衬底温度对碲化镉薄膜结构及光学性能的影响

碲化镉(CdTe)因具有良好的光电性能和吸收性能经常被作为太阳电池的吸收层材料.以纯度为99.99;的CdTe陶瓷靶为靶材在玻璃衬底上采用射频磁控溅射的方法制备了一系列的CdTe薄膜,研究了衬底温度对样品薄膜的厚度、结构和光学性能的影响.结果表明:随着衬底温度的增加薄膜的厚度在逐渐地减少;制备的薄膜都是立方闪锌矿结构且具有高度的(111)面择优取向;薄膜对可见光有较好的吸收性能,随衬底温度的增加而减小.     

Synthesis and epitaxial growth of CdTe films by neutral and ionized beams

The growth of CdTe thin films has been studied by epitaxial processes on the cleavage surface of rock salt in vacuum, using electron microscopic and electron diffraction techniques. The crystallinity and structure of the films depend largely upon the intensities and species of the incident beams. The use of two beams effused separately from the Knudsen cells resulted in the growth of films of good crystallinity when the intensity ratio N_Cd : N_Te was 10 : 1. The epitaxial relationships were studied over the range of substrate temperatures between room temperature and 350°C. The co-existence of α-hexagonal and β-cubic modifications of CdTe and their proportions in the film were revealed as a function of the growth processes and substrate temperature. If two beams were ionized by electron bombardment inside the cells and were incident upon the substrate by applying a dc voltage between source and substrate, the epitaxial temperature can be lowered to near room temperature, giving good epitaxy. The epitaxial relationships in the CdTe/NaCl system have been studied.     

Photostimulated changes of properties of CdTe films

The effect of illumination during the close‐spaced sublimation (CSS) growth on composition, structural, electrical, optical and photovoltaic properties of CdTe films and CdTe/CdS solar cells were investigated. Data on comparative study by using X‐ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectra and conductivity‐temperature measurements of CdTe films prepared by CSS method in dark (CSSD) and under illumination (CSSI) were presented. It is shown that the growth rate and the grain size of CdTe films grown under illumination is higher (by factor about of 1.5 and 3 respectively) than those for films prepared without illumination. The energy band gap of CdTe films fabricated by both technology, determined from absorption spectra, is same (about of 1.50 eV), however conductivity of the CdTe films produced by CSSI is considerably greater (by factor of 10⁷) than that of films prepared by CSSD. The photovoltaic parameters of pCdTe/nCdS solar cells fabricated by photostimulated CSSI technology (J_sc = 28 mA/cm², V_oc =0.63 V) are considerably larger than those for cells prepared by CSSD method (J_sc = 22 mA/cm², V_oc = 0.52 V). A mechanism of photostimulated changes of properties of CdTe films and improvement of photovoltaic parameters of CdTe/CdS solar cells is suggested. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Polycrystalline CdTe thin films for photovoltaic applications

The CdTe/CdS thin film solar cells can be most conveniently fabricated in the form of thin films. Solar cells based on CdTe have been studied for several years now and the technology seems to be ripe for starting significant industrial production. Recently CdTe thin film solar cells have achieved an energy conversion efficiency record of 16.5% on a laboratory scale.In this paper we review the process needed to prepare high efficiency CdTe/CdS solar cells from the point of view of thin film deposition techniques.Furthermore we show that thin film CdTe technology is sufficiently mature to be easily transferred to form the basis of a large-scale module production.     

Physical properties of Ag-doped cadmium telluride thin films fabricated by closed-space sublimation technique

Cadmium telluride (CdTe) thin films were prepared by the closed-space sublimation (CSS) technique, using CdTe powder as evaporant onto substrates of water-white glass. In the next step, the annealed films at 450 °C for 30 min were dipped in AgNO₃–H₂O solution at room temperature. These films were again annealed at 450 °C for 1 h to obtain silver-doped samples. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), electrically i.e. DC electrical resistivity as well as photo resistivity by van der Pauw method at room temperature, dark conductivity, activation energy analysis as a function of temperature by two-probe method under vacuum, and spectrophotometry. The electron microprobe analyzer (EMPA) results showed an increase of Ag content composition in the samples by increasing the immersion time of films in solution. The Hall measurements indicated the increase in mobility and carrier concentrations of CdTe films by doping of Ag. A significant change in the shape and size of the CdTe grains were observed.     

Evidence of VLS growth in CdTe film preparation by NH4Cl closed-tube CVD

By thermodynamical calculations of the vapour phase composition expected to occur in the closed — tube CVD of CdTe films on CdTe substrates, it is shown that a VLS growth mechanism should be active in the growth process when use is made of the thermal decomposition of NH₄Cl for producing the proper amount of HCl as a transport agent. Responsible of this VLS mechanism is the liquid tellurium, which is always present when the NH₄Cl concentration reaches values sufficiently high for the epitaxial deposition of CdTe films.     

Effects of CdCl2 treatment on properties of CdTe thin films grown by evaporation at low substrate temperatures

The structural, morphological and optical properties of vacuum‐evaporated CdTe thin films were investigated as a function of substrate temperature and post‐deposition annealing without and with CdCl₂/treatment at 400°C for 30 min. Diffraction patterns are almost the same exhibiting higher preferential orientation corresponding to (111) plane of the cubic phase. The intensity of the (111) peak increased with the CdCl₂/annealing treatment. The microstructure observed for all films following the CdCl₂/annealing treatment are granular, regardless of the as‐deposited microstructure. The grain sizes are increased after the CdCl₂/annealing treatment but now contain voids around the grain boundaries. The optical band gaps, E_g, were found to be 1.50, 1.50 and 1.48 eV for films deposited at 200 K and annealed without and with CdCl₂/treatment at 400°C for 30 min respectively. A progressive sharpening of the absorption edge upon heat treatment particularly for the CdCl₂/treated was observed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermo emf studies on CdTe:Sb Thin Films

Thermal transport properties have been studied on as-grown and annealed CdTe:Sb thin films of different thicknesses and concentrations of Sb. These films were prepared by sequential vacuum deposition of CdTe and Sb on clean and hot glass substrates held at 210 °C temperature at a constant rate of deposition. From these studies all the films were found to be p-type. It is also observed that the thermoelectric power increases with Sb concentgration, thickness of the film and with annealing process. Fermi-energy variation with temperature have been calculated on the basis of thermo emf data. All these results have been explained on the basis of defects introduced by Sb doping.     

Ultrahigh Vacuum Atomic Layer Epitaxy of Ternary II-VI Semiconductor Compounds

A concise discussion concerning the UHV ALE growth of ternary II-VI compounds is presented in this paper. Simultaneous reflection mass spectrometry (REMS) and reflection high energy electron diffraction (RHEED) measurements of the surface kinetic and structural parameters, respectively, governing the UHV ALE growth of Cd_1-xZn_xTe and Cd_1-xMn_xTe heteroepitaxial films are reported. In addition, a Monte-Carlo-based method for simulation of the UHV ALE process of CdTe (the model-compound for this growth technique) has been used for investigation of the Cd cation's fluxes reflected from the growing epilayer surface in different phases of the ALE process. The Cd⁺ ion-related REMS signals measured during CdTe growth have been compared with the simulation results.     

Specific features of the growth of A II B VI films on (0001)Al2O3 substrates

The structure and orientation of CdTe and ZnO films on sapphire have been investigated for different techniques of pregrowth substrate treatment. Polycrystalline CdTe films are found to grow of substrates unannealed or annealed in vacuum at a residual pressure P < 0.13 Pa. Epitaxial CdTe films with the sphalerite cubic structure, oriented parallel to the substrate by the (111) plane, grow on substrates annealed in air at a temperature of 1000°C or more and having a system of smooth terraces and steps on the surface. For ZnO films with a wurtzite hexagonal structure obtained by magnetron sputtering, a similar correlation between the structural quality and the regime of treatment of sapphire substrates is observed. It is shown that thermal annealing of (0001) sapphire plates in air is the optimal way of substrate preparation for growing epitaxial ZnO films with the base orientation. The obtained epitaxial CdTe films contain a certain amount of structural defects (mosaicity and twins), while the epitaixal ZnO films treated in the same way are close to perfect.     

Properties of Hg1‐xCdxTe epitaxial films grown on (211)CdTe and (211)CdZnTe

Hg_1‐xCd_xTe (MCT) epitaxial films have been grown employing single crystalline substrates of CdTe and Cd_0.96Zn_0.04Te with (211)Cd and (211)Te crystalline orientations. The Isothermal Vapor Phase Epitaxy (ISOVPE) technique without Hg overpressure has been used for the epitaxial growth. Substrates and films were characterized by optical microscopy, chemical etching and x ray diffraction (Laue technique). The electrical properties were determined by Hall effect measurements. The characterization results allowed to evaluate the crystalline quality of MCT films. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterization of CdTe thin films fabricated by close spaced sublimation technique and a study of Cu doping by ion exchange process

CdTe thin films were prepared onto water-white glass substrates by the close spaced sublimation technique. The films annealed right after the deposition were then immersed in copper nitrate solution for different periods of time. These films were again annealed at 500 ^oC for 1 h to ensure the diffusion of copper in the films. The samples were characterized by X-ray diffraction and scanning electron microscopy. The electron microprobe analyzer showed an increase of copper-content in composition. The dc electrical conductivity showed a credible increase with increasing copper-content in the films. With the increase of copper-content, the hole mobility increased systematically. The optical parameters were deduced by fitting the optical transmittance in the wavelength range 300–2500 nm.     

On the occurrence of polytypism in single crystal CdTe thin films

Cadmium telluride thin films have been found to exhibit polytypism. The polytypes are formed when the as grown amorphous CdTe thin films undergo amorphous to crystalline transformation. The transformed single crystal regions correspond to different polytypes. Besides the well known zinc blende type 3 C cubic phase and less often found wurtzite type 2 H phase, four new polytypes (5 H, 6 H, 6 R and 15 R) the only ones known to-date have been found in the present investigation. In addition to the new polytypes, a new structural variant has also been found. This has the same ‘c’ parameter as that of the 2 H phase but has its ‘a’ lattice parameter as ‘a₀ \documentclass{article}\pagestyle{empty}\begin{document}$ a_{\rm o} \sqrt {3} $\end{document}’ (a₀ being the common lattice parameter of the polytypes). A feasible mechanism making the formation of polytypes intelligible has been suggested.     

Preparation and properties of titanium silicide coating glass by CVD

Titanium silicide thin films were prepared on glass substrates by chemical vapor deposition using SiH₄ and TiCl₄ as the precursors. The phase structure of the thin films was identified by XRD. The surface morphology of the thin films was observed by FESEM. The sheet resistance and optical behaviors of the thin films were measured by the four point resistivity test system and FTIR spectrometer, respectively. Titanium disilicide (TiSi₂) thin films with the face-centered orthorhombic structure are formed. The suitable formation temperature of the TiSi₂ crystalline phase is about 710 °C. The formation of TiSi₂ crystalline phase is dependent on the thickness of thin films and a quantity of the crystalline phase of TiSi₂ in the thin film is directly related to mole ratio of SiH₄/TiCl₄. The sheet resistance of the TiSi₂ thin films is dependent on the formation of the TiSi₂ crystalline phase. With the mole ratio of SiH₄/TiCl₄ of 3, the lowest sheet resistance (0.7 Ω/□) of titanium silicide thin film is formed at 710 °C. The maximum reflectance of the TiSi₂ thin films is about 0.95 on the broad IR heat radiation. A related reaction mechanism was proposed.     

Optical properties and chemical bonding characteristics of amorphous SiNX:H thin films grown by the plasma enhanced chemical vapor deposition method

Amorphous silicon nitride (SiN_X:H) thin films grown by the plasma enhanced chemical vapor deposition (PECVD) method are presently the most important antireflection coatings for crystalline silicon solar cells. In this work, we investigated the optical properties and chemical bonding characteristics of the amorphous SiN_X:H thin films deposited by PECVD. Silane (SiH₄) and ammonia (NH₃) were used as the reactive precursors. The dependence of the growth rate and refractive index of the SiN_X:H thin films on the SiH₄/NH₃ gas flow ratio was studied. The chemical bonding characteristics and the surface morphologies of the SiN_X:H thin films were studied using the Fourier transform infrared spectroscopy and atomic force microscopy, respectively. We also investigated the effect of rapid thermal processing on the optical properties and surface morphologies of the SiN_X:H thin films. It was found that the rapid thermal processing resulted in a decrease in the thickness, increase in the refractive index, and coarser surfaces for the SiN_X:H thin films.     

Crystallization of bismuth titanate and bismuth silicate grown as thin films by atomic layer deposition

Bismuth silicate and bismuth titanate thin films were deposited by atomic layer deposition (ALD). A novel approach with pulsing of two Bi-precursors was studied to control the Si/Bi atomic ratio in bismuth silicate thin films. The crystallization of compounds formed in the Bi₂O₃–SiO₂ and Bi₂O₃–TiO₂ systems was investigated. Control of the stoichiometry of Bi–Si–O thin films was studied when deposited on Si(1 0 0) and crystallization was studied for films on sapphire and MgO-, ZrO₂- and YSZ-buffered Si(1 0 0). The Bi–Ti–O thin films were deposited on Si(1 0 0) substrate. Both Bi–Si–O and Bi–Ti–O thin films were amorphous after deposition. Highly a-axis oriented Bi₂SiO₅ thin films were obtained when the Bi–Si–O thin films deposited on MgO-buffered Si(1 0 0) were annealed at 800 °C in nitrogen. The full-width half-maximum values for 200 peak were also studied. An excess of bismuth was found to improve the crystallization of Bi–Ti–O thin films and the best crystallinity was observed with Ti/Bi atomic ratio of 0.28 for films annealed at nitrogen at 1000 °C. Roughness of the thin films as well as the concentration depth distribution were also examined.     

Ablation of CdTe with 100 µs Nd:YAG laser pulses: dependence on target preparation method

The results of experimental studies of the ablation of CdTe with a pulsed Nd:YAG laser (wavelength 1064 nm) performed with 100 µs pulses and repetition time of 35 Hz are presented for the pulse energy range from 0.13 to 0.25 J. The main goal is to elucidate the dependence of the ablation process on the target preparation method. The investigation of the vapour stream intensity and chemical composition and their evolution with time are performed with a quadrupole mass spectrometer synchronized with the laser pulses. These studies are performed for three kinds of targets: a target made of CdTe bulk crystal (BC target), a target made of CdTe fine powder pressed under the pressure of 700 atm (PP target), and a target made of loose CdTe powder (N‐PP target). The applicability of these targets for obtaining high quality CdTe thin films is determined. The best chemical composition of the vapour stream can be obtained with the BC target. A major drawback of this target is the energetic threshold for ablation with Nd:YAG laser and resulting delay in the ablation process above the threshold. The advantage of powder targets over BC target is the lack of any ablation threshold or delay. Weaker angular dependence of the particle emission (associated with the surface roughness), if confirmed in further experiments, can be the most important advantage of PP and N‐PP targets. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of temperature on the microcrystalline structure of thermally evaporated Sb2S3 thin films

Thin films of antimony trisulfide (Sb₂S₃) were prepared by thermal evaporation under vacuum (p=5×10^–5 torr) on glass substrates maintained at various temperatures between 293 K and 523 K. Their microstructural properties have obtained by transmission electron microscopy (TEM). The electron diffraction analysis showed the occurrence of amorphous to polycrystalline transition in the films deposited at higher temperature of substrates (523 K). The polycrystalline thin films were found to have an orthorhombic structure. The interplanar distances and unit‐cell parameters were determined by high‐resolution transmission electron microscopy (HRTEM) and compared with the standard values for Sb₂S₃. The surface morphology of Sb₂S₃ thin films was investigated by scanning electron microscopy (SEM). The optical transmission spectra at normal incidence of Sb₂S₃ thin films have been measured in the spectral range of 400–1400 nm. The analysis of the absorption spectra revealed indirect energy gaps, characterizing of amorphous films, while the polycrystalline films exhibited direct energy gap. From the photon energy dependence of absorption coefficient, the optical band gap energy, E_g, were calculated for each thin films. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Properties of Sm‐doped CaNb2O6 thin films deposited by radio‐frequency magnetron sputtering

Sm‐doped CaNb₂O₆ (CaNb₂O₆:Sm) phosphor thin films were prepared by radio‐frequency magnetron sputtering on sapphire substrates. The thin films were grown at several growth temperatures and subsequently annealed at 800 °C in air. The crystallinity, surface morphology, optical transmittance, and photoluminescence of the thin films were investigated by X‐ray diffraction, scanning electron microscopy, ultraviolet‐visible spectrophotometry, and fluorescence spectrophotometry, respectively. All of the thin films showed a main red emission radiated by the transition from the ⁴G_5/2 excited state to the ⁶H_9/2 ground state of the Sm³⁺ ions and several weak bands under ultraviolet excitation with a 279 nm wavelength. The optimum growth temperature for depositing the high‐quality CaNb₂O₆:Sm thin films, which was determined from the luminescence intensity, was found to be 400 °C, where the thin film exhibited an orthorhombic structure with a thickness of 370 nm, an average grain size of 220 nm, a band gap energy of 3.99 eV, and an average optical transmittance of 85.9%. These results indicate that the growth temperature plays an important role in controlling the emission intensity and optical band gap energy of CaNb₂O₆:Sm thin films.     

Electrodeposited and selenized CIGS thin films for solar cells

Cu(In,Ga)Se₂ polycrystalline thin films were deposited adopting the potentiostatic electrochemical method on Mo/soda lime glass substrate. All the as-deposited Cu(In,Ga)Se₂ thin films were annealed in a selenium atmosphere at 550 °C for 1 h to improve the film crystalline properties. The selenized CIGS thin films were characterized by energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and scanning electron microscopy (SEM).The results indicate Cu(In,Ga)Se₂ thin films have single chalcopyrite structure and the grain size varies from 0.8 to 2.5 μm.