Preparation of Cu（In,Ga）Se2 Thin Film Solar Cells by Selenization of Metallic Precursors in an Ar Atmosphere

Cu（In, Ga）Se2 thin films are deposited on Mo-coated glass substrates by Se vapour selenization of sputtered metallic precursors in the atmosphere of Ar gas flow under a pressure of about 10 Pa. The in situ heat treatment of as-grown precursor leads to the formation of a better alloy. During selenization, the growth of CuInSe2 phase preferably proceeds through Se-poor phases as CuSe and InSe at relatively low substrate temperature of 250℃, due to the absence of In2Se3 at intermediate stage at low reactor pressure. Subsequently, the Cu（In,Ga）Se2 phase is produced by the reactive diffusion of CuInSe2 with a Se-poor GaSe phase at high temperature of up to 560℃. The final film exhibits smooth surface and large grain size. The absorber is used to fabricate a glass/Mo/Cu（In, Ga）Se2/CdS/ZnO cell with the total-area efficiency of about 7%. The low open-circuit voltage value of the cell fabricated should result from the nonuniform distribution of In and Ga in the absorber, due to the diffusion-controlled reaction during the phase formation. The films, as well as devices, are characterized.     

Phase analysis of TaN/Ta barrier layers in sub-micrometer trench structures for Cu interconnects

The resistance behavior of TaN/Ta diffusion barrier bilayers has been investigated. The dependence of the Ta-phase on the TaN layer thickness was examined by means of X-ray micro-diffraction and resistivity measurements. Furthermore, the influence of the geometry of a damascene trench structure on the Ta-phase of the deposited TaN/Ta barrier bilayers has been studied and compared to the results obtained with blanket wafers. The influence of the Ta-phase on the via resistance of Cu interconnects is discussed.     

Mo Back Contact for Flexible Polyimide Substrate Cu（In,Ga）Se2 Thin-Film Solar Cells

A dc magnetic sputtering process is applied to growth of a Mo back. contact layer onto the flexible polyimide （PI） and rigid soda-lime glass （SLC） substrates. The structural and electrical properties of the Mo layer coated on the two kinds of substrates are investigated by x-ray diffraction （XRD） and Hall effect measurements. The results show that the Mo layer on SLG indicate more better crystal quality and lower resistivity than that on the PI sheets. In contrast to the SLG substrate, the resistivity of the Mo layer on PI is increased by the vacuum annealing process at the substrate temperature of 450℃ under Se atmosphere, which is attributed to the cracked Mo layer induced by the mismatch of the coefficient of thermal expansion between PI and Mo material. The Cu（In,Ga）Se2 （CIGS） solar cells based on the PI and SLO substrates show the best conversion efficiencies of 8.16% and 10.98% （active area, 0.2cm^2）, respectively. The cell efficiency of flexible CIGS solar cells on PI is limited by its relatively lower fill factor caused by the Mo back contact.     

Flexible Cu（In,Ga）Se2 Thin-Film Solar Cells on Polyimide Substrate by Low-Temperature Deposition Process

The electrical and structural properties of polycrystalline Cu（In, Ga）Se2 films grown on polyimide （PI） substrates below 400℃ via one-stage and three-stage co-evaporation process have been investigated by x-ray diffraction spectra （XRD）, scanning electron microscopy （SEM） and Hall effect measurement. As shown by XRD spectra, the stoichiometric CIGS films obtained by one-stage process exhibit the characteristic diffraction peaks of the （In0.68Ga0.32）2Se3 and Cu（In0.7Ga0.3）2Se. It is also found that the film structures indicate more columnar and compact than the three-stage process films from SEM images. The stoichiometric CIGS films obtained by three-stage process exhibit the coexistence of the secondary phase of （In0.68Ga0.32）2Se3, Cu2-xSe and Cu（In0.7Ga0.3）2Se. High net carrier concentration and sheet conductivity are also observed for this kind of film, related to the presence of Cu2-xSe phase. As a result, when the CIGS film growth temperature is below 400℃, the three-stage process is inefficient for solar cells. By using the one-stage co-evaporation process, the flexible CIGS solar cell on a PI substrate with the best conversion efficiency of 6.38% is demonstrated （active area 0.16cm^2）.     

Systematic theoretical investigations for contribution of lattice constraint to novel atomic arrangements in alloy semiconductor thin films

The atomic arrangements in zinc blende structured GaN_xAs_1−x thin films coherently grown on V-grooved substrates are theoretically investigated using empirical interatomic potentials and Monte Carlo simulation. The resultant atomic arrangements in GaN_xAs_1−x strongly depend on concentration x and substrate lattice parameter a_sub. Surface segregation of As or N is mainly found in GaN_xAs_1−x with large lattice mismatch to the substrate. On the other hand, the novel atomic arrangements such as layered segregation or ordered structure are found in GaN_xAs_1−x at the specific region such as (x, a_sub) = (0.5, 5.3), (0.3, 5.3), and (0.3, 5.1). This specific region corresponds to that with negative excess energy and with sufficient N and As atoms remaining in thin film layers even after their surface segregation. The formation of the novel atomic arrangements is discussed in terms of bond lengths in the surface layers. These results suggest that various novel atomic arrangements in alloy semiconductor thin films appear depending on x and a_sub which control degree of lattice constraint.     

Substrate and orientation influence on electrical properties of sputtered La-doped PZT thin films

Pb_1−2y/3La_yZr_xTi_1−xO₃ (PLZT) thin films have been prepared “in situ” by multi-target sputtering on Silicon, LaAlO₃ (LAO) and MgO substrates covered with a Pt bottom electrode. The purpose was to grow tetragonal PLZT films (Zr/Ti = 28/72 with different La contents) on these various substrates and to compare their electrical properties. To this aim, Pt was first deposited on the three different substrates to get (1 1 1)Pt/Si, (1 1 1)Pt/LAO and (2 0 0)Pt/MgO. Then PLZT was deposited in a same run on these three kinds of substrates and the influence of La contents and film orientation on electrical properties was investigated. The La content was varied from y = 0 to y = 32 in order to explore the phase transition between ferroelectric and paraelectric phases as a function of the substrate. For large amount of Lanthanum, relaxor behavior has been observed and studied.     

Microstructure and mechanical properties of CrN films fabricated by high power pulsed magnetron discharge plasma immersion ion implantation and deposition

CrN films with strong adhesion with the substrate have been fabricated on Ti6Al4V alloy using novel plasma immersion ion implantation and deposition (PIII&D) based on high power pulsed magnetron sputtering (HPPMS). A macro-particle free chromium plasma is generated by HPPMS while the samples are subjected to high voltage pulses to conduct PIII&D. The CrN coatings have a dense columnar structure and low surface roughness. The grains in the films have the face-center cubic (fcc) structure with the (2 0 0) preferred orientation. An excellent adhesion is achieved with a critical load up to 74.7 N. An implantation voltage of 18 kV yields a hardness of 18 GPa and better wear resistance and a low friction coefficient of 0.48 are achieved.     

Growth of High-Quality Decagonal Al-Cu-Co Quasicrystals from Ternary Melt

By changing the initial elements, we obtain high-quality samples of Al-Cu-Co decagonal quasicrystals with a wide range of composition. The sizes of the samples are typically several centimetres in length and 2-3 mm in diameter. These samples are identified to be decagonal single grains by powder x-ray diffraction method, and the composition is homogeneous confirmed by EDX and chemical method.     

Microstructure, porosity and roughness of RF sputtered oxide thin films: Characterization and modelization

Spinel CoMnFeO₄ thin films are stable materials useful to study the influence of radio-frequency (RF) sputtering experimental conditions on the microstructure of oxide films. It has been demonstrated by various techniques such as electronic and atomic force microscopy (AFM), gas adsorption techniques and ellipsometry, that films prepared with 0.5 Pa sputtering argon pressure and 5 cm target-substrate distance are very dense. On the other hand, the samples obtained under higher pressure and/or longer distances are microporous with a mean pore size generally lower than 2 nm. The specific surface areas of such films reach about 75 m²/g.According to the simple model proposed, the films are made of three layers. From the bottom to the top of the film, the first one at the interface with the substrate is 100% dense. The second layer is made of cylindrical rods set up according to a compact plane. Its porosity is due to the lattice interstices. Hemispheric domes covering each rod make up the third layer, which displays a degree of roughness related to the shape and the hexagonal arrangement of the domes. The surface enhancement factor (SEF), the porosity and roughness, calculated from the model, are in corroboration with the experimental values. The porosity factor is however slightly underestimated by the model for very porous samples.     

Effects of Substrate Temperature and Nitrogen Pressure on Growth of AIN Films by Pulsed Laser Deposition

Highly oriented aluminium nitride （AIN） films are grown on p-Si （100） substrates by pulsed laser deposition, and their characteristics of structure and composition are studied by x-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. The results show that the deposited films exhibit good crystalline properties with a sharp x-ray diffraction peak at 2θ= 33.15 ° corresponding to AIN h （100） crystalline orientation. The influences of substrate temperature and ambient nitrogen （N2） pressure on the crystallinity of A1N films are remarkable. At room temperature, when the ambient N2 pressure arises from 5 × 10^-6 Pa to 5 Pa, the crystallinity of the film becomes better. When the substrate temperature is 600℃, the film has the best crystallinity at 0.05 Pa. Furthermore, the effects of substrate temperature and ambient N2 pressure on the combination of A1-N bonds and surface morphology of AIN films are also studied.     

Natural variability in the surface roughness of combinatorial libraries of materials

Using a conventional method for the fabrication of solid-state combinatorial libraries, we have produced the binary libraries Fe_1−xCr_x and Mo_1−xSn_x (0 < x < 1) and found that their surface roughness is highly dependent on chemical composition. Roughness enhancements of up to 20-fold have been observed on the nanometer scale and were manifested in the boundaries between structurally dissimilar phases. It is anticipated that this is a common occurrence in thin-film libraries of metals and an obstacle in separating the influence of roughness and composition on the performance of library materials in biomaterial studies.     

High-throughput synthesis and characterization of Mg1−xCaxO films as a lattice and valence-matched gate dielectric for ZnO based field effect transistors

Using composition-spread technique, we have grown metastable Mg_1−xCa_xO solid solution films on ZnO layers by pulsed laser deposition. All the films exhibited (1 1 1) oriented cubic phase. Despite a large miscibility gap, no phase separation took place at growth temperatures up to 700 °C, whereas an optimal growth temperature was found at 400 °C in terms of the crystallinity. The composition-spread films were characterized by X-ray diffraction mapping technique. Both lattice parameters and diffraction intensity increased with increasing the CaO composition. The present isovalent heterointerfaces realized the perfect lattice-matching by properly adjusting the CaO composition, leading to particular interest for ZnO based field effect transistors.     

Production of biologically inert Teflon thin layers on the surface of allergenic metal objects by pulsed laser deposition technology

Allergic-type diseases are current nowadays, and they are frequently caused by certain metals. We demonstrated that the metal objects can be covered by Teflon protective thin layers using a pulsed laser deposition procedure. An ArF excimer laser beam was focused onto the surface of pressed PTFE powder pellets; the applied fluences were 7.5–7.7 J/cm². Teflon films were deposited on fourteen-carat gold, silver and titanium plates. The number of ablating pulses was 10000. Post-annealing of the films was carried out in atmospheric air at oven temperatures between 320 and 500 °C. The thickness of the thin layers was around 5 μm. The prepared films were granular without heat treatment or after annealing at a temperature below 340 °C. At 360 °C a crystalline, contiguous, smooth, very compact and pinhole-free thin layer was produced; a melted and re-solidified morphology was observed above 420 °C. The adhesion strength between the Teflon films and the metal substrates was determined. This could exceed 1–4 MPa depending on the treatment temperature. It was proved that the prepared Teflon layers can be suitable for prevention of contact between the human body and allergen metals and so for avoidance of metal allergy. Received: 12 June 2002 / Accepted: 13 June 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. E-mail: bhopp@physx.u-szeged.hu     

Ordered InAs Quantum Dots with Controllable Periods Grown on Stripe-Patterned GaAs Substrates

GaAs （001） substrates are patterned by electron beam lithography and wet chemical etching to control the nucleation of lnAs quantum dots （QDs）. InAs dots are grown on the stripe-patterned substrates by solid source molecular beam epitaxy. A thick buffer layer is deposited on the strip pattern before the deposition of InAs. To enhance the surface diffusion length of the In atoms, InAs is deposited with low growth rate and low As pressure. The AFM images show that distinct one-dimensionally ordered InAs QDs with homogeneous size distribution are created, and the QDs preferentiMly nucleate along the trench. With the increasing amount of deposited InAs and the spacing of the trenches, a number of QDs are formed beside the trenches. The distribution of additional QDs is long-range ordered, always along the trenchs rather than across the spacing regions.     

Structural and optical properties of sputtered ZnO thin films

Zinc oxide (ZnO) and aluminium-doped zinc oxide (ZnO:Al) thin films were prepared by RF diode sputtering at varying deposition conditions. The effects of negative bias voltage and RF power on structural and optical properties were investigated. X-ray diffraction measurements (XRD) confirmed that both un-doped and Al-doped ZnO films are polycrystalline and have hexagonal wurtzite structure. The preferential 〈0 0 1〉 orientation and surface roughness evaluated by AFM measurements showed dependence on applied bias voltage and RF power. The sputtered ZnO and ZnO:Al films had high optical transmittance (>90%) in the wavelength range of 400-800 nm, which was not influenced by bias voltage and RF power. ZnO:Al were conductive and highly transparent. Optical band gap of un-doped and Al-doped ZnO thin films depended on negative bias and RF power and in both cases showed tendency to narrowing.     

Epitaxial growth of yttria-stabilised zirconia buffer layers on X-cut LiNbO3 for superconducting electrodes

We report on the epitaxial growth of yttria-stabilised zirconia (YSZ) buffer layers on X-cut LiNbO₃ (LNO) single crystals by pulsed laser deposition. Despite the low chemical stability of the substrates at high temperature, high quality fully reproducible films were obtained over a relatively broad range of processing conditions. The films were (00h) out-of-plane single oriented and the in-plane edge of the YSZ unit cell was aligned with the polar axis of the LNO. However, the YSZ deposition also promoted the formation of the compound LiNb₃O₈. This compound is epitaxial and located at the interface. The homogeneous YSZ film presents a uniform surface, free of outgrowths and with a low roughness. These characteristics are suitable for the epitaxial growth of other oxides, as has been demonstrated with the preparation of YBa₂Cu₃O₇/CeO₂/YSZ/LNO heterostructures. The superconducting YBa₂Cu₃O₇ films were epitaxial, with the c axis perpendicular to the surface and single in-plane orientation, and presented good transport properties (critical temperatures around 86 K and critical current densities close to 10⁶ A/cm² at 77 K). Received: 5 April 2001 / Accepted: 30 July 2001 / Published online: 30 October 2001     

Raman spectroscopic studies of PbxLa1−xTi1−x/4O3 thin films grown on Si substrates by RF magnetron sputtering

A systematic spectroscopic investigation of Pb_xLa_1−xTi_1−x/4O₃ (PLT) thin films grown on PbO_x/Pt/Ti/SiO₂/Si substrate by RF magnetron sputtering was performed by using confocal Raman spectroscopy. Influence of the growth condition modification including different growth temperatures, with various buffer layer thickness, and post-annealing treatments were analyzed with taking advantages of the corresponding Raman spectral band variation in the respective process. Significant change in the spectral bands occurred with the alteration of the growth condition, and the related mechanisms were discussed after spectral deconvolution, providing reliable information about the direction for film growth.     

Effect of a LaSrCoO3 buffer layer on Pb1 − xLaxTi1 − x/4O3 films studied by polarized Raman spectroscopy

A confocal Raman investigation of Pb_1 − xLa_xTi_1 − x/4O₃ (PLT) thin films grown by RF magnetron sputtering on PbO_x/Pt/Ti/SiO₂/Si substrates with an intermediate LaSrCoO₃ (LSCO) layer was performed. The influence of the LaSrCoO₃ buffer layer was analyzed taking advantage of the observed Raman spectral band variation, which varied according to different manufacturing procedures. In the presence of a LSCO layer, the A1(1TO) Raman mode, which was indicative of tetragonal distortion, was pronouncedly enhanced, and a slight deviation from the (0 0 1) plane of the film was observed from the angular dependence of the polarized Raman spectral intensity. Furthermore, the spectral band variation as well as the residual stress along the in-depth direction was measured in the film from cross-sectional spectral line scans. This latter measurement showed a relaxation of the lattice mismatch in the presence of LSCO and PbO layers.     

Epitaxial growth La0.67Ca0.33MnO3 thin film by radio frequency sputtering method

Perfect epitaxial growth of La_0.67Ca_0.33MnO₃ (LCMO) thin film has been achieved on (1 0 0) LaAlO₃ (LAO) single crystal substrate by radio frequency sputtering method. X-ray diffraction (XRD) and electron diffraction analysis indicates that La_0.67Ca_0.33MnO₃ film grows epitaxially on LaAlO₃ along [1 0 0] direction of the substrate. The resistivity variation with temperature of the film shows a sharp metal to semiconductor transition peak around 253 K, which is close to that of the target. The magnetoresistance (MR) also reveals high quality epitaxy film characteristic at low temperatures and near the metal to semiconductor transition temperature.     

Crystallization and surface morphology evolution of erbium fluoride films on different substrates

Erbium fluoride (ErF₃) films were thermally deposited on Ge(1 1 1), Si(0 0 1) and copper mesh grid with different substrate temperature. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and morphology of the films. The structure of ErF₃ films deposited on germanium and silicon changed from amorphous to crystalline with increasing the substrate temperature, while the crystallization temperature of the films on silicon is higher than that of on germanium. The infrared optical properties of the films change greatly with the evolution of crystal structure. It is also found that the morphology of ErF₃ film on Ge(1 1 1) at 200 °C is modulated by the stress between the substrate and film. The SEM and TEM results confirmed that the ErF₃ films on copper mesh grid were crystalline even at 100 °C. Interestingly, the ErF₃ films show flower-like surface morphology when deposited on copper mesh at 200 °C. The crystallization temperature (T_c) of ErF₃ films on the three substrates has the relation which is which is induced by the wetting angle of ErF₃ films on different substrates.