Room-temperature deposition of transparent conductive Al-doped ZnO thin films using low energy ion bombardment

Al-doped zinc oxide (AZO) films are prepared on quartz substrates by dual-ion-beam sputtering deposition at room temperature (∼25°C). An assisting argon ion beam (ion energy E _i =0–300 eV) directly bombards the substrate surface to modify the properties of AZO films. The effects of assisted-ion beam energy on the characteristics of AZO films were investigated in terms of X-ray diffraction, atomic force microscopy, Raman spectra, Hall measurement and optical transmittance. With increasing assisting-ion beam bombardment, AZO films have a strong improved crystalline quality and increased radiation damage such as oxygen vacancies and zinc interstitials. The lowest resistivity of 4.9×10⁻³Ω cm and highest transmittance of above 85% in the visible region were obtained under the assisting-ion beam energy 200 eV. It was found that the bandgap of AZO films increased from 3.37 to 3.59 eV when the assisting-ion beam energy increased from 0 to 300 eV.     

Influence of solvent on solution processed Cu2ZnSnS4 nanocrystals and annealing induced changes in the optical,structural properties of CZTS film

The well-known quaternary Cu₂ZnSnS₄ (CZTS) chalcogenide thin films are playing an important role in modern technology. The CZTS nanocrystal were successfully prepared by solution method using water, ethylene glycol and ethylenediamine as different solvent. The pure phase material was used for thin film coating by thermal evaporation method. The prepared CZTS thin films were characterized by XRD, Raman spectroscopy, FESEM, XPS and FT-IR spectroscopy. The XRD and Raman spectroscopy analysis revealed the formation of polycrystalline CZTS thin film with tetragonal crystal structure after annealing at 450 ^°C. The oxidation state of the annealed film was studied by XPS. A direct band gap about 1.36 eV was estimated for the film from FT-IR studies, which is nearly close to the optimum value of band gap energy of CZTS materials for best solar cell efficiency. The CZTS annealed thin films are more suitable for using as a p-type absorber layer in a low-cost solar cell.     

Band gap tunable and improved microstructure characteristics of Cu2ZnSn(S1−x,Sex)4 thin films by annealing under atmosphere containing S and Se

Cu₂ZnSn(S_xS_1?x)₄ (CZTSSe) thin films were prepared by annealing a stacked precursor prepared on Mo coated glass substrates by the sputtering technique. The stacked precursor thin films were prepared from Cu, SnS₂, and ZnS targets at room temperature with stacking orders of Cu/SnS₂/ZnS. The stacked precursor thin films were annealed using a tubular two zone furnace system under a mixed N₂ (95%) + H₂S (5%) + Se vaporization atmosphere at 580 °C for 2 h. The effects of different Se vaporization temperature from 250 °C to 500 °C on the structural, morphological, chemical, and optical properties of the CZTSSe thin films were investigated. X-ray diffraction patterns, Raman spectroscopy, and X-ray photoelectron spectroscopy results showed that the annealed thin films had a single kesterite crystal structure without a secondary phase. The 2θ angle position for the peaks from the (112) plane in the annealed thin films decreased with increasing Se vaporization temperature. Energy dispersive X-ray results showed that the presence of Se in annealed thin films increased from 0 at% to 42.7 at% with increasing Se vaporization temperatures. UV–VIS spectroscopy results showed that the absorption coefficient of all the annealed thin films was over 10⁴ cm^?1 and that the optical band gap energy decreased from 1.5 eV to 1.05 eV with increasing Se vaporization temperature.     

Swift heavy ion irradiation induced modification of BiFeO3 thin films prepared by sol-gel method

We report the preparation of multiferroic BiFeO₃ thin films on ITO coated glass substrates through sol-gel spin coating method followed by thermal annealing and their modification by swift heavy ion (SHI) irradiation. X-ray diffraction and Raman spectroscopy studies revealed amorphous nature of the as deposited films. Rhombohedral crystalline phase of BiFeO₃ evolved on annealing the films at 550°C. Both XRD and Raman studies indicated that SHI irradiation by 200 MeV Au ions result in fragmentation of particles and progressive amorphization with increasing irradiation fluence. The average crystallite size estimated from the XRD line width decreased from 38 nm in pristine sample annealed at 550°C to 29 nm on irradiating these films by 200 MeV Au ions at 1 × 10¹¹ ions cm⁻². Complete amorphization of the rhombohedral BiFeO₃ phase occurs at a fluence of 1 × 10¹² ions.cm⁻². Irradiation by another ion (200 MeV Ag) had the similar effect. For both the ions, the electronic energy loss exceeds the threshold electronic energy loss for creation of amorphized latent tracks in BiFeO₃.     

Optical properties of indium nitride powder and films

Using photoluminescence and transmission measurements, we have studied the optical properties of indium nitride powder and thin films grown by molecular beam epitaxy. The bandgap for InN powder with electron concentration ∼ 4·10¹⁹ cm⁻³ was 0.94 eV, and for InN films with electron concentrations ∼10¹⁸ cm⁻³ it was 0.7 eV. We have established that when the electron concentration is increased to 8·10¹⁹ cm⁻³, the bandgap of InN increases to 1.0 eV. The change in the bandgap as a function of the concentration is due to the appearance of the Burstein-Moss effect. Report given at the Fifth Belorussian-Russian Seminar on Semiconductor Lasers and Systems Based on Semiconductor Lasers, June 1–5, 2005, Minsk, Belarus. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 86–89, January–February, 2006.     

Optical properties of single-phase β-FeSi2 films fabricated by electron beam evaporation

Single-phase semiconducting iron disilicide (β-FeSi₂) films on silicon substrate were fabricated by electron beam evaporation (EBE) technique. For preventing the oxidation of Fe film, silicon/iron/silicon sandwich structure films with different thickness of silicon and iron were deposited and then annealed at different temperatures. X-ray diffraction (XRD), Raman and Fourier transform infrared spectroscopy (FTIR) measurements were carried out to study the phase distribution and crystal quality of the films. Single-phase β-FeSi₂ with high crystal quality was achieved after annealing at 800 °C for 5 h. An apparent direct bandgap E_g of approximately 0.85-0.88 eV was observed in the β-FeSi₂ films. It is considered that the silicon/iron/silicon sandwich structure is suited for formation of single-phase β-FeSi₂ with high crystal quality.     

Temperature-dependent photoreflectance of SnS crystals

The optical properties of single-crystal SnS were studied by photoreflectance (PR) spectroscopy. Temperature-dependent PR spectra were measured in the range 20–200 K. A room-temperature bandgap energy value of E_g=1.317 eV was estimated by fitting the temperature dependence of the bandgap energy obtained from the PR spectra. The vibrational properties of orthorhombic SnS were studied using Raman spectroscopy. Four vibrational modes were detected at 95, 163, 191, and 218 cm^–1.     

Electrical and optical properties of titanium dioxide films

A method is described for producing insulating films of titanium dioxide by vacuum evaporation. Photomicrographs showing the growth of crystallites in the layer are presented, and X-ray and electron diffraction data are given. Sputtering regimes by means of which it is possible to produce compact layers of specific resistance 10¹³ ohm · · cm, dielectric strength 10⁶V/cm, and dielectric constant of 30 are given.By investigating optical density spectra and temperature variation of electrical conductivity for these specimens values were obtained for the optical and thermal forbidden band widths in titanium dioxide; these were 4.2 and 3.9 eV respectively. It was found that insulating films of titanium dioxide were completely transparent over a wide range of wavelengths from 300 to 1000 m. Using the same investigations in layers with electrical conductivity greater than 10^–13/ohm · · cm defects were discovered, which were connected with oxygen deficiency and gave three impurity energy levels in the forbidden band of titanium dioxide.In conclusion the authors would like to express their gratitude to Prof. K. V. Shalimova under whose guidance the work was executed.     

Characterization of gallium-doped CdS thin films grown by chemical bath deposition

Ga-doped CdS thin films, with different [Ga]/[Cd] ratios, were grown using chemical bath deposition. The effect of Ga-doping on optical properties and bandgap of CdS films is investigated. Resistivity, carrier density, and mobility of doped films were acquired using Hall effect measurements. Crystal structure as well as crystal quality and phase transition were determined using X-ray diffraction (XRD) and Micro-Raman spectroscopy. Film morphology was studied using scanning electron microscopy, while film chemistry and binding states were studied using X-ray photoelectron spectroscopy (XPS). A minimum bandgap of 2.26 eV was obtained at [Ga]/[Cd] ratio of 1.7 × 10⁻². XRD studies showed Ga³⁺ ions entering the lattice substitutionally at low concentration, and interstitially at high concentration. Phase transition, due to annealing, as well as induced lattice defects, due to doping, were detected by Micro-Raman spectroscopy. The highest carrier density and lowest resistivity were obtained at [Ga]/[Cd] ratio of 3.4 × 10⁻². XPS measurements detect an increase in sulfur deficiency in doped films.     

Investigation of thermal annealing effects on microstructural and optical properties of HfO2 thin films

In the present paper, we investigate the effect of thermal annealing on optical and microstructural properties of HfO₂ thin films (from 20 to 190 nm) obtained by plasma ion assisted deposition (PIAD). After deposition, the HfO₂ films were annealed in N₂ ambient for 3 h at 300, 350, 450, 500 and 750 °C. Several characterisation techniques including X-ray reflectometry (XRR), X-ray diffraction (XRD), spectroscopic ellipsometry (SE), UV Raman and FTIR were used for the physical characterisation of the as-deposited and annealed HfO₂ thin films. The results indicate that as-deposited PIAD HfO₂ films are mainly amorphous and a transition to a crystalline phase occurs at a temperature higher than 450 °C depending on the layer thickness. The crystalline grains consist of cubic and monoclinic phases already classified in literature but this work provides the first evidence of amorphous-cubic phase transition at a temperature as low as 500 °C. According to SE, XRR and FTIR results, an increase in the interfacial layer thickness can be observed only for high temperature annealing. The SE results show that the amorphous phase of HfO₂ (in 20 nm thick samples) has an optical bandgap of 5.51 eV. Following its transition to a crystalline phase upon annealing at 750 °C, the optical bandgap increases to 5.85 eV.     

Hardnes and resistivity of amorphous carbon thin films deposited by laser ablation

Amorphous carbon thin films were deposited by laser ablation of a graphite target, using the fundamental line of a 5 ns Nd:YAG laser. Deposition was carried out as a function of the plasma parameters (mean kinetic ion energy and plasma density), determined by means of a planar probe. In the selected working regimes the optical emission from the plasma is mainly due to atomic species, namely C⁺ (426.5 nm); however, there is also emission from other atomic species and molecular carbon. The hardness and resistivity could be varied in the range between 10 and 25 GPa, and 10⁸ and 10¹¹ Ω cm, respectively. The maximum values were obtained at a 200 eV ion energy and 6×10¹³ cm⁻³ plasma density, where the maximum quantity of C–C sp³ bonds was formed, as confirmed by Raman spectroscopy.     

电沉积－退火工艺制备铜铟硒太阳能电池薄膜及表征

利用电沉积硒气氛下后续退火的工艺制备出了高结晶质量的铜铟硒薄膜．通过X射线衍射、扫描电子显微镜、拉曼光谱、紫外-可见-近红外光谱和阻抗谱技术对退火后的铜铟硒薄膜进行表征,结果表明530 oC硒化退火后的铜铟硒薄膜具有四方的黄铜矿晶体结构,晶粒尺寸达到微米量级,光学带隙为0.98 eV,经过KCN溶液去除表面高导电性的铜硒化合物后铜铟硒薄膜的载流子浓度在10¹⁶ cm^-3量级．利用硒化退火的铜铟硒薄膜作为光吸收层制备了结构为AZO/i-ZnO/CdS/CIS/Mo/glass的太阳能电池,在AM1.5光照条件下对其电流-电压特性测试后发现面积为0.2 cm²的电池可以达到0.96％的能量转换效率,并对限制电池效率的原因做出了初步的分析和讨论.     

Evolution of structural and optical properties of rutile TiO2 thin films synthesized at room temperature by chemical bath deposition method

Nanocrystalline thin films of TiO₂ were prepared on glass substrates from an aqueous solution of TiCl₃ and NH₄OH at room temperature using the simple and cost-effective chemical bath deposition (CBD) method. The influence of deposition time on structural, morphological and optical properties was systematically investigated. TiO₂ transition from a mixed anatase–rutile phase to a pure rutile phase was revealed by low-angle XRD and Raman spectroscopy. Rutile phase formation was confirmed by FTIR spectroscopy. Scanning electron micrographs revealed that the multigrain structure of as-deposited TiO₂ thin films was completely converted into semi-spherical nanoparticles. Optical studies showed that rutile thin films had a high absorption coefficient and a direct bandgap. The optical bandgap decreased slightly (3.29–3.07 eV) with increasing deposition time. The ease of deposition of rutile thin films at low temperature is useful for the fabrication of extremely thin absorber (ETA) solar cells, dye-sensitized solar cells, and gas sensors.     

Amorphous/microcrystalline transition of thick silicon film deposited by PECVD

Thick silicon films were deposited by plasma-enhanced chemical vapor deposition at different plasma power densities. Annealing treatment was performed on these deposited films. As-deposited and annealed films were characterized by X-ray diffraction, Raman scattering spectroscopy and reflectance spectroscopy. Before annealing, only the film deposited at the plasma power density of 500 mW/cm² exhibits a diffraction peak corresponding to the (111) plane orientation. Raman spectrum of this film confirms the presence of crystalline phase. After annealing, a transition from amorphous phase to crystalline one occurs for all samples. This transition is accompanied by an increase of the crystalline fraction volume deduced from Raman spectra analysis and by a reduction of optical gap energy.     

Trap characterization for Bi4Ti3O12 thin films by thermally stimulated currents

Thermally stimulated current (TSC) measurements performed in the 100 K–400 K temperature range on Bi₄Ti₃O₁₂ (BiT) thin films annealed at 550 °C and 700 °C had revealed two trapping levels having activation energies of 0.55 eV and 0.6 eV. The total trap concentration was estimated at 10¹⁵ cm⁻³ for the samples annealed at 550 °C and 3×10¹⁵ cm⁻³ for a 700 °C annealing and the trap capture cross-section was estimated about 10⁻¹⁸ cm². From the temperature dependence of the dark current in the temperature range 20 °C–120 °C the conduction mechanism activation energy was found to be about 0.956–0.978 eV. The electrical conductivity depends not only on the sample annealing temperature but also whether the measurement is performed in vacuum or air. The results on the dark conductivity are discussed considering the influence of oxygen atoms and oxygen vacancies. Received: 28 January 1998 / Accepted: 8 January 1999 / Published online: 5 May 1999     

Structural and optoelectronic properties of vacuum evaporated SnS thin films annealed in argon ambient

In this work, 650 nm polycrystalline SnS thin films were grown by thermal evaporation of high purity tin sulfide powder at 250 °C substrate temperature, followed by post deposition annealing at 200 °C and 300 °C for 2, 4 and 6 h, and at 400 °C for 2 and 4 h in argon ambient. The XRD pattern of the as-deposited and annealed SnS films led to the conclusion that the as-deposited films were polycrystalline in nature with preferentially oriented along (1 1 1) direction. The direct bandgap of all the films was found to be observed between 1.33 and 1.53 eV. Except for annealing at 400 °C all the films were nearly stoichiometric in nature, suggesting lower rate of desulfurization at that ambient. However, higher annealing temperature has resulted in the segregation of tin phase. All the films showed good absorption in the visible range. The as-deposited and annealed films showed p-type conductivity. Hall measurement revealed the carrier concentration and mobility ranging from 10¹⁵ to 10¹⁶ cm⁻³ and 0.8 to 31.6 cm² V⁻¹ s⁻¹ respectively. The photoconductivity measurements of all the SnS films were carried out by recording the lowering of resistance of the respective films with time under illumination.     

Low-macroscopic field emission from nanocrystalline Al doped SnO<Subscript>2</Subscript> thin films synthesized by sol–gel technique

We have observed low-macroscopic field electron emission from wide bandgap nanocrystalline Al doped SnO₂ thin films deposited on glass substrates. The emission properties have been studied for different anode-sample spacings and for different Al concentrations in the films. The turn-on field and approximate work function were calculated and we have tried to explain the emission mechanism from this. The turn-on field was found to vary in the range 5.6–7.5 V/μm for a variation of anode sample spacing from 80–120 μm. The turn-on field was also found to vary from 4.6–5.68 V/μm for a fixed anode-sample separation of 80 μm with a variation of Al concentration in the films 8.16–2.31%. The Al concentrations in the films have been measured by energy dispersive X-ray analysis. Optical transmittance measurement of the films showed a high transparency with a direct bandgap ∼3.98 eV. Due to the wide bandgap, the electron affinity of the film decreased. This, along with the nanocrystalline nature of the films, enhanced the field emission properties. PACS 81.20.Fw; 61.10.-i; 79.70.+q     

The relationship between refractive index-energy gap and the film thickness effect on the characteristic parameters of CdSe thin films

CdSe thin films were deposited on glass substrates using Successive Ionic Layer Adsorption and Reaction (SILAR) method at room temperature and ambient pressure. The relationship between refractive index and energy bandgap was investigated. The film thickness effect on the structural, morphological, optical and electrical properties of CdSe thin films was investigated. The X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies showed that all the films exhibit polycrystalline nature with hexagonal structure and are covered well with glass substrates. The crystalline and surface properties of the films improved with increasing film thickness. The optical absorption studies revealed that the films are found to be a direct allowed transition. The energy bandgap values were changed from 1.93 to 1.87 eV depending on the film thickness. The electron effective mass (m_e^?/m_o), refractive index (n), optical static and high frequency dielectric constant (ε_o, ε_∞) values were calculated by using the energy bandgap values as a function of the film thickness. The resistivity of the films changed between 10⁶ and 10² Ω-cm with increasing film thickness at room temperature.     

Synthesis of amorphous boron carbide by single and multiple charged boron ions bombardment of fullerene thin films

In this paper, results of structural modification of fullerene thin films by single and multiple charged boron ions (B⁺, B³⁺) are presented. The applied ion energies were in the range of 15-45 keV. The characterization of as-deposited and irradiated specimens has been performed by atomic force microscopy, Raman and Fourier transform infrared spectroscopy and UV/vis spectrophotometry. The results of Raman analysis have shown the formation of amorphous layer after irradiation of fullerene thin films. Fourier transform infrared spectroscopy has confirmed the formation of new B-C bonds in irradiated films at higher fluences (2 × 10¹⁶ cm⁻²). The morphology of bombarded films has been changed significantly. The optical band gap was found to be reduced from 1.7 to 1.06 eV for irradiated films by B³⁺ ions and 0.7 eV for irradiated films by B⁺ ions.     

Structure and electrical properties of HfO<Subscript>2</Subscript> high-<Emphasis Type="Italic">k</Emphasis> films prepared by pulsed laser deposition on Si (100)

High-k gate dielectric hafnium dioxide films were grown on Si (100) substrate by pulsed laser deposition at room temperature. The as-deposited films were amorphous and that were monoclinic and orthorhombic after annealed at 500°C in air and N₂ atmosphere, respectively. After annealed, the accumulation capacitance values increase rapidly and the flat-band voltage shifts from −1.34 V to 0.449 V due to the generation of negative charges via post-annealing. The dielectric constant is in the range of 8–40 depending on the microstructure. The I–V curve indicates that the films possess of a promising low leakage current density of 4.2×10⁻⁸ A/cm² at the applied voltage of −1.5 V.