In this study we examine variations in the structure of perovskite compounds of LaBa2Cu2O9, LaBa2CaCu3O12 and LaBa2Ca2Cu5O15 synthesized using the solid state reaction method. The samples’ compositions were assessed using X-ray fluorescence (XRF) analysis. The La: Ba: Ca: Cu ratios for samples LaBa2Cu2O9, LaBa2CaCu3O12 and LaBa2Ca2Cu5O15 were found by XRF analysis to be around 1:2:0:2, 1:2:1:3, and 1:2:2:5, respectively. The samples’ well-known structures were then analyzed using X-ray diffraction. The three samples largely consist of phases 1202, 1213, and 1225, with a trace quantity of an unknown secondary phase, based on the intensities and locations of the diffraction peaks. According to the measured parameters a, b, and c, every sample has a tetragonal symmetry structure. Each sample’s mass density was observed to alter as the lead oxide content rose. Scanning electron microscope (SEM) images of the three phases revealed that different Ca-O and Cu-O layers can cause different grain sizes, characterized by elongated thin grains, without a preferred orientation.

The Cu2ZnSn(SxSe1-x)4 (CZTSSe) absorbers are promising thin film solar cells (TFSCs) materials, to replace existing Cu(In,Ga)Se2 (CIGS) and CdTe photovoltaic technology. However, the best reported efficiency for a CZTSSe device, of 13.6 %, is still too low for commercial use. Recently, partially replacing the Zn2+ element with a Cd2+element has attracting attention as one of the promising strategies for improving the photovoltaic characteristics of the CZTSSe TFSCs. Cd2+ elements are known to improve the grain size of the CZTSSe absorber thin films and improve optoelectronic properties by suppressing potential defects, causing short-circuit current (Jsc) loss. In this study, the structural, compositional, and morphological characteristics of CZTSSe and CZCTSSe thin films were investigated using X-ray diffraction (XRD), X-ray fluorescence spectrometer (XRF), and Field-emission scanning electron microscopy (FE-SEM), respectively. The FE-SEM images revealed that the grain size improved with increasing Cd2+ alloying in the CZTSSe thin films. Moreover, there was a slight decrease in small grain distribution as well as voids near the CZTSSe/Mo interface after Cd2+ alloying. The solar cells prepared using the most promising CZTSSe absorber thin films with Cd2+ alloying (8 min. 30 sec.) exhibited a power conversion efficiency (PCE) of 9.33 %, Jsc of 34.0 mA/cm2, and fill factor (FF) of 62.7 %, respectively.

Cu2ZnSn(S,Se)4 (CZTSSe) based thin-film solar cells have attracted growing attention because of their earthabundant and non-toxic elements. However, because of their large open-circuit voltage (Voc)-deficit, CZTSSe solar cells exhibit poor device performance compared to well-established Cu(In,Ga)(S,Se)2 (CIGS) and CdTe based solar cells. One of the main causes of this large Voc-deficit is poor absorber properties for example, high band tailing properties, defects, secondary phases, carrier recombination, etc. In particular, the fabrication of absorbers using physical methods results in poor surface morphology, such as pin-holes and voids. To overcome this problem and form large and homogeneous CZTSSe grains, CZTSSe based absorber layers are prepared by a sputtering technique with different RTA conditions. The temperature is varied from 510 oC to 540 oC during the rapid thermal annealing (RTA) process. Further, CZTSSe thin films are examined with X-ray diffraction, X-ray fluorescence, Raman spectroscopy, IPCE, Energy dispersive spectroscopy and Scanning electron microscopy techniques. The present work shows that Cu-based secondary phase formation can be suppressed in the CZTSSe absorber layer at an optimum RTA condition.

Recent advances in technology using ultra-thin noble metal film in oxide/metal/oxide structures have attracted attention because this material is a promising alternative to meet the needs of transparent conduction electrodes (TCE). AZO/ Ag/AZO multilayer films are prepared by magnetron sputtering for Cu2ZnSn(S,Se)4 (CZTSSe) of kesterite solar cells. It is shown that the electrical and optical properties of the AZO/Ag/AZO multilayer films can be improved by the very low resistivity and surface plasmon effects due to the deposition of different thicknesses of Ag layer between oxide layers fixed at AZO 30 nm. The AZO/Ag/AZO multilayer films of Ag 15 nm show high mobility of 26.4 cm2/Vs and low resistivity and sheet resistance of 3.58*10−5 Ωcm and 5.0 Ω/sq. Also, the AZO/Ag (15 nm)/AZO multilayer film shows relatively high transmittance of more than 65% in the visible region. Through this, we fabricated CZTSSe thin film solar cells with 7.51% efficiency by improving the short-circuit current density and fill factor to 27.7 mV/cm2 and 62 %, respectively.

Due to its favorable optical properties, Cu2SnS3 (CTS) is a promising material for thin film solar cells. Doping, which modifies the absorber properties, is one way to improve the conversion efficiency of CTS solar cells. In this work, CTS solar cells with selenium doping were fabricated on a flexible substrate using sputtering method and the effect of doping on the properties of CTS solar cells was investigated. In XRD analysis, a shift in the CTS peaks can be observed due to the doped selenium. XRF analysis confirmed the different ratios of Cu/Sn and (S+Se)/(Cu+Sn) depending on the amount of selenium doping. Selenium doping can help to lower the chemical potential of sulfur. This effectively reduces the point defects of CTS thin films. Overall improved electrical properties were observed in the CTS solar cell with a small amount of selenium doping, and a notable conversion efficiency of 1.02 % was achieved in the CTS solar cell doped with 1 at% of selenium.

본 연구에서는 구리 이온(Cu2+ ion) 제거를 위한 산화철(Fe3O4)/다공성 탄소 복합체를 합성하였으며, 이를 바탕으로 구리 이온 제거에 대한 특성 평가를 실시하였다. SEM, XRD 분석을 진행하여 수열합성(hydrothermal) 반응을 이용한 산화철/다공성 탄소 복합체의 형태와 구조를 확인하였다. BET 분석을 통해 비표면적과 기공 크기를 확인하였으며, UV-vis 장비를 통해 성능 평가를 실시하여 자성이 있는 Fe3O4와 다공성 탄소와의 시너지효과를 통해 액체 상태에서 존재하는 구리 이온을 제거할 수 있는 가능성을 제시하였다.

Cu2ZnSn(S,Se)4(CZTSSe) thin film solar cells areone of the most promising candidates for photovoltaic devices due to their earth-abundant composition, high absorption coefficient and appropriate band gap. The sputtering process is the main challenge to achieving high efficiency of CZTSSe solar cells for industrialization. In this study, we fabricated CZTSSe absorbers on Mo coated soda lime glass using different pressures during the annealing process. As an environmental strategy, the annealing process is performed with S and Se powder, without any toxic H2Se and/or H2S gases. Because CZTSSe thin films have a very narrow stable phase region, it is important to control the condition of the annealing process to achieve high efficiency of the solar cell. To identify the effect of process pressure during the sulfo-selenization, we experiment with varying initial pressure from 600 Torr to 800 Torr. We fabricate a CZTSSe thin film solar cell with 8.24 % efficiency, with 435 mV for open circuit voltage(VOC) and 36.98 mA/cm2 for short circuit current density(JSC), under a highest process pressure of 800 Torr.

Recent industrialization has led to a high demand for the use of fossil fuels. Therefore, the need for producing hydrogen and its utilization is essential for a sustainable society. For an eco-friendly future technology, photoelectrochemical water splitting using solar energy has proven promising amongst many other candidates. With this technique, semiconductors can be used as photocatalysts to generate electrons by light absorption, resulting in the reduction of hydrogen ions. The photocatalysts must be chemically stable, economically inexpensive and be able to utilize a wide range of light. From this perspective, cuprous oxide(Cu2O) is a promising p-type semiconductor because of its appropriate band gap. However, a major hindrance to the use of Cu2O is its instability at the potential in which hydrogen ion is reduced. In this study, gold is used as a bottom electrode during electrodeposition to obtain a preferential growth along the (111) plane of Cu2O while imperfections of the Cu2O thin films are removed. This study investigates the photoelectrochemical properties of Cu2O. However, severe photo-induced corrosion impedes the use of Cu2O as a photoelectrode. Two candidates, TiO2 and SnO2, are selected for the passivation layer on Cu2O by by considering the Pourbaix-diagram. TiO2 and SnO2 passivation layers are deposited by atomic layer deposition(ALD) and a sputtering process, respectively. The investigation of the photoelectrochemical properties confirmed that SnO2 is a good passivation layer for Cu2O.

Cu2ZnSn(S,Se)4 (CZTSSe) films were prepared on Mo coated soda lime glass substrates by sulfo-selenization of sputtered stacked Zn-Sn-Cu(CZT) precursor films. The precursor was dried in a capped state with aqueous NaOH solution. The CZT precursor films were sulfo-selenized in the S + Se vapor atmosphere. Sodium was doped during the sulfo-selenization treatment. The effect of sodium doping on the structural and electrical properties of the CZTSSe thin films were studied using FE-SEM(field-emission scanning electron microscopy), XRD(X-ray diffraction), XRF(X-ray fluorescence spectroscopy), dark current, SIMS(secondary ion mass spectrometry), conversion efficiency. The XRD, XRF, FE-SEM, Dark current, SIMS and cell efficiency results indicated that the properties of sulfo-selenized CZTSSe thin films were strongly related to the sodium doping. Further detailed analysis and discussion for effect of sodium doping on the properties CZTSSe thin films will be discussed.

We report on the fabrication and photoelectrochemical(PEC) properties of a Cu2O thin film/ZnO nanorod array oxide p-n heterojunction structure with ZnO nanorods embedded in Cu2O thin film as an efficient photoelectrode for solardriven water splitting. A vertically oriented n-type ZnO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type Cu2O thin film was directly electrodeposited onto the vertically oriented ZnO nanorods array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were characterized using X-ray diffraction and scanning electron microscopy as well as Raman scattering. The PEC properties of the fabricated Cu2O/ZnO p-n heterojunction photoelectrode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the Cu2O/ZnO photoelectrode was found to exhibit a negligible dark current and high photocurrent density, e.g., 0.77 mA/cm2 at 0.5 V vs Hg/HgCl2 in a 1 mM Na2SO4 electrolyte, revealing an effective operation of the oxide heterostructure. In particular, a significant PEC performance was observed even at an applied bias of 0 V vs Hg/ HgCl2, which made the device self-powered. The observed PEC performance was attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential, including the light absorption and separation processes of photoinduced charge carriers.

We report on the fabrication and characterization of a novel Cu2O/CuO heterojunction structure with CuO nanorods embedded in Cu2O thin film as an efficient photocathode for photoelectrochemical (PEC) solar water splitting. A CuO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method; then, a Cu2O thin film was electrodeposited onto the CuO nanorod array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were examined using X-ray diffraction and scanning electron microscopy, as well as Raman scattering. The PEC properties of the fabricated Cu2O/CuO heterojunction photocathode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the Cu2O/CuO photocathode was found to exhibit negligible dark current and high photocurrent density, e.g. −1.05 mA/cm2 at −0.6 V vs. Hg/HgCl2 in 1 mM Na2SO4 electrolyte, revealing the effective operation of the oxide heterostructure. The photocurrent conversion efficiency of the Cu2O/CuO photocathode was estimated to be 1.27% at −0.6 V vs. Hg/HgCl2. Moreover, the PEC current density versus time (J-T) profile measured at −0.5 V vs. Hg/HgCl2 on the Cu2O/CuO photocathode indicated a 3-fold increase in the photocurrent density compared to that of a simple Cu2O thin film photocathode. The improved PEC performance was attributed to a certain synergistic effect of the bilayer heterostructure on the light absorption and electron-hole recombination processes.

Refuse-derived fuel (RDF) produced using municipal solid waste was pyrolyzed to produce RDF char. For the first time, the RDF char was used to remove aqueous copper, a representative heavy metal water pollutant. Activation of the RDF char using steam and KOH treatments was performed to change the specific surface area, pore volume, and the metal cation quantity of the char. N2 sorption, Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP-AES), and Fourier transform infrared spectroscopy were used to characterize the char. The optimum pH for copper removal was shown to be 5.5, and the steam-treated char displayed the best copper removal capability. Ion exchange between copper ions and alkali/alkaline metal cations was the most important mechanism of copper removal by RDF char, followed by adsorption on functional groups existing on the char surface. The copper adsorption behavior was represented well by a pseudo-second-order kinetics model and the Langmuir isotherm. The maximum copper removal capacity was determined to be 38.17 mg/g, which is larger than those of other low-cost char adsorbents reported previously.

The morphology, crystal structure and size of aerosol nanoparticles generated by erosion of electrodes made of different materials (titanium, copper and aluminum) in a multi-spark discharge generator were investigated. The aerosol nanoparticle synthesis was carried out in air atmosphere at a capacitor stored energy of 6 J, a repetition rate of discharge of 0.5 Hz and a gas flow velocity of 5.4 m/s. The aerosol nanoparticles were generated in the form of oxides and had various morphologies: agglomerates of primary particles of TiO2 and Al2O3 or aggregates of primary particles of Cu2O. The average size of the primary nanoparticles ranged between 6.3 and 7.4 nm for the three substances studied. The average size of the agglomerates and aggregates varied in a wide interval from 24.6 nm for Cu2O to 46.1 nm for Al2O3.

This study reports the effects of H2S gas concentration on the properties of Cu2ZnSnS4(CZTS) thin films. Specifically, sulfurization process with low H2S concentrations of 0.05% and 0.1%, along with 5% H2S gas, was studied. CZTS films were directly synthesized on Mo/Si substrates by chemical bath deposition method using copper sulfate, zinc sulfate heptahydrate, tin chloride dihydrate, and sodium thiosulfate pentahydrate. Smooth CZTS films were grown on substrates at optimized chemical bath deposition condition. The CZTS films sulfurized at low H2S concentrations of 0.05 % and 0.1% showed very rough and porous film morphology, whereas the film sulfurized at 5% H2S yielded a very smooth and dense film morphology. The CZTS films were fully crystallized in kesterite crystal form when they were sulfurized at 500 oC for 1 h. The kesterite CZTS film showed a reasonably good room-temperature photoluminescence spectrum that peaked in a range of 1.4 eV to 1.5 eV, consistent with the optimal bandgap for CZTS solar cell applications.

Cu2O nanowires were synthesized at large scale on copper plate by thermal oxidation in air. The effect of oxidation time and temperature on the morphology of the nanowires was examined. The oxidation time had no effect on the diameter of the nanowires, while it had a great effect on the density and the length of the nanowires. The density and the length of the nanowires increased, and then decreased, with increasing oxidation time. The oxidation temperature had a tremendous effect on the size-distribution as well as the density of the nanowires. When the oxidation temperature was 700˚C, uniform size-distribution and high density of the nanowires was achieved. At lower and higher temperatures, the density of the nanowires was lower, and they displayed a broader size-distribution. It is suggested that the Cu2O nanowires were grown via a vapor-solid mechanism because no catalyst particles were observed at the tips of the nanowires.

Cu2ZnSn(Sx,Se1-x)4 (CZTSSe) thin films were prepared by sulfurization of evaporated precursor thin films. Precursor was prepared using evaporation method at room temperature. The sulfurization was carried out in a graphite box with S powder at different temperatures. The temperatures were varied in a four step process from 520˚C to 580˚C. The effects of the sulfurization temperature on the micro-structural, morphological, and compositional properties of the CZTSSe thin films were investigated using X-ray diffraction (XRD), Raman spectra, field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The XRD and Raman results showed that the sulfurized thin films had a single kesterite crystal CZTSSe. From the FE-SEM and TEM results, the Mo(Sx,Se1-x)2 (MoSSe) interfacial layers of the sulfurized CZTS thin films were observed and their thickness was seen to increase with increasing sulfurization temperature. The microstructures of the CZTSSe thin films were strongly related to the sulfurization temperatures. The voids in the CZTSSe thin films increased with the increasing sulfurization temperature.

The effect of a sputter deposition sequence of Cu, Zn, and Sn metal layers on the properties of Cu2ZnSnS4 (CZTS) was systematically studied for solar cell applications. The set of Cu/Sn/Zn/Cu multi metal films was deposited on a Mo/SiO2/Si wafer using dc sputtering. CZTS films were prepared through a sulfurization process of the Cu/Sn/Zn/Cu metal layers at 500˚C in a H2S gas environment. H2S (0.1%) gas of 200 standard cubic centimeters per minute was supplied in the cold-wall sulfurization reactor. The metal film prepared by one-cycle deposition of Cu(360 nm)/Sn(400 nm)/Zn(400 nm)/Cu(440 nm) had a relatively rough surface due to a well-developed columnar structure growth. A dense and smooth metal surface was achieved for two- or three-cycle deposition of Cu/Sn/Zn/Cu, in which each metal layer thickness was decreased to 200 nm. Moreover, the three-cycle deposition sample showed the best CZTS kesterite structures after 5 hr sulfurization treatment. The two- and three-cycle Cu/Sn/Zn/Cu samples showed high-efficient photoluminescence (PL) spectra after a 3 hr sulfurization treatment, wheres the one-cycle sample yielded poor PL efficiency. The PL spectra of the three-cycle sample showed a broad peak in the range of 700-1000 nm, peaked at 870 nm (1.425 eV). This result is in good agreement with the reported bandgap energy of CZTS.

In the DBC (direct bonding of copper) process the oxygen partial pressure surrounding the AlN/Cu bonding pairs has been controlled by Ar gas mixed with oxygen. However, the direct bonding of Cu with sound interface and good adhesion strength is complicated process due to the difficulty in the exact control of oxygen partial pressure by using Ar gas. In this study, we have utilized the in-situ equilibrium established during the reaction of + 1/2 by placing powder bed of CuO or around the Cu/AlN bonding pair at . The adhesion strength was relatively better in case of using CuO powder than when powder was used. Microstructural analysis by optical microscopy and XRD revealed that the interface of bonding pair was composed of , Cu and small amount of CuO phase. Thus, it is explained that the good adhesion between Cu and AlN is attributed to the wetting of eutectic liquid formed by reaction of Cu and .