Surface Cu depletion of Cu(In,Ga)Se2 films: An investigation by hard X-ray photoelectron spectroscopy

The origin of surface Cu depletion of polycrystalline chalcopyrite thin films and its consequences for the physics of related solar cells have been discussed for the past 15 years. In order to shed light on the composition and thickness of this Cu-depleted surface layer, depth-dependent compositional analysis by hard X-ray photoelectron spectroscopy was performed. The data from Cu-poor grown Cu(In,Ga)Se₂ samples point to a surface layer in the sub-nanometer regime, which is completely depleted of Cu. This result supports the surface reconstruction model proposed by first-principles calculations by other authors. Analysis of the surface morphology of the investigated samples confirms the conjunction of Cu depletion and faceting of the surface. Theoretical considerations show that the apparent surface concentration ratio of [Cu]/([In] + [Ga]) = 1/3 found by conventional photoelectron spectroscopy studies can be explained by the surface reconstruction model.     

Microstructural characterizations of magnetron sputtered Ti films on glass substrate

Magnetron sputtered Ti thin films deposited on glass substrates under varying deposition parameters were characterized by X-Ray Diffraction, Scanning Electron Microscopy and Atomic Force Microscopy. The textures of the Ti films characterized by X-ray diffraction revealed the initial (1 0 0) preferred orientation but it transformed in to (0 0 2) and (1 0 1) orientation with increase in sputtering power and substrate temperature, respectively. The preferred orientations of (0 0 2) and (1 0 1) were observed for the films deposited with the sputtering pressure of 5 mTorr and 20 mTorr, respectively. The average surface roughness of the Ti films showed an increasing trend with power, pressure, and temperature from the Atomic Force Microscopy analysis. The dense film morphology was observed in the Scanning Electron Microcopy images of Ti thin films deposited with higher substrate temperature (500 °C). X-ray diffraction analysis revealed that the grain size of the Ti thin films exhibits an increasing trend with varying deposition parameters.     

Structure of martensite in Ti-rich Ti–Ni–Cu thin films annealed at different temperatures

After annealing at different temperatures, there are different types of precipitates in Ti-rich Ti–Ni–Cu thin films: plate-like Guinier–Preston (GP) zones, Ti₂Cu precipitates and spherical Ti₂Ni precipitates. The (0 1 1) compound twins and (1 1 1) type I twins are dominant in Ti-rich Ti–Ni–Cu thin films annealed at different temperatures, which suggests that the precipitates do not change the twinning modes of the B19 martensite. However, the amount of the (0 1 1) compound twin increases with increasing annealing temperature due to its small twinning shear. In thin films with GP zones or Ti₂Ni precipitates, the amount of martensite with a single-pair morphology is less than that in thin films without precipitates. And in thin film with Ti₂Cu + Ti₂Ni precipitates, hardly any martensite with a single-pair morphology is observed. For the different types of precipitates at the different annealing temperatures, the obstacle of the precipitates to the growth of the B19 martensite plate also varies. The GP zones slightly hinder the growth in the width of martensite, resulting in wavy twin boundaries at the martensite variant tip. The Ti₂Cu precipitates can change both the width and the direction of the martensite plates. Ti₂Ni precipitates also significantly disturb or impede the growth of the martensite variants. These effects lead to a decrease in the maximum shape recoverable strain with increasing annealing temperature.     

Texture transformations in Ag thin films

A thickness-dependent texture transformation during annealing of initially (1 1 1) fiber-textured face-centered-cubic metal thin films is phenomenologically well known: sufficiently thin films retain the (1 1 1) texture, while sufficiently thick films transform to a (1 0 0) fiber texture. This transformation has been explained based on minimization of strain and interface energies, but recent work calls into question the roles of both of these driving forces. A high-throughput experimental method for the study of this texture transformation has been developed and applied to thin silver films with and without Ti adhesion layers. More than 150 individual samples spanning a range of thicknesses and interface conditions were prepared in a single deposition run. The texture evolution of these samples was characterized using X-ray diffraction as a function of time and temperature during annealing. The transformation proceeds despite the fact that the stresses are too low according to the strain/interface energy model. For films with Ti adhesion layers, the transformation kinetics and extent of transformation depend on the film thickness in a surprising way with intermediate thickness films showing initially fast transformations and stable mixed textures, while thicker films show an incubation time but transform fully. The results are consistent with reduction in defect energy (e.g. dislocations or point defects) as the driving force for secondary grain growth in an environment in which only (1 0 0) recrystallization nuclei can form. The driving force increases with film thickness so the nonmonotonic variation in transformation rate implies that the density of (1 0 0) nuclei decreases with thickness.     

On the effect of grain boundary segregation on creep and creep rupture

The present work investigates the effect of grain boundary chemistry and crystallography on creep and on creep damage accumulation in Cu–0.008 wt.% Bi and Cu–0.92 wt.% Sb at stresses ranging from 10 to 20 MPa and temperatures between 773 and 873 K. Small additions of Bi and Sb significantly reduce the rupture strain and rupture time during creep of Cu. High stress exponents (Cu–Bi) and high apparent activation energies for creep (Cu–Bi and Cu–Sb) are obtained. Sb promotes creep cavitation on random high-angle grain boundaries. Bi, on the other hand, causes brittle failure when small crack-like cavities cause decohesion. Both elements suppress dynamic recrystallization, which occurs during creep of Cu at high stresses and temperatures.     

Structural,electrical and mechanical characterization of magnetron-sputtered V–Ge–C thin films

V₂GeC MAX-phase thin films were deposited by DC magnetron sputter epitaxy in the temperature range 450–850 °C. The MAX-phase nucleates directly on (0 0 0 l)-oriented sapphire-wafer substrates without the need for a seed layer. The films contain, however, a small fraction of binary vanadium carbide (VC_x) inclusions. X-ray diffraction analysis furthermore shows that these inclusions partly consist of the ordered superstructure V₈C₇. The amount of Ge in the films decreases at higher temperatures, which can be attributed to Ge evaporation. At temperatures below 450 °C the films consist of polycrystalline Ge and an X-ray amorphous carbide phase attributed to VC_x or V₂C. No MAX-phase was observed in this temperature region. The electrical and mechanical properties of the films were characterized.     

Structural and optical properties of epitaxial ZnO thin films on 4H–SiC (0 0 0 1) substrates prepared by pulsed laser deposition

Epitaxially grown ZnO thin films on 4H–SiC (0 0 0 1) substrates were prepared by using a pulsed laser deposition (PLD) technique at various substrate temperatures from room temperature to 600 °C. The crystallinity, in-plane relationship, surface morphology and optical properties of the ZnO films were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL) measurements, respectively. XRD analysis showed that highly c-axis oriented ZnO films were grown epitaxially on 4H–SiC (0 0 0 1) with no lattice rotation at all substrate temperatures, unlike on other hexagonal-structured substrates, due to the very small lattice mismatch between ZnO and 4H–SiC of ～5.49%. Further characterization showed that the substrate temperature has a great influence on the properties of the ZnO films on 4H–SiC substrates. The crystalline quality of the films was improved, and surfaces became denser and smoother as the substrate temperature increased. The temperature-dependent PL measurements revealed the strong near-band-edge (NBE) ultraviolet (UV) emission and the weak deep-level (DL) blue-green band emission at a substrate temperature of 400 °C.     

Preparation and characterization of Ca0.18Na0.32Bi0.50TiO3 ferroelectric thin films by metalorganic solution deposition

Ca_0.18Na_0.32Bi_0.50TiO₃ (CNBT) ferroelectric thin films were prepared by metalorganic solution deposition on silicon substrate and annealed at different temperatures. The morphology and structure of the films were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The crystal structure of Ca-doped Na_0.50Bi_0.50TiO₃ films shows no obvious lattice distortion compared with that of un-doped one. The optimal heat treatment process for CNBT films were determined to be high-temperature drying at 400 °C for no less than 15 min followed by annealing at 600 °C for 5 min, which leads to the formation of compact films with uniform grains of 30–50 nm. Ferroelectric property measurement shows that the remanent polarization of CNBT films is 18 times higher than that of un-doped Na_0.50Bi_0.50TiO₃ (NBT) thin films.     

Effect of particle/matrix interfacial character on the high-temperature deformation and recrystallization behavior of Cu with dispersed Fe particles

The effect of particle/matrix interfacial character on the high-temperature deformation and recrystallization behavior of Cu was systematically investigated at various temperatures from 723 to 973 K and at true strain rates between 4.1 × 10⁻⁴ and 3.2 × 10⁻² s⁻¹. Cu with dispersed coherent γ-Fe precipitates (Cu–γ-Fe alloy) displayed lower yield stresses and higher flow stresses than Cu containing incoherent α-Fe precipitates (Cu–α-Fe alloy) under all testing conditions. Dynamic recrystallization (DRX) took place more easily in the Cu–α-Fe alloy than in the Cu–γ-Fe alloy. Although DRX was strongly impeded by the presence of the coherent precipitates at low to medium strains, the recrystallized regions gradually spread, accompanied by transformation of the coherent precipitates into incoherent ones. Such a large difference in the deformation and DRX behaviors depending on the particle/matrix interfacial character is attributed to the stronger interaction between dislocations and the coherent particles.     

Elaboration and characterization of nanocrystalline TiO2 thin films prepared by sol–gel dip-coating

Nanocrystalline TiO₂ thin films were deposited on a ITO coated glass substrate by sol–gel dip coating technique, the layers undergo a heat treatment at temperatures varying from 300 to 450 °C. The structural, morphological and optical characterizations of the as deposited and annealed films were carried out using X-ray diffraction (XRD), Raman spectroscopy, Atomic Force Microscopy (AFM), visible, (Fourier-Transform) infrared and ultraviolet spectroscopy, Fluorescence and spectroscopic ellipsometry. The results indicate that an anatase phase structure TiO₂ thin film with nanocrystallite size of about 15 nm can be obtained at the heat treatment temperature of 350 °C or above, that is to say, at the heat treatment temperature below 300 °C, the thin films grow in amorphous phase; while the heat treatment temperature is increased up to 400 °C or above, the thin film develops a crystalline phase corresponding to the titanium oxide anatase phase. We have accurately determined the layer thickness, refractive index and extinction coefficient of the TiO₂ thin films by the ellipsometric analysis. The optical gap decreases from 3.9 to 3.5 eV when the annealing temperature increases. Photocatalytic activity of the TiO₂ films was studied by monitoring the degradation of aqueous methylene blue under UV light irradiation and was observed that films annealed above 350 °C had good photocatalytic activity which is explained as due to the structural and morphological properties of the films.     

Rapid phase transformation kinetics on a nanoscale: Studies of the α → β transformation in pure,nanocrystalline Ti using the nanosecond dynamic transmission electron microscope

Using the unique capabilities and high time resolution of dynamic transmission electron microscopy (DTEM), the fast kinetics of α → β-phase transformation in nanocrystalline Ti films were investigated using single-shot electron diffraction and bright-field TEM images. From quantitative analysis of the diffraction patterns, the transformation rates were determined for temperatures between transition start (1155 K) and melt temperature (1943 K). The experimental data were summarized in a time–temperature-transformation (TTT) curve with nanosecond time resolution. Theoretical TTT curves were calculated using analytical models for isothermal martensite and available thermodynamic data. Above 1300 K, there is excellent agreement between the experiment and the discrete–obstacle interaction model, suggesting that the nucleation rate and thermally assisted motion of the martensite interface are controlled by interface–solute atom interactions. However, theory predicts much slower transformation rates near the transition temperature than experiment. Experimental data fits using the Pati–Cohen model suggests that an increase in autocatalytic nucleation may partially account for the fast transformation rates at lower temperatures.     

Electrical,structural, photoluminescence and optical properties of p-type conducting,antimony-doped SnO2 thin films

P-type transparent conducting antimony-doped tin oxide (ATO) films were successfully fabricated on quartz glass substrates by radio-frequency magnetron sputtering using a 20 mol.% Sb-doped SnO₂ ceramic target. The deposited films were annealed at different temperatures for different durations. Hall effect results indicated that 973 K was the optimum annealing temperature to get p-type ATO films with the highest hole concentration (5.83 × 10¹⁹ cm^–3). X-ray diffraction studies indicated that the preferred (1 0 1) orientation favored the formation of p-type conducting films. Photoluminescence spectra showed an intense UV luminescence peak near 362 nm resulting from the band-edge exciton transition observed for p-type ATO films. UV–visible transmission spectra showed that p-type ATO films had high transparence. In addition, p-type conductivity was also confirmed by the non-linear characteristics of a p-type ATO/n-type ATO structure; the diode structure has an optical transmission of ～60–85% in the visible light range.     

Structural,electrical and optical properties of p-type transparent conducting SnO2:Al film derived from thermal diffusion of Al/SnO2/Al multilayer thin films

Highly transparent, p-type conducting SnO₂:Al films derived from thermal diffusion of a sandwich structure Al/SnO₂/Al multilayer thin films deposited on quartz substrate have been prepared by direct current and radio-frequency magnetron sputtering using Al and SnO₂ targets. The deposited films were annealed at various temperatures for different durations. The effect of thermal diffusing temperature and time on the structural, electrical and optical performances of SnO₂:Al films has been studied. X-ray diffraction results show that all p-type conducting films possessed polycrystalline SnO₂ with tetragonal rutile structure. Hall-effect results indicate that 450 °C for 4 h were the optimum annealing parameters for p-type SnO₂:Al films, resulting in a relatively high hole concentration of 7.2 × 10¹⁸ cm^?3 and a low resistivity of 0.81 Ω cm. The transmission of the p-type SnO₂:Al films was above 80%.     

Synthesis of nanocrystalline magnesium diboride (MgB2) metallic superconductor by mechano-chemical reaction and post-annealing

MgB₂ is recently discovered superconducting compound with a record-breaking transition temperature (T_c = 39 K) for a conventional metallic superconductor. Nanocrystallinity can improve its electrical properties by strong pinning. In the present work we report the results of the synthesis of nanocrystalline MgB₂ superconducting compound by mechano-chemical reaction followed by post-annealing. The first stage of synthesis was carried out from elemental crystalline Mg and amorphous B powders by controlled mechanical alloying (CMA) in the magneto-mill Uni-Ball-Mill 5. X-ray diffraction studies reveal that the nucleation of small amount of MgB₂ is initiated after two-step milling for combined 100 h under protective helium gas. Further reaction to form MgB₂ is accelerated by subsequent annealing of the milled powder at various temperatures. X-ray diffraction shows formation of a well-developed nanocrystalline MgB₂ after annealing of the pre-nucleated powder at the 630–650 °C range for a few hours.     

Highly (1 0 0)-textured Pb(Zr0.52Ti0.48)O3 film derived from a modified sol–gel technique using inorganic zirconium precursor

Highly (1 0 0)-textured Pb(Zr_0.52Ti_0.48)O₃ films have been prepared on platinized silicon substrate by a modified sol–gel technique using inorganic zirconium precursor. The X-ray diffraction analysis on the crystallinity and texture evolution of sol–gel lead zirconate titanate (PZT) films revealed that the films were well crystallized to perovskite phase when annealed at 550 °C, and that highly (1 0 0) preferred orientation dominated in the PZT films after annealed at 650 °C. The (1 0 0)-oriented PZT film exhibited the remnant polarization of 26.3 μC/cm² and the coercive field of 100 kV/cm.     

Size-independent stresses in Al thin films thermally strained down to −100 °C

Size and temperature dependencies of thermal strains of {1 1 1} textured Al thin films were determined by in situ X-ray diffraction (XRD) in the temperature range of −100 to 350 °C. The experiments were performed on 50–2000 nm thick Al films sputter-deposited on oxidized silicon (1 0 0) substrates. The in-plane stresses were assessed by measuring the {3 3 1} lattice plane spacing at each temperature in steps of 25 °C during thermal cycling. At high temperatures, the films could only sustain small compressive stresses. The obtained stress–temperature evolutions show the well-known increase of flow stresses with decreasing film thickness for films thicker than 400 nm. However, for thinner films, the measured stress on cooling is independent of the film thickness. This lack of size effect is caused by the flow stresses in the thinnest films exceeding the maximum stress that can be applied to these samples using thermomechanical loading down to −100 °C. Thus, the measured stresses of ∼770 MPa in the thinnest film represent a lower limit for the actual flow stresses. The observed stresses are also discussed taking microstructural information and possible constraints on dislocation processes into account.     

Substrate heterostructure effects on interface composition,microstructure development and functional properties of PZT thin films

Platinum- and (La_0.8,Sr_0.2)MnO₃ (LSMO)-terminated silicon substrates were used for the liquid-phase deposition of Pb(Zr_0.52,Ti_0.48)O₃ (PZT) thin films. Different layer thicknesses ranging from 100 to 600 nm were processed by sequential coating. Characterization of the films involved X-ray diffraction, atomic force microscopy and X-ray photoelectron spectroscopy (XPS) combined with depth profiling to probe the interface composition. The films deposited on Pt exhibit an intermetallic layer, Pt_xPb, after annealing at 500 °C in air. This film has been used to establish the XPS signature of the intermetallic phase which consists of a negative shift of the peak position of Pt(4f) due the electron transfer from Pb to Pt. In all cases pure phase perovskite thin films were obtained after short annealing at 700 °C. XPS depth profiling shows unambiguously the existence of an intermetallic layer, Pt_xPb, of approximately 10 nm at the interface between Pt and PZT, while an interdiffusion layer of ～30 nm was observed between LSMO and PZT. The impacts of interfacial layers on microstructure development and functional properties translate in the formation of specific textures, i.e. a pronounced (1 1 1)-texture on Pt due to lattice matching between (1 1 1)-PZT and (1 1 1)-Pt_xPb, and a random film orientation on LSMO, and a substantial thickness dependence of the dielectric and ferroelectric properties, though specific behaviors were observed for the two different substrate heterostructures.     

Discrepancies in the morphology and physical properties of amorphous and crystalline sprayed lanthanum nickel oxide films

Amorphous LaNiO₃ (a-LNO) and crystalline LaNiO₃ (c-LNO) films were prepared by spraying an aqueous precursor solution of lanthanum and nickel chlorides on hot (450 °C) fused silica substrates followed by annealing at high temperatures (550–850 °C). Thermal analysis of a dried precursor indicated that a stable oxide phase is formed at 560 °C with no distinct crystallization peak. Scanning electron microscopy (SEM) powered with energy-dispersive X-ray spectroscopy (EDX) of as-sprayed films showed rough surfaces with particulate-like deposits and incomplete pyrolysis chloride composition. No chloride contents were detected in annealed films. X-ray diffraction showed that films annealed at 550 °C and 650 °C were a-LNO and those annealed at 750 °C and 850 °C were c-LNO. The c-LNO phase was indexed as a single-phase perovskite structure with (1 1 0) orientation. SEM/EDX showed that a-LNO films have rough surfaces and c-LNO films have uniform crack-free smooth surfaces. Electrical properties measurements showed that c-LNO films have lower resistivity than a-LNO films and both types of LNO films have semiconductor resistant temperature dependence. The activation energy of electric conduction of a-LNO films was found to be much higher than that of c-LNO films. The optical transmittance and reflectance of the films were studied in the UV–visible–near IR range. The optical constants were obtained by modeling the measured transmission and reflection spectra. Because of the discrepancies in the morphology and in the physical properties of a-LNO and c-LNO films, the best fit modeling of transmission and reflection spectra was obtained by using different theoretical models and different geometrical configurations. While the Drude model accounting for larger carrier density was found to be significant for c-LNO, using the Bruggmann model and a configuration of a rough layer on top of a compact film was found to be significant for a-LNO.     

Fabrication and diffusion barrier properties of nanoscale Ta/Ta-N bi-layer

One of the most important processes in Cu metallization for ultra large scale integrated circuits (ULSI) is to fabricate better diffusion barrier. In this paper, Ta/Ta-N films were fabricated by dc magnetron reactive sputtering (DCMS) in N₂/Ar ambient, then Cu/Ta/Ta-N/Si multi-structures were prepared in suite. The thin-film samples were rapid thermal annealed (RTA) at variational temperatures in N₂ ambient. Alpha-Step IQ Profiler, four-point probe (FPP) sheet resistance measurer, atomic force microscope (AFM), scanning electron microscope (SEM), X-ray diffraction (XRD) and tape test were used to characterize the microstructure and diffusion properties of the thin-films. The results show that the nanoscale Ta/Ta-N thin-films have smooth surface, and the thermal stability and barrier performance are good. After 600 °C/300 s RTA, Ta (40 nm)/Ta-N (60 nm) thin-films can effectively block against Cu diffusion and keep good adhesion strength with Cu films. After higher temperature RTA process, Cu atoms penetrated through the barrier and reacted with silicon, the barrier fail.     

Shape memory behavior and internal structure of Ti–Ni–Cu shape memory alloy thin films and their application for microactuators

Internal structure and shape memory behavior of Ti–38.3Ni–9.3Cu (at.%) thin films heat-treated at 873 K, 923 K, 973 K and 1023 K were investigated by TEM observation and thermal cycling tests under various constant stresses. The thin film heat-treated at 873 K contained two types of precipitates, i.e., fine platelets and Ti₂Ni particles. The density of the platelets decreased with increasing heat-treatment temperature and annihilated completely when the heat-treatment temperature reached 973 K. The Ti₂Ni precipitates increased in volume fraction with increasing heat-treatment temperature from 873 K to 923 K, then their volume fraction was almost kept constant above 923 K. The recoverable strain decreased and the M_s increased with increasing heat-treatment temperature from 873 K to 923 K. Both the recoverable strain and the M_s became almost constant when the heat-treatment temperature was above 923 K. A diaphragm-type microactuator utilizing a Ti–38.0Ni–10.0Cu (at.%) thin film was fabricated. The diaphragm was square with the width of 500 μm. The actuation properties were investigated under conditions of both quasi-static and dynamic actuation. The M_s and the transformation temperature hysteresis of the microactuator were determined to be 352 K and 6 K, respectively. The microactuator operated at a working frequency of 100 Hz.