Cu2ZnSnSe4 films by selenization of Sn–Zn–Cu sequential films

This paper deals with the formation of Cu₂ZnSnSe₄ (CZTS) in the process of selenization of metal precursor layers in elemental selenium vapour. Metallic precursors were sequentially evaported from Sn, Zn and Cu sources. Precursor Sn–Zn–Cu films have a “mesa-like” structure and consist mainly of Cu₅Zn₈ and Cu₆Sn₅ phases. It was confirmed that the formation of different binary copper selenides is the dominating process of selenization in elemental Se vapour at temperatures up to 300 °C. The formation of kesterite CZTS films begins at 300 °C and dominates at higher temperatures, always resulting in multiphase films that consist of high-quality Cu₂ZnSnSe₄ crystals and of a separate phase of ZnSe.     

Fabrication and characterization of Cu–CdSe–Cu nanowire heterojunctions

The Cu–CdSe–Cu nanowire heterojunctions were fabricated by sequential electrochemical deposition of layers of Cu metal and CdSe semiconductor within the nano-pores of anodic alumina membrane templates. X-ray diffraction reveals the cubic phase for Cu and hexagonal phase for CdSe in the electrodeposited Cu–CdSe–Cu nanowire heterojunctions. The composition of the nanowire heterojunction segments is characterized by energy dispersive X-ray spectroscopy. The morphological study of nanowire heterojunctions has been made using scanning electron microscope and high resolution transmission microscopy. The nanowire heterojunctions grown in 100 and 300 nm nano-pore size templates have been found to have optical band gaps of 1.92 and 1.75 eV, respectively. The absorption spectra of 100 nm nanowire heterojunctions show a blue shift of 0.18 eV. The collective nonlinear current–voltage (I–V) characteristics of the 300 and 100 nm nanowire heterojunctions show their rectifying and asymmetric behaviour, respectively.     

Improvement of Cu2ZnSnS4 thin film morphology using Cu–Zn–Sn–O precursor fabricated by sputtering

The new precursor of Cu–Zn–Sn–O (CZTO) was proposed for Cu₂ZnSnS₄ (CZTS) thin film fabrication to improve film morphology. The CZTS thin film grown from Cu–Zn–Sn (CZT) precursors has many bumps. We deposited CZTO precursors on Mo/soda-lime glass (SLG) substrates by RF sputtering using a CZT (Cu:Zn:Sn = 2:1:1) target in Ar and O₂ atmosphere at various O₂ partial pressures (0%, 5%, 17% and 20%). Subsequently, the CZTO precursors were sulfurized in Ar and S atmosphere to fabricate CZTS thin films. The CZTO precursors were amorphous. The morphology of the CZTS thin films was improved by the CZTO precursors. All of the CZTS films fabricated in this study had the same crystal structure. Composition analysis revealed that 50% of O were detected in the CZTO precursor, but O was not detected after sulfurizing process, indicating that O was substituted by S. The CZTS thin film from the CZTO precursor fabricated at O₂ partial pressure of 20% had similar composition for solar cell absorber.     

Internal stresses in cold-deformed Cu–Ag and Cu–Nb wires

The co-deformation of Cu–Ag or Cu–Nb composite wires used for high-field magnets has a number of important microstructural consequences, including the production of very-fine-scale structures, the development of very high internal surface-area-to-volume ratios during the drawing, and the storage of defects at interphase interfaces. In addition, the fabrication and co-deformation of the Cu and Ag or Nb, which differ in crystal structure, thermal expansion, elastic modulus and lattice parameter, lead to the development of short-wavelength internal stresses in both composites. In this paper, these internal stresses are characterized by neutron diffraction and transmission electron microscopy as a function of the imposed drawing strain. The internal stresses lead to important changes in the elastic–plastic response, which is related to both magnet design and service life. The second derivative ?² σ/?² ε of the stresses with respect to strain is used to describe the low-strain anelasticity of the composites. The internal stresses in Cu–Nb are higher than in Cu–Ag and, consequently, the absolute values of (?² σ/?² ε)_Cu–Nb are higher than those of (?² σ/?² ε)_Cu–Ag at low strains.     

Electrodeposited Co–Cu/Cu multilayered microposts

X-ray lithography and electrodeposition were combined to deposit an array of Co–Cu/Cu multilayer microposts of 500 μm tall into deep recesses for novel giant magnetoresistance (GMR) architectures. A citrate-boric acid electrolyte was used with pulsed potential. The applied potential was determined through inspection of the polarization curve from linear sweep voltammetry, and scanning electron microscopy (SEM)/transmission electron microscope (TEM) confirmed the micropost layered structure. Room temperature magnetoresistance was reported for different bilayer sizes of the micropost, and up to 4% current perpendicular-to-plane giant magnetoresistance (CPP-GMR) with saturation values less than 1 T was observed.     

Stability of Thin-Film Cu–As2S3 and Ag–As2S3 Structures

Technical Physics - Thin-film Cu–As2S3 and Ag–As2S3 structures obtained by successively evaporating Cu(Ag) and As2S3 in vacuum on glass substrates have been studied. Samples of these...     

Stability and stabilization of 2H martensite in Cu–Zn–Al single crystals

The stabilization of the 2H martensitic phase in Cu–Zn–Al single crystals with an electron concentration e/a?=?1.53 was investigated. This orthorhombic 2H martensite was first induced from the cubic β phase by the direct β?→?2H or the indirect β?→?18R?→?2H transformations. On loading the 2H martensite, a transition without hysteresis is observed at a stress which was denoted σ_T1. It was found that this stress is associated with a change in the behaviour of the 2H martensite. A high stabilization of the 2H martensite, around 300?K, is only obtained if an ageing is performed at a stress above σ_T1. Additionally, the stresses of the transformation to another martensitic phase, called 18R₂, were found to be constant when the value of σ_T1 is below the retransformation stress. The 2H martensite and its behaviour on ageing were studied by dilatometry, calorimetry, mechanical testing, optical microscopy and transmission electron microscopy (TEM). Models accounting for the stabilization of the 2H martensite on ageing are proposed.     

63Cu NMR analysis of microstructure evolution in Al–Cu–Mg alloys

⁶³Cu NMR spectroscopy has been used to detect metastable Guinier–Preston–Bagaryatsky (GPB) zones and nanoscale precipitates of equilibrium S-phase (Al₂CuMg) in dilute alloys of aluminium containing copper and magnesium with compositions which lie in the α?+?S phase field. The GPB zones are observed to form rapidly at room temperature with a time development closely related to the Vickers hardness. The final development of S-phase in the alloy has been confirmed by the observation of a line shape in the alloy identical to that observed in a specimen prepared from stoichiometric Al₂CuMg. Analysis of the hyperfine structure of the ⁶³Cu line shape observed for S-phase shows clearly that two Cu sites are present with approximately equal population. This result suggests that possibly two crystallographically distinct Al₂CuMg phases are present. The addition of small amounts of silver to Al–Cu–Mg alloys in the α?+?θ phase field is known to induce the formation of Ω-phase: a slight distortion of tetragonal θ-phase Al₂Cu. A hyperfine-structured ⁶³Cu line shape assigned to Ω-phase, indicating one distinct Cu site, has been observed in two separate Al–1.7?at.%?Cu–0.33?at.%?Mg alloys containing 0.1 and 0.18?at.%?Ag, but not in the same Al–Cu–Mg alloy without Ag.     

I–V characteristics of ZnO/Cu2O thin film n–i–p heterojunction

ZnO/Cu₂O thin film n–i–p heterojunctions were fabricated by magnetron sputtering. The microstructure, optical, and electrical properties of n-type (n‐) ZnO, insulating (i‐) ZnO, and p-type (p‐) Cu₂O films deposited on glass substrates were characterized by X-Ray diffraction (XRD), spectrophotometer, and the van der Pauw method, respectively. XRD results show that the mean grain size of i-ZnO film is much larger than that of n-ZnO film. The optical band gap energies of n-ZnO, i-ZnO, and p-Cu₂O film are 3.27, 3.47, and 2.00 eV, respectively. The carrier concentration of n-ZnO film is two orders of magnitude larger than that of p-Cu₂O film. The current–voltage (I–V) characteristics of ZnO/Cu₂O thin film n–i–p heterojunctions with different i-ZnO film thicknesses were investigated. Results show that ZnO/Cu₂O n–i–p heterojunctions have well-defined rectifying behavior. All ideality factors of these n–i–p heterojunctions are larger than 2.0. The forward bias threshold voltage and ideality factor increase when i-ZnO layer thickness increases from 100 to 200 nm. An energy band diagram was proposed to analyze the I–V characteristics of these n–i–p heterojunctions.     

Approaches to the synthesis of High-TC superconducting oxides in La–Ba–Cu–O and Y–Ba–Cu–O systems

Abstract

High-T_C superconducting oxides of nominal La_1.85Ba_0.15 CuO₄ and YBa₂ Cu₃ O₇ have been prepared by using nitrate, carbonate, oxalate/malonate and citrate precursors. While the samples in the Y-system are generally monophasic YBa₂Cu₃O_7?δ with T_C around 90K, the preparations in the La-system are biphasic containing K₂NiF₄-like La_1.85Ba_0.15 CuO₄ (T_C = 30K) and a perovskite-like phase with' a much higher T_C (200–300K). Effect of Ca, Zr, Ce as well as S substitution in YBa₂Cu₃O_7?δ has also been investigated     

Molecular dynamics simulation of thermal conductivity of Cu–Ar nanofluid using EAM potential for Cu–Cu interactions

Mechanism of heat conduction in copper-argon nanofluids is studied by molecular dynamics simulation and the thermal conductivity was obtained using the Green–Kubo method. While the interatomic potential between argon atoms is described using the well-known Lennard–Jones (L–J) potential, a more accurate embedded atom method (EAM) potential is used in describing the interatomic interaction between copper atoms. It is found that the heat current autocorrelation function obtained using L–J potential to describe the copper-copper interatomic interaction fluctuates periodically due to periodic oscillation of the instantaneous microscopic heat fluxes. Thermal conductivities of nanofluids using EAM potentials were calculated with different volume fractions but the same nanoparticle size. The results show that thermal conductivity of nanofluids are almost a linear function of the volume fraction and slightly higher than the results predicted by the conventional effective media theory for a well-dispersed solution. A solid-like base fluid liquid layer with a thickness of 0.6 nm was found in the simulation and this layer is believed to account for the small discrepancy between the results of MD simulation and the conventional effective media theory.     

Directional solidification of Al–Cu–Ag alloy

Al–Cu–Ag alloy was prepared in a graphite crucible under a vacuum atmosphere. The samples were directionally solidified upwards under an argon atmosphere with different temperature gradients (G=3.99–8.79 K/mm), at a constant growth rate (V=8.30 μm/s), and with different growth rates (V=1.83–498.25 μm/s), at a constant gradient (G=8.79 K/mm) by using the Bridgman type directional solidification apparatus. The microstructure of Al-12.80-at.%–Cu-18.10-at.%–Ag alloy seems to be two fibrous and one lamellar structure. The interlamellar spacings (λ) were measured from transverse sections of the samples. The dependence of interlamellar spacings (λ) on the temperature gradient (G) and the growth rate (V) were determined by using linear regression analysis. According to these results it has been found that the value of λ decreases with the increase of values of G and V. The values of λ ² V were also determined by using the measured values of λ and V. The experimental results were compared with two-phase growth from binary and ternary eutectic liquid.     

Hume-Rothery electron concentration rule across a whole solid solution range in a series of gamma-brasses in Cu–Zn,Cu–Cd,Cu–Al,Cu–Ga,Ni–Zn and Co–Zn alloy systems

The aim of the present work is to examine if the Hume-Rothery stabilisation mechanism holds across whole solid solution ranges in a series of gamma-brasses with especial attention to the role of vacancies introduced into the large unit cell. The concentration dependence of the number of atoms in the unit cell, N, for gamma-brasses in the Cu–Zn, Cu–Cd, Cu–Al, Cu–Ga, Ni–Zn and Co–Zn alloy systems was determined by measuring the density and lattice constants at room temperature. The number of itinerant electrons in the unit cell, e/uc, is evaluated by taking a product of N and the number of itinerant electrons per atom, e/a, for the transition metal element deduced earlier from the full-potential linearised augmented plane wave (FLAPW)-Fourier analysis. The results are discussed within the rigid-band model using as a host the density of states (DOS) derived earlier from the FLAPW band calculations for the stoichiometric gamma-brasses Cu₅Zn₈, Cu₉Al₄ and TM₂Zn₁₁ (TM = Co and Ni). A solid solution range of gamma-brasses in Cu–Zn, Cu–Cd, Cu–Al, Cu–Ga and Ni–Zn alloy systems is found to fall inside the existing pseudogap at the Fermi level. This is taken as confirmation of the validity of the Hume-Rothery stability mechanism for a whole solute concentration range of these gamma-brasses. An exception to this behaviour was found in the Co–Zn gamma-brasses, where orbital hybridisation effects are claimed to play a crucial role in stabilisation.     

Synthesis of smooth and superconducting (Cu, C)–Ba–O/CaCuO2/(Cu, C)–Ba–O films using SrCuO2 buffer

Artificially stacked structures of [(infinite layer CaCuO₂)_k/(superconducting (Cu, C)Ba₂CuO_x:(Cu, C)-1201)_l]_m were fabricated on SrCuO₂ buffer layer by means of sequential deposition of each block using pulsed laser deposition. Smooth and epitaxial growth all over the deposition cycles of (Cu, C)-1201 and CaCuO₂ were confirmed by streak patterns of in situ RHEED. In comparison with (Cu, C)-1201 single layer films, the artificial stacking resulted in a rise of superconducting properties, T_c-onset and T_c(ρ=0) up to 95 K and 65 K, respectively.     

Study of inverse a.c. Josephson effect in Y–Ba–Cu–O and Y–8a–Sr–Cu–O

Microwave induced d.c. voltage due to inverse a.c. Josephson effect has been observed across bulk samples of Y-Ba-Cu-O and Y-Ba-Sr-Cu-O. The d.c. voltage is found to vary with microwave power, frequency and also with small external magnetic fields. Although the resistivity curve of Y-Ba-Cu-O does not show any appreciable resistance drop around 230 K, the microwave induced d.c. voltage due to the inverse a.c. Josephson effect has been found to exist upto 230 K. The resistivity behaviour of Y-Ba-Sr-Cu-O shows a sharp resistivity drop above 230 K. In this sample the inverse Josephson effect is found to exist upto +26 °C, indicating the presence of a phase having a superconducting onset around this temperature.     

Superconductivity of Y–Ba–Cu–O and substituted systems

Superconductivity of Y-Ba-Cu-O system is studied in the composition 2:2:3 and 1:2:3 of Y:Ba:Cu. The effect of replacement of Y or Ba by divalent Sr and Ca, trivalent Ce and tetravalent Zr is studied. X-ray diffraction, SEM and TEM techniques are used for materials characterization. Superconducting transition temperatures are measured resistively. Rapid resistance drop observed above 230 K in Y-Ba-Sr-Cu-O and Y-Ba-Ca-Cu-O systems indicate the possible existence of superconductivity above 230 K. Substitution of Ce in place of Y is found to reduce the onset Tc from 95 K to 80 K. For the first time, replacement of Cu by Zr in Y-Ba-Cu-O has yielded the onset Tc of about 105 K.     

High-Temperature superconductivity in the Y–Ba–Cu–O system

High-temperature superconductivity in the Y-Ba-Cu-O system has been discussed with special reference to the identification and characterization of the pure monophasic compound responsible for the superconductivity. The crucial role of oxygen has been examined in the light of the structure and thermogravimetric analysis.     

Electrical contact properties of Cu2S nanowires grown vertically on Cu foil by gas–solid reaction

We grew Cu₂S nanowires vertically on Cu foil by gas–solid reaction with a gas mixture of O₂ and H₂S. The electrical contact properties between the Cu₂S nanowires and Cu foil were investigated using a modified current–voltage–temperature plot. The Cu/Cu₂S layer exhibited the characteristics of a Schottky barrier with a barrier height of ∼0.72 eV, which was closer to the value for Cu/Cu₂O than to Cu/Cu₂S. Energy dispersive spectroscopy results showed the presence of Cu-oxide between the Cu₂S nanowires and Cu foil. The overall structure was Cu/Cu-oxide/Cu₂S and the electrical properties were controlled by the Cu/Cu-oxide.     

Abnormal resistivity behavior of Cu–Ni and Cu–Co alloys in undercooled liquid state

The resistivity behavior of undercooled liquid Cu–Ni and Cu–Co alloys had been studied in the contactless method, to probe the structure transition in undercooled melts during the cooling process. Over the entire concentration range, linear behavior of resistivity with temperature was obtained in liquid and undercooled liquid Cu–Ni system. It implied that the formation of icosahedral order might not influence the electron scattering in undercooled liquid Cu–Ni alloys. Similar results were obtained in Cu–Co system in the vicinity of liquidus temperature. A turning point was obvious in temperature coefficient of resistivity for undercooled liquid Cu–Co alloys around the bimodal line, which was interpreted to be responsible for metastable liquid–liquid phase separation. During liquid phase separation process, resistivity decreased and the temperature coefficient of resistivity was larger than that of homogeneous melts. In combination with transmission electron microscopy and scanning electron microscope studies on the as-solidified microstructure, this was interpreted as the formation of egg-type structure and concentration change in Cu-rich and Co-rich phases. The mechanism controlling the separation and droplets motion was also discussed in undercooled liquid Cu–Co system.     

Vortex pinning in bulk-processed Y–Ba–Cu–O with ZrO2 nano-particles: Optimum pinning center size

Crystalline defects on the nano-scale were successfully introduced into YBCO high-temperature superconductors (HTS) by ZrO₂ nanometer particles addition in order to strongly pin the quantized vortices. Three batches of ZrO₂ nano-particles with different particle size distributions were used. The corresponding mean nano-particle diameters are respectively, 287, 536 and 764 nm. Serving as artificial pinning centers (APC), non-superconducting nano-particles cause a remarkable enhancement of critical current density (J_c) at T = 77 K. This improvement has been shown to depend on the size of APC. The pinning strength of nano-particles inclusions has been found to be greater with wide size dispersed nano-particles. Our results indicate that pinning properties and vortex dynamics depend on the size of APCs. The introduction of APCs with controlled size is indispensable to achieve a high J_c.