Photoluminescence and X-ray diffraction studies on Cu2O

Cuprous oxide (Cu₂O) crystals were grown by the two-step crystallization method in air atmosphere conditions from polycrystalline thin copper foils. The method comprises two stages; in the first one the copper plates are oxidized at 1020 °C by some hours in line with its initial thickness. In the second stage, the growth of large crystalline areas is promoted by annealing the Cu₂O samples at 1100 °C for long periods. Raman scattering an X-ray measurements demonstrates the existence of the single-phase Cu₂O. The effects on the crystalline structure and photoluminescence (PL) response were studied as a function of the conditions used in the second stage of the synthesis method. PL spectra were taken from 10 to 180 K to define the main radiative recombination paths. Besides the near band excitonic transitions, two strong emission bands at 720 and 920 nm associated with relaxed excitons at oxygen and copper vacancies were detected. Both excitonic-vacancy bond transitions presented similar intensities that are related to the growth method. X-ray and Raman scattering measurements help to assess the samples crystalline quality.     

Photoluminescence study of disordering in the cation sublattice of Cu2ZnSnS4

In this study we investigated the influence of the degree of disordering in the cation sublattice on low temperature photoluminescence (PL) properties of Cu₂ZnSnS₄ (CZTS) polycrystals. The degree of disordering was changed by using different cooling rates after post-annealing at elevated temperatures. The results suggest that in the case of higher degree of cation sublattice disorder radiative recombination involving defect clusters dominates at T = 10 K. These defect clusters induce local band gap energy decrease in CZTS. The concentration of defect clusters can be reduced by giving more time for establishing ordering in the crystal lattice. As a result, radiative recombination mechanism changes and band-to-impurity recombination involving deep acceptor defect with ionization energy of about 200 meV starts to dominate in the low temperature PL spectra of CZTS polycrystals.     

N掺杂Cu2O薄膜的光学性质及第一性原理分析

采用射频磁控溅射技术, 在不同温度下制备了N掺杂Cu₂O薄膜．透射光谱分析发现, N掺杂导致Cu₂O成为允许的带隙直接跃迁半导体, 并使Cu₂O的光学禁带宽度增加．不同温度下沉积的薄膜光学禁带宽度E_g=2.52± 0.03 eV．第一性原理计算表明, N掺杂导致Cu₂O的禁带宽度增加了约25%, 主要与价带顶下移和导带底上移有关, 与实验报道基本符合．N的2p电子态分布不同于O原子, 在价带顶附近具有较大的态密度是N掺杂Cu₂O变成允许的带隙直接跃迁半导体的根本原因．     

Investigations on co-evaporated Cu2SnSe3 and Cu2SnSe3-ZnSe thin films

Cu₂SnSe₃ is an important precursor material for the growth of Cu₂ZnSnSe₄, an emerging solar cell absorber layer via solid state reaction of Cu₂SnSe₃ and ZnSe. In this study, we have grown Cu₂SnSe₃ (CTSe) and Cu₂SnSe₃-ZnSe (20%) films onto soda-lime glass substrates held at 573 K by co-evaporation technique. The effect of annealing of these films at 723 K for an hour in selenium atmosphere is also investigated. XRD studies of as-deposited Cu₂SnSe₃ and Cu₂SnSe₃-ZnSe films indicated SnSe as secondary phase which disappeared on annealing. The direct optical band gap of annealed Cu₂SnSe₃ and Cu₂SnSe₃-ZnSe films were found to be 0.90 eV and 0.94 eV respectively. Raman spectroscopy studies were used to understand the effect of ZnSe on the properties of Cu₂SnSe₃.     

Oxygen vacancy in N-doped Cu2O crystals: A density functional theory study

The N-doping effects on the electronic properties of Cu2O crystals are investigated using density functional theory. The calculated results show that N-doped Cu2O with or without oxygen vacancy exhibits different modifications of electronic band structure. In N anion-doped Cu2O, some N 2p states overlap and mix with the O 2p valence band, leading to a slight narrowing of band gap compared with the undoped Cu2O. However, it is found that the coexistence of both N impurity and oxygen vacancy contributes to band gap widening which may account for the experimentally observed optical band gap widening by N doping.     

Preparation of flower-like Cu2O nanoparticles by pulse electrodeposition and their electrocatalytic application

A pulsed electrodeposition technique based on a multipulse sequence of potentials of equal amplitude, duration and polarity was employed for preparation of highly dispersed flower-like cuprous oxide (Cu₂O) nanoparticles. The morphology analysis of the particles using scanning electron microscope (SEM) reveals that the flower-like particles were from sequential growth of Cu₂O along the (1 1 1) direction on the cubic Cu₂O (1 0 0). The structure and the chemical composition of the deposits were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Optical property and band gap of the Cu₂O was investigated using UV/vis diffuse reflection spectra (DRS), and the measured value of energy gap is 2.18 eV. The dark and light open circuit potential-time characterization study showed that the flower-like Cu₂O nanoparticles exhibited good photoelectric response. Cyclic voltammetry carried out in the presence of p-nitrophenol (p-NP) shows that the electrocatalytic performance of the Cu₂O particles for the reduction of p-NP, which was characterized by a cathodic peak at around −0.6 V. The influence of the incidence of light on the electrocatalysis is also discussed.     

A novel one-step electron beam irradiation method for synthesis of Ag/Cu2O nanocomposites

In this paper, a novel method for fabrication of silver/cuprous oxide (Ag/Cu₂O) nanocomposites is reported. The method involves the reduction of Ag⁺ and Cu²⁺ in the aqueous solution to Ag/Cu₂O without adding any reducing reagent under electron beam (EB) irradiation. Dye methyl orange is used as the pollutant model to investigate the photocatalytic properties of these nanocomposites. The results reveal that they have higher photocatalytic efficiencies than that of Cu₂O under visible light. These visible light-sensitive catalysts may have potential application in the field of environmental remediation.     

Fabrication of coaxial p-Cu2O/n-ZnO nanowire photodiodes

The authors report the deposition of Cu₂O onto vertically well aligned ZnO nanowires by DC sputtering. The average length, average diameter and density of these VLS-synthesized ZnO nanowires were 1 μm, 100 nm and 23 wires/μm², respectively. With proper sputtering parameters, the deposited Cu₂O could fill the gaps between the ZnO nanowires with good step coverage to form coaxial p-Cu₂O/n-ZnO nanowires with a rectifying current–voltage characteristic. Furthermore, the fabricated coaxial p-Cu₂O/n-ZnO nanowire photodiodes exhibit reasonably large photocurrent-to-dark-current contrast ratio and the fast responses.     

Fast and selective Cu2O nanorod growth into anodic alumina templates via electrodeposition

The fast and selective growth of cuprous oxide (Cu₂O) nanorods into anodic aluminum oxide (AAO) templates is achieved under optimized alkaline conditions via electrochemical deposition. The growth rate of Cu₂O nanorods at room temperature reached 360 nm/min, the fastest rate reported to date. The synthesis of Cu₂O nanorods by applying a constant current by using Cu₂O nanotubes as a transition state is extensively discussed; a Pt pottery-shaped layer played a key role as a seed layer for the fast Cu₂O growth. We report here the existence of regions of nanostructured Cu₂O based on our studies and previous relevant works, which include potential-pH curves for Cu²⁺-lactate solutions.     

A density functional theory study on the adsorption of CO and O2 on Cu-terminated Cu2O （111） surface

The adsorptions of CO and 02 molecules individually on the stoichiometric Cu-terminatcd Cu20 （111） surface are investigated by first-principles calculations on the basis of the density functional theory. The calculated results indicate that the CO molecule preferably coordinates to the Cu2 site through its C atom with an adsorption energy of-1.69 eV, whereas the 02 molecule is most stably adsorbed in a tilt type with one O atom coordinating to the Cu2 site and the other O atom coordinating to the Cul site, and has an adsorption energy of -1.97 eV. From the analysis of density of states, it is observed that Cu 3d transfers electrons to 2π orbital of the CO molecule and the highest occupied 5σ orbital of the CO molecule transfers electrons to the substrate. The sharp band of Cu 4s is delocalized when compared to that before the CO molecule adsorption, and overlaps substantially with bands of the adsorbed CO molecule. There is a broadening of the 2π orbital of the 02 molecule because of its overlapping with the Cu 3d orbital, indicating that strong 3d-2π interactions are involved in the chemisorption of the 02 molecule on the surface.     

“In situ” XPS study of band structures at Cu2O/TiO2 heterojunctions interface

In an attempt to investigate influence of the defects on electronic structure of Cu₂O/TiO₂ heterojunctions, thin Cu₂O layers were successively deposited on TiO₂ that has different levels of defect concentrations, and the resultant band bending and offset characteristics were studied by in situ X-ray photoelectron spectroscopy (XPS). The TiO₂ substrates with defects were prepared by Ar⁺ sputtering, followed by annealing at different temperatures in oxygen atmosphere. Presence of the defects in TiO₂ surface dramatically influences on the band bending and band offset at the interface: more defects are on TiO₂ surface, less band bending are at the interface, inducing smaller conduction band offsets. On the reduced TiO₂ surface, Cu₂O was disproportionately decomposed to form CuO and Cu.     

Preparing Cu2ZnSnS4 films using the co-electro-deposition method with ionic liquids

Cu2ZnSnS4（CZTS） films are successfully prepared by co-electrodeposition in aqueous ionic solution and sulfurized in elemental sulfur vapor ambient at 400 C for 30 min using nitrogen as the protective gas.It is found that the CZTS film synthesized at Cu/（Zn＋Sn）=0.71 has a kesterite structure,a bandgap of about 1.51 eV,and an absorption coefficient of the order of 10 4 cm 1.This indicates that the co-electrodeposition method with aqueous ionic solution is a viable process for the growth of CZTS films for application in photovoltaic devices.     

Effects of copper and oxygen vacancies on the ferromagnetism of Mn- and Co-doped Cu2O

The ferromagnetic properties of Mn- and Co-doped Cu₂O with copper and oxygen vacancies (V_Cu and V_O) are studied by first-principles calculations. The results indicate that Mn-doped Cu₂O has an antiferromagnetic state in the near configuration, while it has a ferromagnetic state for the far configuration. On the contrary, Co-doped Cu₂O possess a ferromagnetic state regardless of the distance between the two Co atoms. The observed ferromagnetism can be attributed to the 90° ferromagnetic super-exchange mechanism. The presence of V_O can enhance the ferromagnetism, whereas V_Cudepresses it.     

Temperature dependence of Cu2O orientations in oxidation of Cu (111)/ZnO (0001) by oxygen plasma

The role of temperature on the oxidation dynamics of Cu₂O on ZnO (0001) was investigated during the oxidation of Cu (111)/ZnO (0001) by using the oxygen plasma as oxidant. A transition from single crystalline Cu₂O (111) orientation to micro-zone phase separation with multiple orientations was revealed when the oxidation temperature increased from 300 ℃ to higher. The experimental results clearly showed the effect of oxidation temperature with the assistance of oxygen plasma on changing the morphology of Cu (111) film and enhancing the lateral nucleation and migration abilities of cuprous oxides. A vertical top-down oxidation mode and a lateral migration model were proposed to explain the different nucleation and growth dynamics of the temperature-dependent oxidation process in the oxidation of Cu (111)/ZnO (0001).     

Cu2ZnSnSe4 thin films prepared by selenization of co-electroplated Cu-Zn-Sn precursors

A novel technique for growth of high quality Cu₂ZnSnSe₄ (CZTSe) thin films is reported in our work. The CZTSe thin films were fabricated onto Mo layers by co-electroplating Cu-Zn-Sn precursors followed by annealing in the selenium vapors at the substrate temperature of 550 °C. The morphology and structure of CZTSe thin films were characterized using scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD) and Raman scattering spectrum, respectively. The results revealed that the single phase was in the CZTSe thin films, and the other impurities such as ZnSe and Cu₂SnSe₃ were not existed though they were difficult to distinguish both from EDS and XRD.     

Synthesis and characterization of Cu2ZnSnSe4 nanotube arrays on fluorine-doped tin oxide glass substrates

Highly ordered arrays of Cu₂ZnSnSe₄ nanotubes have been successfully synthesized on fluorine-doped tin oxide glass substrate using ZnO nanorod arrays as sacrificial templates. The structure, morphology and optical properties of the Cu₂ZnSnSe₄ arrays were characterized by X-ray diffraction, Raman spectrometry, field-emission scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray, and UV–Vis absorption spectroscopy. The diameter and length of the Cu₂ZnSnSe₄ nanotubes can be adjusted by tuning the diameter and length of the ZnO nanorods. In addition, the effect of the length on the performance of the photoelectrochemical cells was also investigated.     

A density functional theory study on the adsorption and dissociation of N2O on Cu2O(1 1 1) surface

Density functional theory has been employed to investigate the adsorption and the dissociation of an N₂O at different sites on perfect and defective Cu₂O(1 1 1) surfaces. The calculations are performed on periodic systems using slab model. The Lewis acid site, Cu_CUS, and Lewis base site, O_SUF are considered for adsorption. Adsorption energies and the energies of the dissociation reaction N₂O → N₂ + O(s) at different sites are calculated. The calculations show that adsorption of N₂O is more favorable on Cu_CUS adsorption site energetically. Cu_CUS site exhibits a very high activity. The Cu_CUS-N₂O reaction is exothermic with a reaction energy of 77.45 kJ mol⁻¹ and an activation energy of 88.82 kJ mol⁻¹, whereas the O_SUF-N₂O reaction is endothermic with a reaction energy of 205.21 kJ mol⁻¹ and an activation energy of 256.19 kJ mol⁻¹. The calculations for defective surface indicate that O vacancy cannot obviously improve the catalytic activity of Cu₂O.     

H2对Ar稀释SiH4等离子体CVD制备多晶硅薄膜的影响

以SiH₄，Ar和H₂为反应气体，采用射频等离子体化学气相沉积方法在300℃下制备了低温多晶Si薄膜.实验发现，反应气体中H₂的比例是影响薄膜结晶质量的重要因素，在适量的H₂比例下制备的多晶Si薄膜具有结晶相体积分数高，氢含量低，生长速率快、抗杂质污染等特性. 关键词： 低温多晶Si薄膜 等离子体CVD 4')" href="#">Ar稀释SiH₄ 2比例')" href="#">H₂比例     

The Raman spectra and cross-sections of the ν2 band of H2O, D2O, and HDO

We report the experimental Raman spectra of the ν₂ band of H₂O, D₂O, and HDO in the vapor phase at room temperature. A complete interpretation of the Raman intensities is carried out employing the variational rovibrational wavefunctions obtained from a Hamiltonian in Radau coordinates and an ab initio polarizability surface at 514.5 nm. We show the importance of the rotation-vibration coupling to obtain the correct line intensities. Several tables with the assignments of the individual rotational-vibrational transitions and their Raman scattering strengths are reported. From these tables, the ν₂ Raman spectra can be simulated up to 2000 K for H₂O, and up to 300 K for D₂O and HDO.     

Phase relations in the ZnO-V2O5-K2O system

The subsolidus phase relations of a ZnO-V 2 O 5-K 2 O system are investigated by X-ray powder diffraction.There is 1 ternary compound,11 binary compounds and 14 three-phase regions in this system.The phase diagrams of V 2 O 5 K 2 O with the K 2 O content ranging from 0 to 71 mol% and pseudo-binary system of ZnO-K 2 ZnV 2 O 7 are also studied by X-ray powder diffraction and differential thermal analysis methods.