Effect of vacuum annealing and hydrogenation on ZnSe/Mn multilayer diluted magnetic semiconductor thin films

Multilayer thin films of ZnSe/Mn diluted magnetic semiconductor have been physically deposited onto a glass substrate using thermal evaporation technique and vacuum annealed at 333 K for 1 h at base pressure of 10⁻⁵ Torr. These thin films have been hydrogenated at different pressures (15-45 psi) for half an hour at room temperature. Hydrogenation process has been performed for as- grown as well as annealed thin films and named as-grown hydrogenated and annealed hydrogenated DMS thin films respectively. Structural characteristics of as-grown and vacuum annealed thin films have been performed by X-ray diffractometer. Current-voltage measurement has been studied for both as- grown hydrogenated and annealed hydrogenated DMS thin films by Keithly electrometer. X-ray diffraction pattern has been revealed nanocrystalline single phase of cubic zinc blende structure of film. Due to the annealing the conductivity has been found to be increased indicating the mixing of multilayer whereas the conductivity for as-grown hydrogenated and annealed hydrogenated ZnSe/Mn DMS thin films was found to be reduced indicating the electronic passivation effect of hydrogenation. Raman spectra of as-grown and annealed hydrogenated samples have been taken to see the presence of hydrogen in these samples. Surface topography of as-grown and annealed multilayer thin films has been confirmed by optical microscopy. Surface topography of annealed hydrogenated samples clearly shows the effect of hydrogenation at the surface.     

Photoluminescence of Eu-doped TiO2 thin films prepared by low pressure hot target magnetron sputtering

In this work Eu-doped TiO₂ thin films prepared by reactive magnetron co-sputtering of Ti-Eu metallic target have been studied. The results of photoluminescence (PL) and its correlation with microstructure have been described. Structural properties were examined by X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). XRD studies have shown that thin films consisted of TiO₂-anatase and AFM images display their high quality and dense nanocrystalline structure. PL spectra, measured at room temperature, show a dominating strong red luminescence corresponding to ⁵D₀-⁷F₂ transition at ∼ 617 nm and ∼ 623 nm. The evolution of photoluminescence and microstructure of the thin films has been examined as they were additionally annealed in an air ambient.     

Effects of annealing temperatures on optical and electrical properties of vacuum evaporated Ga15Se77In8 chalcogenide thin films

The optical constants (absorption coefficient, optical band gap, refractive index, extinction coefficient, real and imaginary parts of dielectric constants) of amorphous and thermally annealed thin films of Ga₁₅Se₇₇In₈ chalcogenide glasses with thickness 4000 Å have been investigated from absorption and reflection spectra as a function of photon energy in the wave length region 400-800 nm. Thin films of Ga₁₅Se₇₇In₈ chalcogenide glasses were thermally annealed for 2 h at three different annealing temperatures 333 K, 348 K and 363 K, which are in between the glass transition and crystallization temperature of Ga₁₅Se₇₇In₈ glasses. Analysis of the optical absorption data shows that the rule of non-direct transitions predominates. It was found that the optical band gap decreases with increasing annealing temperature. It has been observed that the value of absorption coefficient and extinction coefficient increases while the values of refractive index decrease with increasing annealing temperature. The decrease in optical band gap is explained on the basis of the change in nature of films, from amorphous to crystalline state. The dc conductivity of amorphous and thermally annealed thin films of Ga₁₅Se₇₇In₈ chalcogenide glasses is also reported for the temperature range 298-393 K. It has been observed that the conduction is due to thermally assisted tunneling of the carriers in the localized states near the band edges. The dc conductivity was observed to increase with the corresponding decrease in activation energy on increasing annealing temperature in the present system. These results were analyzed in terms of the Davis-Mott model.     

Si nanocrystals in SiO2 films analyzed by small angle X-ray scattering

Amorphous SiO/SiO₂ multilayers were studied using grazing-incidence small-angle X-ray scattering (GISAXS). Such SiO/SiO₂ superlattices were prepared by alternately magnetron sputtering of 3 nm thin films of SiO and 3 nm of SiO₂ (10 layers each) on Si (100) substrate. Rotation of the Si substrate during evaporation ensures the homogeneity of the films over the whole substrate. After evaporation the samples were annealed at 1050 °C for 2 h in vacuum or in air. The analysis of the 2D GISAXS pattern has shown that Si nanocrystals are formed in the annealed samples. Using a Guinier approximation, the inter-nanocrystal distance (10.5 nm) and radius of gyration (2.3 nm) have been obtained for the samples annealed in vacuum. Samples annealed in air have shown similar peak values which were however, much wider distributed.     

The copper influence on the PL spectra of CdTe thin film as a component of the CdS/CdTe heterojunction

The influence of annealing in the presence of CdCl₂ and a thin copper layer deposited onto CdTe on the photoluminescence spectra of CdTe, as a component of CdS/CdTe heterojunction, has been studied for two excitation wavelengths: 0.337 μm and 0.6328 μm. The behavior of the PL was studied as a function of the measurement temperature and excitation intensity. At 0.6328 μm excitation, the interface PL consists of a known 1.43X band, and the chloride annealing enhances radiative transitions at 1.536 eV. The intensity of the 1.536 eV transitions increases when Cu is present. The PL of as-deposited CdTe films prepared in the presence of oxygen has the 1.45X band attenuated when excited with 0.337 μm excitation wavelength.     

Effect of pre-deposition annealing on physical properties of CZTSSe thin films deposed by RF-sputtering based on nanoparticles synthesized by solvothermal technique

This work aims to highlight the beneficial effect of annealing of Cu₂ZnSn(S,Se)₄ (CZTSSe) nanoparticles (NPs) on the properties of the obtained films by RF-magnetron sputtering at room temperature (RT) and at 200 °C. The CZTSSe targets used for the deposition are obtained using nanoparticles synthesized by solvothermal technique. It is denoted that the elemental composition of thin films becomes independent of the growth temperature in the case of annealed CZTSSe NPs. The optical investigation gives that the gap energy is ranging between 1.26 and 1.40 eV with an Urbach’s energy between 100 and 200 meV. By using the Wemple and Didominico model to analyze the refractive index spectra, we have identified common oscillator energy for all CZTSSe thin films and dispersion energy ranging from 2.63 to 5.81 eV. CZTSSe thin films obtained by means of annealed NPs exhibit higher dielectric constant and refractive index. The dispersion of different parameters with experimental conditions is analyzed via a common relationship that illustrates the linear dependence of n₀, E_d, ε_s, and ε_L on the square of the valence difference (ΔZ). The conductivity spectra are deduced, and a theoretical model was identified to fit the permittivity spectra. The obtained results are promising for solar cell applications.

     

Structural and optical properties of thermally evaporated zinc phthalocyanine thin films

Thermally evaporated zinc phthalocyanine (ZnPc) films in the as deposited condition were identified to be as-amorphous. It undergoes structural transformation upon annealing up to 613 K. The optical properties and spectral behavior of as deposited and annealed thin films of ZnPc were studied using spectrophotometric measurements of the transmissivity and reflectivity at normal incidence of light in the wavelength range 200–2500 nm. The refractive index, n, and absorption index, k, were calculated and it was found that they are independent of film thickness in the thickness range 205–530 nm. Annealing at 613 K increases absorbance of films by 5–6 times in comparison with absorbance of as deposited ones and shifts peak positions of all bands towards low energy side of spectra except the peak position of N-band is shifted towards high energy side of spectra. The absorption spectra in the UV–VIS. region has been analyzed in terms of both molecular orbital and band theories. Indirect allowed transitions near the onset and fundamental absorption edges were observed. The energy at the onset was obtained and equals to 1.45 and 1.51 eV for as deposited and annealed films, respectively. The fundamental energy gap was obtained and equals to 2.94 and 2.88 eV for as deposited and annealed films, respectively. The absorption spectra shows four absorption bands. The oscillator strength, f, the electric dipole strength, q², the molar extinction coefficient, ζ_molar, were calculated for as deposited and annealed ZnPc thin films.     

Optical characterization of vacuum evaporated CdZnTe thin films deposited by a multilayer method

CdZnTe thin films of thickness 450–1400 nm have been evaporated under vacuum onto unheated glass substrates, using a multilayer method. During film deposition, the two evaporation sources, separated by two glass cylinders, were maintained at temperatures of 720 K for Zn and at 925–1200 K for CdTe, respectively. After deposition, the samples were annealed in air up to 775 K. The structural and optical properties of both as-deposited and heat-treated samples were investigated. Depending on the preparation conditions and the annealing temperature, the value of the optical band gap, E_g, of respective films varied between 1.16 and 1.63 eV. The obtained results are discussed in correlation with the structure of the films and the role of Zn atoms in CdTe films.     

Role of thermal treatment on the luminescence properties of CdTe thin films for photovoltaic applications

The efficiency of CdTe based solar cells is strongly enhanced by a thermal treatment in HCF₂Cl ambient. CdTe thin films deposited on CdS/ZnO/ITO/glass by Closed Space Sublimation before and after the annealing are characterised. The CdTe morphology is studied by atomic force microscopy and scanning electron microscopy. In the treated films the non-homogeneous distribution of the grain size disappears, in addition an increasing of the dimensions of the grains is observed. Cathodoluminescence analyses show a remarkable difference in the spectra between the treated and untreated structures. A strong increase in the intensity of the 1.4 eV band is observed by increasing the HCF₂Cl content. A model of the electronic levels inside the CdTe band gap, due to incorporation of Cl (or F) is proposed.     

Structural and electrical characteristics of chemical solution derived (Bi3.2La0.4Nd0.4)Ti3O12 thin films

(Bi_3.2La_0.4Nd_0.4)Ti₃O₁₂ (BLNT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by using chemical solution deposition technique, and the effects of annealing temperatures in the range of 550-750 °C on structure and electrical properties of the thin films were investigated. X-ray diffraction analysis shows that the thin films have a bismuth-layered perovskite structure with preferred (117) orientation. The surface morphology observation by field-emission scanning electron microscopy confirms that films are dense and smooth with uniformly distributed grains. The grain size of the thin films increases with increasing annealing temperature; meanwhile, the structural distortion of the thin films also increases. It was demonstrated that the thin films show good electrical properties. The dielectric constant and dielectric loss are 191 and 0.028, respectively, at 10 kHz for the thin film annealed at 600 °C, and the 2Pr value of the thin film annealed at 700 °C is 20.5 μC/cm² at an electric field of 500 kV/cm.     

Formation of F-doped ZnO transparent conductive films by sputtering of ZnF2

Fluorine-doped ZnO transparent conductive thin films were successfully deposited on glass substrate by radio frequency magnetron sputtering of ZnF₂. The effects of rapid thermal annealing in vacuum on the optical and electrical properties of fluorine-doped ZnO thin films have been investigated. X-ray diffraction spectra indicate that no fluorine compounds, such as ZnF₂, except ZnO were observed. The specimen annealed at 500 °C has the lowest resistivity of 6.65 × 10^? 4 Ω cm, the highest carrier concentration of 1.95 × 10²¹ cm^? 3, and the highest energy band gap of 3.46 eV. The average transmittance in the visible region of the F-doped ZnO thin films as-deposited and annealed is over 90%.     

Photoluminescence studies of CdTe films and junctions

Device quality CdTe films and junctions have been studied using low-temperature photoluminescence (PL) measurements. The behavior of the PL was studied as a function of the measurement temperature and excitation intensity. The CdTe films and junctions were prepared under various deposition conditions to determine the effect of film deposition and solar cell fabrication parameters, such as the effect of oxygen, and chloride treatment. A PL band located at 1.232 eV has been attributed to the presence of oxygen. This band is present only in as-deposited samples excited at the CdTe surface. Samples annealed in the presence of CdCl₂ exhibit a single PL band located at 1.42 eV. A model explaining the behavior of these bands is presented.     

Enhancement of photosensitivity by annealing in Bi2S3 thin films grown using SILAR method

Bi₂S₃ thin films were grown by successive ionic layer adsorption and reaction method (SILAR) onto the glass substrates at room temperature. The as prepared thin film were annealed at 250 °C in air for 30 min. These films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrical measurement systems. The X-ray diffraction patterns reveal that Bi₂S₃ thin film have orthorhombic crystal structure. SEM images showed uniform deposition of the material over the entire glass substrate. The optical energy band gap observed to be decreased from 1.69 to 1.62 eV for as deposited and annealed films respectively. The I–V measurement under dark and illumination condition (100 W) show annealed Bi₂S₃ thin film gives good photoresponse as compared to as deposited thin film and Bi₂S₃ thin film exhibits photoconductivity phenomena suggesting its useful in sensors device. The thermo-emf measurements of Bi₂S₃ thin films revealed n-type electrical conductivity.     

Influence of thermal annealing on microstructural,morphological, optical properties and surface electronic structure of copper oxide thin films

In this study, effect of the post-deposition thermal annealing on copper oxide thin films has been systemically investigated. The copper oxide thin films were chemically deposited on glass substrates by spin-coating. Samples were annealed in air at atmospheric pressure and at different temperatures ranging from 200 to 600°C. The microstructural, morphological, optical properties and surface electronic structure of the thin films have been studied by diagnostic techniques such as X-ray diffraction (XRD), Raman spectroscopy, ultraviolet–visible (UV–VIS) absorption spectroscopy, field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The thickness of the films was about 520 nm. Crystallinity and grain size was found to improve with annealing temperature. The optical bandgap of the samples was found to be in between 1.93 and 2.08 eV. Cupric oxide (CuO), cuprous oxide (Cu₂O) and copper hydroxide (Cu(OH)₂) phases were observed on the surface of as-deposited and 600 °C annealed thin films and relative concentrations of these three phases were found to depend on annealing temperature. A complete characterization reported herein allowed us to better understand the surface properties of copper oxide thin films which could then be used as active layers in optoelectronic devices such as solar cells and photodetectors.     

Fabrication and ferroelectric properties of sol–gel derived 1–1 intergrowth-superlattice-structured Bi<Subscript>3</Subscript>TiNbO<Subscript>9</Subscript>-Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

1–1 intergrowth-superlattice-structured Bi₃TiNbO₉–Bi₄Ti₃O₁₂ (BTN–BIT) ferroelectric thin films have been prepared on p-Si substrates by sol-gel processing. The precursor films are crystallized in the desired intergrown BTN–BIT superlattice structures by optimizing the processing conditions. Synthesized BTN–BIT thin films annealed below 750 °C are polycrystalline, uniform and crack-free, no pyrochlore phase or other second phase, and exhibited good ferroelectric properties. As the annealing temperature increases from 600 to 700 °C, both remanent polarization P _r and coercive electric field E _c of BTN–BIT thin films increase, but the pyrochlore phase in BTN–BIT films annealed above 750 °C will impair the ferroelectric properties. The BTN–BIT thin films annealed at 700 °C have a P _r value ~19.1μC/cm² and an E _c value ~135 kV/cm.     

Nanoporous TiO2 thin film based conductometric H2 sensor

Nanoporous titanium dioxide (TiO₂) based conductometric sensors have been fabricated and their sensitivity to hydrogen (H₂) gas has been investigated. A filtered cathodic vacuum arc (FCVA) system was used to deposit ultra-smooth Ti thin films on a transducer having patterned inter-digital gold electrodes (IDTs). Nanoporous TiO₂ films were obtained by anodization of the titanium (Ti) thin films using a neutral 0.5% (wt) NH₄F in ethylene glycol solution at 5 V for 1 h. After anodization, the films were annealed at 600 °C for 8 h to convert the remaining Ti into TiO₂. The scanning electron microscopy (SEM) images revealed that the average diameters of the nanopores are in the range of 20 to 25 nm. The sensor was exposed to different concentrations of H₂ in synthetic air at operating temperatures between 100 °C and 300 °C. The sensor responded with a highest sensitivity of 1.24 to 1% of H₂ gas at 225 °C.     

Structural and optical properties of nanocrystalline WO<Subscript>3</Subscript> thin films

The nanocrystalline WO₃ thin films were deposited by r.f. magnetron sputtering on quartz and p- type Si (100) substrates at a constant power of 25 W and at three different sputtering pressures (0.05, 0.01 and 0.5 mbar) and post annealed at different temperatures. The deposited films were characterized by XRD, UV–VIS spectrophotometry, ellipsometry and atomic force microscopy (AFM). The structural studies from XRD spectra reveals that the films deposited at 0.05 mbar and post annealed at 573 and 673 K have the predominant orthorhombic phase, whereas at 0.1 mbar and 573, 673 K triclinic phase is predominant. When sputtering pressure is at 0.5 mbar the predominant phase is monoclinic when annealed at 473 K and triclinic at 673 K. The optical energy gap is influenced significantly by sputtering pressure and post annealing temperatures. The optical energy gap of the films deposited at higher sputtering pressures and post annealed at lower temperatures is high due to smaller crystallite sizes. The thickness of all deposited films at different conditions is around 200 nm.     

Studies of key technologies for large area CdTe thin film solar cells

The structure and main manufacturing technologies of CdTe film solar cells of large area are reviewed. Among the technologies, some have been developed for application in a pilot manufacturing line. The high resistant SnO₂ (HRT) thin films have been fabricated by PECVD. The effects of annealing on the structure and properties have been studied. A surface etching process of CdTe in low temperature and lower concentration of nitric acid has been developed. The Cd_1 − xZn_xTe ternary compound films have been studied. In order to improve the back contact layer, Cd_0.4Zn_0.6Te layer with 1.8 eV band gap as a substitute for ZnTe layer is introduced in CdTe cells. The effects of the technologies on performance of CdTe cells and feasibility of application in the modules are discussed.     

CdTe thin film solar cells: Interrelation of nucleation, structure, and performance

The performance of CdTe solar cells as prototype of thin film solar cells strongly depends on film morphology. The needs for high solar cell performance using thin film materials will be addressed covering nucleation and growth control of thin film materials. In order to understand the basic growth mechanisms and their impact on cell performance, we have systematically investigated the growth of CdTe thin films by Close Spaced Sublimation (CSS) using the integrated ultra-high vacuum system DAISY-SOL. CdTe thin films were deposited on TCO/CdS substrates (transparent conductive oxide) held at 270 °C to 560 °C. The properties of the films were determined before and after CdCl₂ treatment using X-ray diffraction and electron microscopy. In addition, solar cells were prepared to find correlations between material properties and cell efficiency. At low sample temperature the films tend to form compact layers with preferred (111) orientation which is lost at elevated temperatures above 450 °C. For CdS layers without (0001) texture there is in addition a low temperature regime (350 °C) with (111) texture loss. After activation treatment the (111) texture is lost for all deposited layers leading to strong recrystallisation of the grains. But the texture still depends on the previous growth history. The loss of (111) texture is evidently needed for higher performance. A clear correlation between cell efficiency and the texture of the CdTe film is observed.     

Effects of post-deposition annealing temperature and ambient on RF magnetron sputtered Sm<Subscript>2</Subscript>O<Subscript>3</Subscript> gate on n-type silicon substrate

Samarium oxide (Sm₂O₃) thin films with thicknesses in the range of 15–30 nm are deposited on n-type silicon (100) substrate via radio frequency magnetron sputtering. Effects of post-deposition annealing ambient [argon and forming gas (FG) (90% N₂ + 10% H₂)] and temperatures (500, 600, 700, and 800 °C) on the structural and electrical properties of deposited films are investigated and reported. X-ray diffraction revealed that all of the annealed samples possessed polycrystalline structure with C-type cubic phase. Atomic force microscope results indicated root-mean-square surface roughness of the oxide film being annealed in argon ambient are lower than that of FG annealed samples, but they are comparable at the annealing temperature of 700 °C (Argon—0.378 nm, FG—0.395 nm). High frequency capacitance–voltage measurements are carried out to determine effective oxide charge, dielectric constant and semiconductor-oxide interface trap density of the annealed oxide films. Sm₂O₃ thin films annealed in FG have smaller amount of effective oxide charge and semiconductor-oxide interface trap density than those oxide films annealed in argon. Current–voltage measurements are conducted to obtain barrier heights of the annealed oxide films during Fowler–Nordheim tunneling.