Growth of Cu2ZnSnS4 thin films using sulfurization of stacked metallic films

We fabricated Cu₂ZnSnS₄ (CZTS) thin films through sulfurization of stacked metallic films. Three types of Cu-Zn-Sn metallic films, i.e., Cu-rich, Cu-correct and Cu-poor precursor films were sputtered onto Mo-coated glass. The sulfurization of stacked Cu-Zn-Sn alloy films was performed at a relatively high temperature, 570 °C, with S-powder evaporation. CZTS films from Cu-rich and Cu-correct precursors showed a Cu_2 − xS phase on the film surface, while CZTS films from Cu-poor precursors didn't show the Cu_2 − xS phase. However, all films didn't exhibit any extra secondary phase and exhibited good crystalline textures even with Cu-ratio differences in metallic precursor films. Fabricated CZTS films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and Raman scattering measurements. SEM cross-section images of CZTS films showed that Cu-poor CZTS films were grown with more smooth film surface compared with other types of CZTS films.     

Hot-injection synthesis and characterization of quaternary Cu2ZnSnSe4 nanocrystals

Cu₂ZnSnSe₄ (CZTSe) is one of promising materials in the use of absorber layers of solar cells. It contains earth-abundant elements of zinc and tin, a near-optimal direct band gap of ∼ 1.5 eV, as well as a large absorption coefficient ∼ 10⁴ cm-1. The CZTSe nanocrystals in oleylamine (OLA) was successfully prepared via hot-injection method. The characterization of its structure, composition, morphology and absorption spectra were done using powder X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and UV-vis absorption spectra. The results revealed that the monodispersed nanocrystals were single phase polycrystalline within the range of 15-20 nm. Optical measurements showed a direct band gap of 1.52 eV, which was optimal for low cost solar cells. The capping property of OLA was also demonstrated by examining Fourier Transform Infrared Spectroscopy (FTIR) feature peaks of CZTSe and OLA, respectively.     

Green hydrothermal synthesis and characterization of CdO2 nanoparticles

A green hydrothermal method has been developed for the synthesis of CdO₂ nanoparticles from Cd(OH)₂ powder and 6 vol.% H₂O₂ aqueous solution at 80-150 °C. The characterization results from X-ray diffraction, transmission electron microscopy, and thermal gravimetric and differential scanning calorimetry analysis disclosed that the resultant products were pure cubic phase CdO₂ nanoparticles with the sizes in the range of about 11-13 nm. The UV-vis absorption spectra revealed that the as-synthesized CdO₂ nanoparticles had similar optical band gaps of about 3.85 eV. The Raman spectra of the as-synthesized CdO₂ nanoparticles displayed two obvious peaks at about 348 and 830/833 cm^-1, a characteristic of pyrite-type IIB-peroxides.     

Cu2ZnSnS4 solar cells prepared with sulphurized dc-sputtered stacked metallic precursors

In the present work we report the details of the preparation and characterization results of Cu₂ZnSnS₄ (CZTS) based solar cells. The CZTS absorber was obtained by sulphurization of dc magnetron sputtered Zn/Sn/Cu precursor layers. The morphology, composition and structure of the absorber layer were studied by scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction and Raman scattering. The majority carrier type was identified via a hot point probe analysis. The hole density, space charge region width and band gap energy were estimated from the external quantum efficiency measurements. A MoS₂ layer that formed during the sulphurization process was also identified and analyzed in this work. The solar cells had the following structure: soda lime glass/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Al grid. The best solar cell showed an open-circuit voltage of 345 mV, a short-circuit current density of 4.42 mA/cm², a fill factor of 44.29% and an efficiency of 0.68% under illumination in simulated standard test conditions: AM 1.5 and 100 mW/cm².     

The crystallisation of Cu2ZnSnS4 thin film solar cell absorbers from co-electroplated Cu-Zn-Sn precursors

The best CZTS solar cell so far was produced by co-sputtering continued with vapour phase sulfurization method. Efficiencies of up to 5.74% were reached by Katagiri et al. The one step electrochemical deposition of copper, zinc, tin and subsequent sulfurization is an alternative fabrication technique for the production of Cu₂ZnSnS₄ based thin film solar cells. A kesterite based solar cell (size 0.5 cm²) with a conversion efficiency of 3.4% (AM1.5) was produced by vapour phase sulfurization of co-electroplated Cu-Zn-Sn films. We report on results of in-situ X-ray diffraction (XRD) experiments during crystallisation of kesterite thin films from electrochemically co-deposited metal films. The kesterite crystallisation is completed by the solid state reaction of Cu₂SnS₃ and ZnS. The measurements show two different reaction paths depending on the metal ratios in the as deposited films. In copper-rich metal films Cu₃Sn and CuZn were found after electrodeposition. In copper-poor or near stoichiometric precursors additional Cu₆Sn₅ and Sn phases were detected. The formation mechanism of Cu₂SnS₃ involves the binary sulphides Cu_2 − xS and SnS₂ in the absence of the binary precursor phase Cu₆Sn₅. The presence of Cu₆Sn₅ leads to a preferred formation of Cu₂SnS₃ via the reaction educts Cu_2 − xS and SnS₂ in the presence of a SnS₂(Cu₄SnS₆) melt. The melt phase may be advantageous in crystallising the kesterite, leading to enhanced grain growth in the presence of a liquid phase.     

Preparation of Cu2ZnSnS4 thin films by sulfurization of stacked metallic layers

Stacked precursors of Cu, Sn, and Zn were fabricated on glass/Mo substrates by electron beam evaporation. Six kinds of precursors with different stacking sequences were prepared by sequential evaporation of Cu, Sn, and Zn with substrate heating. The precursors were sulfurized at temperatures of 560 °C for 2 h in an atmosphere of N₂ + sulfur vapor to fabricate Cu₂ZnSnS₄ (CZTS) thin films for solar cells. The sulfurized films exhibited X-ray diffraction peaks attributable to CZTS. Solar cells using CZTS thin films prepared from six kinds of precursors were fabricated. As a result, the solar cell using a CZTS thin film produced by sulfurization of the Mo/Zn/Cu/Sn precursor exhibited an open-circuit voltage of 478 mV, a short-circuit current of 9.78 mA/cm², a fill factor of 0.38, and a conversion efficiency of 1.79%.     

Decoration of carbon nanotubes with nearly monodisperse MFe2O4 (MFe2O4, M = Fe, Co, Ni) nanoparticles

Magnetic monodisperse ferrite MFe₂O₄ (M = Fe, Co, Ni) nanoparticles have been successfully deposited on carbon nanotubes (CNTs) by in situ high-temperature hydrolysis and inorganic polymerization of metal salts and CNTs in polyol solution. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectrometry (EDS) and vibrating sample magnetometer (VSM) investigations were used to characterize the final products. The influencing factors for formation of CoFe₂O₄ nanoparticles along CNTs have also been discussed briefly. The main advantage of this synthetic strategy is that it is beneficial for the fabrication of magnetic CNTs with a compact layer of nanoparticles and could be extended to prepare series of ferrite/CNTs nanocomposites via the substitution of metal cations.     

Synthesis and spectroscopic investigations of Mn3O4 nanoparticles

Trimanganese tetraoxide (Mn₃O₄) nanoparticles have been synthesized via hydrothermal process. Nevertheless, homogeneous nanoparticles of Mn₃O₄ with platelet lozange shape were obtained. The crystallite size ranged from 40 to 70 nm. The Mn₃O₄ product was investigated by X-ray diffraction, transmission electron microscopy (MET), and impedance spectroscopy. Electrical conductivity measurements showed that the as-synthesized Mn₃O₄ nanomaterial has a conductivity value which goes from 1.8 10⁻⁷ Ω⁻¹ cm⁻¹ at 298 K, to 23 10⁻⁵ Ω⁻¹ cm⁻¹ at 493 K. The temperature dependence of the conductivity between 298 and 493 K obeys to Arrhenius law with an activation energy of 0.48 eV.     

Photocatalytic degradation of RhB over MgFe2O4/TiO2 composite materials

MgFe₂O₄/TiO₂ (MFO/TiO₂) composite photocatalysts were successfully synthesized using a mixing-annealing method. The synthesized composites exhibited significantly higher photocatalytic activity than a naked semiconductor in the photodegradation of Rhodamine B. Under UV and visible light irradiation, the optimal percentages of doped MgFe₂O₄ (MFO) were 2 wt.% and 3 wt.%, respectively. The effects of calcination temperature on photocatalytic activity were also investigated. The origin of the high level of activity was discussed based on the results of X-ray diffraction, UV-vis diffuse reflection spectroscopy, scanning electron microscopy, transmission electron microscopy, and nitrogen physical adsorption. The enhanced activity of the catalysts was mainly attributed to the synergetic effect between the two semiconductors, the band potential of which matched suitably.     

Structure and phase relations in the 2(CuInS2)-Cu2ZnSnS4 solid solution system

The intermixing of roquesite (CuInS₂) and kesterite (Cu₂ZnSnS₄), i. e. Cu(In_x(ZnSn)_1−xS₂ was investigated by a combination of neutron and X-ray powder diffraction. Samples with 0 ≤ × ≤ 1 were synthesized by a solid state reaction of the pure elements in evacuated silica tubes at 800 °C and cooled with a 10 K/h rate after the final annealing. The structural parameters of CuIn_x(ZnSn)_1−xS₂ were determined by simultaneous Rietveld refinement of neutron and X-ray diffraction data. The microstructure and chemical composition of the samples were investigated by electron microprobe analysis. A broad miscibility gap exists in the region 0.4 ≤ × < 0.8 indicated by the coexistence of two phases, an In-rich (x ~ 0.77) and a Zn-Sn-rich (x ~ 0.33) phase. Cu(In_x(ZnSn)_1−xS₂ mixed crystals with 0 ≤ x < 0.4 crystallize in the kesterite type structure, and with 0.8 ≤ × ≤ 1.0 in the chalcopyrite type structure. In the latter In, Zn and Sn are disordered on the In site. In the mixed crystals the lattice constant a and c show a linear dependence on chemical composition, whereas the tetragonal deformation Δ = 1−c/2a varies nonlinearly. Moreover in the mixed crystal with x ~ 0.15 the tetragonal deformation is equal zero and thus its structure is characterized by a pseudo-cubic unit cell.     

Aqueous bath process for deposition of Cu2ZnSnS4 photovoltaic absorbers

Chemical bath deposition and ion exchange were used to incorporate copper, zinc, tin and sulfur into a thin film precursor stack. The stack was then sulfurized to form the photovoltaic absorber material Cu₂ZnSnS₄ (CZTS). The morphology and elemental composition of the films at each process stage were analyzed by Auger electron spectroscopy and scanning electron microscopy, and the structural and optical properties of the sulfurized film were determined by a combination of X-ray diffraction, Raman scattering, and diffuse reflectance UV-Vis spectroscopy. Compositionally uniform microcrystalline CZTS with kesterite structure and a bandgap of 1.45 eV were observed. A preliminary solar cell device was produced exhibiting photovoltaic and rectifying behavior.     

Synthesis of Co3O4 nanoparticles via the CTAB-assisted method

Cobalt oxide (Co₃O₄) nanoparticles were successfully synthesized by the cetyltrimethylammonium bromide (CTAB)-assisted method at normal pressure for the first time. The structure and morphology of the as-prepared Co₃O₄ nanoparticles were characterized by powder X-ray diffracton (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and N₂-sorption analysis. XRD studies indicated that the as-prepared product was well-crystallized cubic phase of Co₃O₄ with a cell constant of α = 8.0722 Å. The EM images showed that the obtained Co₃O₄ sample consisted of dispersive quasi-spherical particles with the size ranged from 15 to 25 nm.     

Flame-made single phase Zn2TiO4 nanoparticles

Using zinc naphthenate and titanium tetra isopropoxide (1:1 mol.%) dissolved in ethanol as precursors, single phase Zn₂TiO₄ nanoparticles were synthesized by the flame spray pyrolysis technique. The Zn₂TiO₄ nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). The BET surface area (SSA_BET) of the nanoparticles was measured by nitrogen adsorption. The average diameter of Zn₂TiO₄ spherical particles was in the range of 5 to 10 nm under 5/5 (precursor/oxygen) flame conditions. All peaks can be confirmed to correspond to the cubic structure of Zn₂TiO₄ (JCPDS No. 25-1164). The SEM result showed the presence of agglomerated nanospheres with an average diameter of 10-20 nm. The crystallite sizes of spherical particles were found to be in the range of 5-18 nm from the TEM image. An average BET equivalent particle diameter (d_BET) was calculated using the density of Zn₂TiO₄.     

Synthesis of micro-sized Sb2O3 hierarchical structures by carbothermal reduction method

Micro-sized Sb₂O₃ hierarchical structures were prepared by carbothermal reduction method, using antimony doped tin oxide (ATO) nanoparticles and graphite powder as source materials. The products were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and field-emission scanning electron microscopy (FE-SEM). Furthermore, the possible growth mechanism of the as-synthesized samples was discussed. The room-temperature photoluminescence (PL) measurement exhibited one relatively strong violet emission peak at about 420 nm under the 325 nm excitation wavelength and another violet emission peak, about three times stronger in intensity than the former, at about 435 nm under the 365 nm excitation wavelength. In addition, the optimal excitation wavelength of 363 nm was obtained and the luminescence causes were speculated.     

Synthesis of worm-like Ag2S nanocrystals in W/O reverse microemulsion

High-aspect-ratio of worm-like Ag₂S nanocrystal with length up to several micrometers and a diameter of 25-50 nm has been successfully prepared by a Triton X-100/cyclohexane/hexanol/water W/O reverse microemulsion in the presence of TAA (Thioacetamide) as a sulfur source and EDTA (ethylene diamine tetraacetic acid) as a chelating ligand. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and UV-vis diffuse reflectance absorption spectra. The results indicate that the morphology and size of Ag₂S nanocrystal can be readily controlled by modulating the mole ratio of Ag⁺ to EDTA, the molar ratio of water to surfactant (ω₀), and the aging time.     

Facile synthesis and electrochemical properties of Mn3O4 nanoparticles with a large surface area

Mn₃O₄ nanoparticles were prepared by a novel oxidation-precipitation method at a low temperature. The crystal phase, microstructure, surface area and electrochemical properties of the products were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), N₂ adsorption-desorption isotherms and cyclic voltammetry (CV). The results indicate that the addition of citric acid and tartaric acid remarkably reduced the particle size and increased the specific surface area of Mn₃O₄ nanoparticles. The samples prepared by the addition of citric acid and tartaric acid have a narrow particle size distribution of 5-10 nm, a surface area of 119 and 122 m²/g, and a capacitance of 171 and 172 F g⁻¹, respectively.     

Low temperature synthesis and optical properties of CaTiO3 nanoparticles from Ca(NO3)2·4H2O and TiO2 nanocrystals

Choosing low-melting-point Ca(NO₃)₂·4H₂O and high-reactive-activity TiO₂ nanocrystals as the raw materials, a simple and cost-effective route was developed for the synthesis of CaTiO₃ nanoparticles at 600 °C, which is much lower than that (about 1350 °C) used in the conventional solid state reaction methods. X-ray diffraction, energy dispersive X-ray spectroscopy and field emission scanning electron microscopy revealed the formation of orthorhombic phase CaTiO₃ nanoparticles with oxygen-deficiency at the surface. UV-vis absorption spectrum of the as-obtained CaTiO₃ nanoparticles displayed an absorption peak centered at around 325 nm (3.8 eV), together with a tail at lower energy side. Room temperature photoluminescence spectrum of the as-obtained CaTiO₃ nanoparticles upon laser excitation at 325 nm demonstrated a strong and broad visible light emission ranging from about 527 to 568 nm, which may be originated from the surface states and defect levels.     

The enhanced visible light photocatalytic activity of nanosheet-like Bi2WO6 obtained by acid treatment for the degradation of rhodamine B

Bi₂WO₆ samples were fabricated by chemical solution decomposition (CSD) method and nanosheet-like Bi₂WO₆ samples could be obtained by concentrated nitric acid treatment at 70 °C for 20 min. The products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and UV-vis diffuse reflectance spectra. Photocatalytic activities of the samples were evaluated by the degradation of rhodamine B (RhB) under visible light irradiation. The temperature of acid treatment obviously influenced morphology and the visible light photocatalytic activity of the Bi₂WO₆ samples. The nanosheet-like Bi₂WO₆ photocatalysts obtained by acid treatment exhibited the highest photocatalytic activity under visible light irradiation.     

Synthesis and magnetic behavior of spinel FeAl2O4 nanoparticles

Nanocrystalline FeAl₂O₄ has been synthesized from furnace heating of corresponding iron and aluminium acetylacetonate complexes. The nanoparticles obtained were characterized using powder X-ray diffraction (XRD), EDX and transmission electron microscopy (TEM). The particles were faceted with a diameter in the range of 10-20 nm. The magnetic property of the FeAl₂O₄ nanoparticles was studied for the first time by plotting M vs H hysteresis curves, at different temperature and also by recording the temperature dependence of zero-field-cooled M_ZFC and field-cooled M_FC magnetization curves. On decreasing the temperature to 4 K, the magnetization shows deviation from linear behavior.     

Third-order optical nonlinear absorption in Bi1.95La1.05TiNbO9 thin films

Single phase Bi_1.95La_1.05TiNbO₉ (LBTN-1.05) thin films with a layered aurivillius structure have been fabricated on fused silica substrates by pulsed laser deposition at 700 °C. The X-ray diffraction pattern revealed that the films are single-phase aurivillius. The band gap, linear refractive index and linear absorption coefficient were obtained by optical transmittance measurements. The film exhibits a high transmittance (> 70%) in visible-infrared region and the dispersion relation of the refractive index vs. wavelength follows the single electronic oscillator model. The nonlinear optical absorption property of the film was determined by the single beam Z-scan method using 800 nm with a duration of 100 fs. A large positive nonlinear absorption coefficient β = 5.95 × 10^− 8 m/W was determined experimentally. The results showed that the LBTN-1.05 is a promising material for applications in absorbing-type optical devices.