Se₃ phases while increasing the annealing temperature could be responsible for the continuous decrease of the optical gap of the Ge₂₀Sb₄₀Se₄₀ film. Received: 4 November 1997/Accepted: 16 December 1997     

Influence of γ-irradiation on the optical and electrical properties of Se(0.85) Te(0.15) films

Abstract

Se_(0.85) Te_(0.15) films were prepared by thermal evaporation under vacuum on glass substrate. The optical and electrical properties of as deposited and irradiated Se_(0.85) Te_(0.15) films with different γ-doses are reported.

The optical constants (absorption coefficient (α), extinction coefficient (k), refractive index (n) and dielectric constants (?, ?) of unirradiated and irradiated films were calculated. The value of allowed direct optical energy gap of Se_(0.85) Te_(0.15) films increased from 1.47 eV. to 1.72 eV. with increasing the γ-doses to 2.5 Mrad. The irradiated films have lower resistivity than those as deposited films (unirradiated). The activation energy (ΔE) increases from 0.72 eV. to 0.86 eV. with increasing γ-doses to 2.5 Mrad.     

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     

Effect of Cd and Pb impurities on the optical properties of?fresh?evaporated amorphous (As2Se3)90Ge10 thin films

Transmission spectra (400–1500 nm) of thermally evaporated amorphous [(As₂Se₃)₉₀Ge₁₀]₉₅M₅ thin films have been analyzed to study the effect of impurities (M = Cd and Pb) on their optical properties. The refractive index increases with addition of metal impurities. The dispersion of refractive index has been studied using Wemple–DiDomenico single oscillator model. The optical gap has been estimated using Tauc’s extrapolation and was found to decrease with the addition of metal impurities from 1.46 to 1.36 eV (Cd) and 1.41 eV (Pb) with an uncertainty of ±0.01 eV. The change in optical properties with metal impurities has been explained on the basis of density, polarizability and bond energy of the system.     

Experimental study and configurational-coordinate model for photo-induced effects in amorphous As2Se3 films

The optical absorption of As₂Se₃ thin films is studied in the UV–VIS spectral range and the value of the optical energy gap is determined. The effect of photo-irradiation on the optical absorption and transmission of thin film samples is also investigated. The optical energy gap was found to decrease with photo-irradiation time. The results of photo-irradiation are discussed in correlation with the structural aspects of As₂Se₃. A model is proposed to account for the structural changes, resulting from photo-irradiation, causing the decrease of the energy gap. The effect of γ-radiation on the optical absorption of As₂Se₃ thin films was studied also and no detectable effect on the value of the optical energy gap was observed.     

Band alignments in the Cu(In,Ga)(S,Se)2 alloy system determined from deep-level defect energies

The composition dependence of defect energies in polycrystalline Cu(In_1-xGa_x)(Se_1-yS_y)₂ chalcopyrite semiconductor thin films is investigated by admittance spectroscopy. Alloying CuInSe₂ with S increases the energy of the dominant acceptor from 300 meV to approximately 380 meV in CuIn(Se_0.4S_0.6)₂, whereas in the alloy system Cu(In_1-xGa_x)Se₂, the acceptor energy remains unchanged over the whole composition range 0≤x≤1. Using the acceptor energy as a reference, we extrapolate the valence-band offsets ΔE_V=-0.23 eV for the combination CuInSe₂/CuInS₂ and ΔE_V=-0.04 eV for CuInSe₂/CuGaSe₂. Received: 19 July 2001 / Accepted: 27 July 2001 / Published online: 2 October 2001     

Composition dependence of the energy gap and thermal diffusivity in bulk As-Se glasses

We have measured the composition dependence of the optical energy gap and thermal diffusivity in bulk As _x Se_1−x (0.10⩽x⩽0.50) glasses using photoacoustic technique. The energy gap shows a threshold minimum value and thermal diffusivity has a threshold maximum value at the stoichiometric composition As₂Se₃ corresponding tox=0.40. The decrease in energy gap is explained on the basis of chemical bonding. It is argued that the threshold percolation of rigidity in the random network is responsible for the peaking of the thermal diffusivity at the stoichiometric composition.     

Influence of indium content on the optical, electrical and crystallization kinetics of Se100−xInxthin films deposited by flash evaporation technique

Thin films of Se _100−xIn_x (x=10, 20 and 30 at%) have been prepared by the flash evaporation technique. The effect of the indium content on optical band gap of the Se_100−x In_x films has been investigated by the optical characterization. The optical band gap values of the Se_100−x In_x thin films were determined and are found to decrease with increasing indium content. This indium content changes the width of localized states in the optical band gaps of the thin films. It was found that the optical band gap, E_g, of the Se_100−x In_x films changes from 1.78 to 1.37 eV with increasing indium content from 10 to 30 at%, while the width of localized states in optical band gap changes from 375 to 342 meV. The temperature dependence of the dark electrical conductivity were studied in the temperature range 303-433 K and revealed two activation energies providing two electrical conduction mechanisms. The activation energy of the Se_100−x In_x films in the high temperature region changes from 0.49 to 0.32 eV with increasing indium content from 10 to 30 at%, while the hopping activation energy in the lower temperature region changes from 0.17 to 0.22 meV. The change in the electrical conductivity with time during the amorphous-to-crystalline transformation is recorded for amorphous Se_100−xIn_x films at two points of isothermal temperatures 370 and 400 K. The formal crystallization theory of Avrami has been used to calculate the kinetic parameters of crystallization.     

Preparation and characterization of electrodeposited Sb2Se3 thin films from non-aqueous media

Semiconducting Sb₂Se₃ thin films have been prepared onto the stainless steel and fluorine doped tin oxide coated glass substrates from non-aqueous media using an electrodeposition technique. The electrodeposition potentials for different bath compositions and concentrations of solution have been estimated from the polarization curves. SbCl₃ and SeO₂ in the volumetric proportion as 1:1 with their equimolar solution concentration of 0.05 M form good quality films. The films are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and optical absorption techniques. The SEM studies show that the film covers the total substrate surface with uneven surface morphology. The XRD patterns of the films obtained by varying compositions and concentrations show that the as-deposited films are polycrystalline with relatively higher grain size for 1:1 composition and 0.05 M concentration. The optical band gap energy for indirect transition in Sb₂Se₃ thin films is found to be 1.195 eV.     

Structural and optical properties of CuIn1−xAlxSe2 thin films prepared by four-source elemental evaporation

CuIn_1−xAl_xSe₂ (CIASe) thin films with x=0.25, 0.5 and 0.65 were prepared by four-source elemental evaporation. The structural and optical properties were investigated by X-ray diffraction, scanning electron microscopy, energy dispersive analysis, and optical transmission. The results showed that these films contain chalcopyrite structure with preferred orientation along (112) direction. The morphology, grain distribution and composition of CIASe films were studied and compared for different Al content. The optical studies revealed that the films were highly absorbing and the energy band gap calculated from transmission spectra for x=0.25, 0.5 and 0.65 were 1.2, 1.51 and 1.73 eV, respectively. The variation of Al content in the CIASe composition offered a very effective change in the optical band gap.     

Optical and electrical properties of flash-evaporated Pb1−xHgxSe films

Results of optical and electrical properties of flash-evaporated Pb_1−xHg_xSe films, in the composition range 0.07 ⩽ x ⩽ 0.93, show that the alloy films are formed by alloying of PbSe and HgSe. The optical band gaps of films grown on substrates at 25 and 100°C decrease linearly from 0.20 to 0.09 eV and from 0.15 to 0.065 eV, respectively, as the Hg concentration in the films is increased from 0.07 to 0.93. Activation energy values, as obtained from conductivity measurements, suggest that between 225 and 400 K the conduction results mainly from thermally-generated charge carriers, whereas at the lower temperatures (<225 K) impurity conduction dominates. Irreversible changes in the properties of the films are observed at > 400 K.     

Influence of composition on electrical and optical properties of new chalcogenide thin films from Ge-Se-Tl system

Bulk Ge₂₀Se_80−xTl_x (x ranging from 0 to 15 at%) chalcogenide glasses were prepared by conventional melt quenching technique. Thin films of these compositions were prepared by thermal evaporation, on glass and Si wafer substrates at a base pressure of 10⁻⁶ Torr. X-ray diffraction studies were performed to investigate the structure of the thin films. The absence of any sharp peaks in the X-ray diffractogram confirms that the films are amorphous in nature. The optical constants (absorption coefficient, optical band gap, extinction coefficient and refractive index) of Ge₂₀Se_80−xTl_x thin films are determined by absorption and reflectance measurements in a wavelength range of 400-900 nm. In order to determine the optical gap, the absorption spectra of films with different Tl contents were analyzed. The absorption data revealed the existence of allowed indirect transitions. The optical band gap showed a sharp decrease from 2.06 to 1.79 eV as the Tl content increased from 0% to 15%. It has been found that the values of absorption coefficient and refractive index increase while the extinction coefficient decreases with increase in Tl content in the Ge-Se system. These results are interpreted in terms of the change in concentration of localized states due to the shift in Fermi level. DC electrical conductivity of Ge₂₀Se_80−xTl_x thin films was carried out in a temperature range 293-393 K. The electrical activation energy of these films was determined by investigating the temperature dependence of dc conductivity. A decrease in the electrical activation energy from 0.91 to 0.55 eV was observed as the Tl content was increased up to 15 at% in Ge₂₀Se_80−xTl_x system. On the basis of pre-exponential factor, it is suggested that the conduction is due to thermally assisted tunneling of the carriers in the localized states near the band edges.     

Influence of thermal annealing on optical and structural properties change in Bi-doped Ge30Se70 thin films

The effect of annealing on the structural and optical properties of thermally evaporated Ge₃₀Se₇₀ and Ge₃₀Se₆₀Bi₁₀ thin films is reported in this paper. The prepared films were thermally annealed at 250°C to optimize the optical properties which can be used for the optical device fabrication. X-ray diffraction study revealed no structural transformation whereas the surface morphology changed as observed from scanning electron microscopy. The optical properties of the deposited and annealed films have been investigated by using a UV–VIS–NIR spectrophotometer in the wavelength range of 400–1100?nm. The optical band gap of the Ge₃₀Se₇₀ annealed film is found to be increased while the energy gap of the Bi-doped annealed Ge₃₀Se₆₀Bi₁₀ thin film decreased which is explained by the chemical disorderness, defect states and density of localized states in the mobility gap. The Tauc parameter and Urbach energy which measure the degree of disorder changed with the annealing process. The transmittivity increases and the absorption power decreases in the Ge₃₀Se₇₀ annealed film, whereas the reverse effect is noticed for the annealed Ge₃₀Se₆₀Bi₁₀ thin film. The irreversible nature of this change can be useful for optical recording purposes.     

Effect of annealing on structure and optical properties of Ga5Se95 films

To investigate the effect of annealing on the structural and optical properties of a binary compound Ga₅Se₉₅, thin films of Ga₅Se₉₅ have been deposited on quartz substrates at room temperature by the thermal evaporation technique. X-ray diffraction patterns showed that the films before and after annealing at 573 K have polycrystalline texture and exhibit tetragonal structure. The dependences of the optical constants, the refractive index n and extinction coefficient k were studied in the spectral range of 200 nm to 2500 nm. The normal dispersion of the refractive index of the films could be described using the Wemple–DiDomenco single-oscillator model. Analysis of absorption index data reveals that as-deposited Ga₅Se₉₅ films has indirect transitions with optical energy gap of 1.685 eV.     

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.     

Studies on Structural,Morphological and Optical Properties of Chemically Deposited CdS<Subscript>1-x</Subscript>Se<Subscript>x</Subscript> Thin Films

The thin films of CdS_1-xSe_x were successfully deposited over glass substrates by chemical bath deposition technique. Cadmium acetate, thiourea and sodium selenosulfate were used as source materials for Cd²⁺, S^2? and Se^2? ions, while 2-mercaptoethanol was used as capping agent. The various deposition conditions such as precursor concentration, deposition temperature, pH and deposition time were optimized for the deposition of CdS_1-xSe_x thin films of good quality and the films were annealed at 200° and 300 °C. The structural, morphological, chemical and optical properties were examined by various characterization techniques and discussed in detail. The optical band gap of CdS_1-xSe_x thin film samples were estimated and found in the range from 2.11 to 1.79 eV for as-deposited and annealed thin films.     

Structural,optical and electrical properties of laser irradiated Pb doped Ga–Se chalcogenide thin films

Using the Transverse Electrical Excitation at Atmospheric Pressure (TEA) nitrogen laser, we had irradiated the amorphous thin films of Ga₁₀Se₈₁Pb₉ chalcogenide glass and the results have been discussed in terms of the structural aspects of Ga₁₀Se₈₁Pb₉ glass. The observed changes are associated with the interaction of the incident photon and the lone-pairs electrons which affects the band gap. The X-ray structural characterization revealed the amorphous nature of as prepared films and polycrystalline nature of the laser irradiated films. The optical band gap of these thin films is measured by using the absorption spectra as a function of photon energy in the wavelength region 400–1200 nm. It is found that the optical band gap decreases while the absorption coefficient increases with increasing the irradiation time. The decrease in the optical band gap has been explained on the basis of change in nature of films, from amorphous to polycrystalline state, with the increase in exposure time. The dc conductivities and activation energies of these thin films are measured in temperature range 303–403 K. It has been found that the activation energy in Ga₁₀Se₈₁Pb₉ chalcogenide thin films decreases whereas the dc conductivity increases at each temperature by increasing the irradiation time.     

Spectroscopic study of nanocrystalline V2O5·nH2O films doped with Li ions

Optical properties of nanocrystalline, Li_xV₂O₅·nH₂O films (0<x<22 mol%), are explored in the present work. These films have been produced by the sol–gel technique (colloidal route), which was used for the preparation of high purity and homogeneity films. Optical measurements were carried out using a double-beam spectrophotometer. The optical constants such as refractive index n, the extinction coefficient k, absorption coefficient α, and optical band gap of the films material have been evaluated. The optical absorption coefficient was calculated from the measured normal reflectance, R, and transmittance, T, spectra. The optical spectra of all samples exhibited two distinct regions: at high energy, which suggests a direct forbidden transition with optical gap ranging from 1.75 to 2.0 eV and increases with increase in Li-content. On the other hand a second low-energy band suggests a direct allowed transition with optical gap ranging from 0.40 to 0.42 eV. The width of the localized states (band tail) E_e was also estimated for all samples. Additional calculations applying the real part of the optical dielectric function led to the evaluation of the charge carrier concentration and their effective mass.     

Optical and IR studies on r.f. magnetron sputtered ultra-thin MoO3 films

Ultra-thin MoO₃ films were deposited onto glass and Si substrates by r.f. magnetron sputtering. The optical and IR properties of the films were studied in the range of 250 to 1000 nm and 400 to 1500 cm⁻¹, respectively. The optical transmission spectra show a significant shift in absorption edge. The energy gap of the films deposited at 373 K and 0.1 mbar was found to be 3.93 eV, and it decreases with increasing substrate temperature and decreasing sputtering pressure. The IR transmittance spectra shows strong modes of vibrations of Mo=O and Mo–O–Mo units of MoO₃ molecule. A significant change in energy gap and a shift in frequency of IR modes were observed in ultra-thin MoO₃ films.