Effect of annealing on the electrodeposited Cu2O films for photoelectrochemical hydrogen generation

Cu₂O films were electrodeposited on stainless steel substrates followed by Ar annealing for photoelectrochemical hydrogen generation. Plating variables including time and pH for the plating bath were explored to obtain desirable film qualities. X-ray diffraction (XRD) patterns indicated that the as-deposited Cu₂O films exhibited preferred orientations in (200) and (111) planes from the plating bath of pH 9 and pH 11, respectively. Images from scanning electron microscope (SEM) revealed pyramid-like grains in 1 µm size for the Cu₂O films from pH 9 plating bath and large plate-like grains in 3-8 µm size from pH 11 plating bath. Identical results from SEM and XRD were obtained from the Cu₂O films at longer plating time. After annealing at 350 °C for 30 and 60 min, the Cu₂O phase was nicely maintained but SEM images demonstrated coarser grains. Photoelectrochemical activity for H₂ generation was obtained on the Cu₂O films before and after annealing by recording relevant photoelectrochemical currents at − 0.3 V in 0.5 M aqueous Na₂SO₄ solution. For the Cu₂O films from both baths, substantial increments in photoelectrochemical current were observed for the annealed samples as opposed to as-deposited ones. The largest photoelectrochemical current was obtained at 0.143 mA/cm² from the Cu₂O film of pH 9 plating bath with 60 min annealing, which exhibited a 560% increase over the as-deposited sample. We attributed the enhanced photoelectrochemical current to the improved crystallinity and reduced defects for the annealed Cu₂O films.     

Opto-electronic properties of sputter-deposited Cu2O films treated with rapid thermal annealing

Cu₂O thin films were first deposited using magnetron sputtering at 200 °C. The samples produced were then annealed by a rapid thermal annealing (RTA) system at 550 °C in a protective atmosphere with or without the addition of oxygen. After annealing, various Cu₂O and CuO films were formed. These films were characterized, as a function of oxygen concentration in RTA, using UV-VIS photometer, four-point probe, and Hall measurement system. The results show that these Cu₂O thin films annealed at 550 °C with more than 1.2% oxygen added in the protective argon atmosphere would transform into the CuO phase. Apparently, the results of RTA are sensitive to the amount of oxygen added in the protective atmosphere. The resistivity of these Cu₂O thin films decreases with the increase in the oxygen amount in the annealing atmosphere, most likely due to the increase in carrier mobility. In addition, Cu₂O/ZnO (doped with AlSc) junctions were produced at 200 °C and annealed. The rectifying effect of P-N junction disappeared after annealing, probably due to the damage of p-n interface, which directly causes current leakage at the junction.     

Effects of Ag contents and deposition temperatures on the electrical and optical behaviors of Ag-doped Cu2O thin films

Cu₂O-Ag thin films were co-deposited by reactive sputtering on glass substrates. During deposition, Ag contents and deposited temperatures were varied. After deposition, a UV-VIS-NIR photometer and a Hall measurement system were used to characterize the optical and electrical properties of these films. The results showed that the Cu₂O-Ag thin films had a decreased optical transmittance with the increase of Ag contents. The resistivity was also decreased, which is most likely due to the formation of Ag phase. Through the measurement of photo-induced conductivity, it was found that, when Ag concentration was at 4 at.%, the film had the highest increase in conductivity under light irradiation. This is due to the co-existence of Ag₂O and Cu₂O. However, when deposited at a temperature higher than room temperature, the photo-induced conductivity of this film became less obvious, apparently due to the dissociation of Ag₂O. The results of Photoluminescence (PL) measurement confirmed that the Cu₂O-Ag(4 at.%) sample might produce more electron-hole pairs than other samples, which caused the increase of conductivity.     

Effect of annealing on the characteristics of Au layers grown on the high-temperature deposited Ni50Fe50 layers

80 nm-thick Ni₅₀Fe₅₀ layers were sputter-deposited on glass substrates at 400 °C and then Au layers were sputter-deposited on the Ni₅₀Fe₅₀ layers. The Au/Ni₅₀Fe₅₀ bilayer films were annealed in a vacuum of 5×10⁻⁴ Pa from 250 to 450 °C for 30 min or 90 min. The characteristics of the Au layers were studied by Auger electron spectroscopy, field emission scanning electron microscopy, X-ray diffraction and a four-point probe technique. When the annealing temperature reaches 450 °C, Fe and Ni atoms diffuse markedly into the Au layer and the Fe content is more than the Ni content. When the annealing temperature is lower than 450 °C, the grain size of the Au layers does not change markedly with annealing temperature. However, as the annealing temperature reaches 450 °C, the annealing promotes the grain growth of the Au layer. As the annealing temperature exceeds 300 °C, the resistivity of the bilayer films increases with increasing annealing temperature. The diffusion of Fe and Ni atoms into the Au layer results in an increase in the resistivity of the annealed bilayer film. Large numbers of Fe and Ni atoms diffusing into the Au layer of the annealed Au/Ni₅₀Fe₅₀ bilayer film lead to a significant decrease in the lattice constant of the Au layer.     

Preparation and characterization of transparent semiconductor RuO2-SiO2 films synthesized by sol-gel route

RuO₂-SiO₂ thin films with different Si/Ru molar ratios were prepared by the sol-gel method, using the hydrate ruthenium (III) chloride (RuCl₃·3.5H₂O) and tetraethylorthosilicate as precursors. The crystal structure, resistivity, chemical bonding configuration, transmittance, carrier concentration, and mobility of the RuO₂-SiO₂ films were investigated before and after annealing in N₂ ambient at 400-700 °C. The resistivity of the RuO₂-SiO₂ films with different Si/Ru molar ratios decreased abruptly after annealing at 400-700 °C. On the other hand, RuO₂ phase precipitated in the RuO₂-SiO₂ films with different Si/Ru molar ratios after annealing. Fourier transform infrared spectroscopy spectra indicated that the water absorption occurs for as-deposited RuO₂-SiO₂ films with different Si/Ru molar ratios. The transmittance of all RuO₂-SiO₂ films presented transmittance maximums after annealing at 700 °C. The carrier concentration and mobility of RuO₂-SiO₂ films are related to the Si/Ru molar ratios and the annealing temperature. This study discusses the connection among the material properties of the RuO₂-SiO₂ films and how they are influenced by the Si/Ru molar ratios and the annealing temperatures of RuO₂-SiO₂ films.     

Single-step sputtered Cu2SnSe3 films using the targets composed of Cu2Se and SnSe2

Cu₂SnSe₃ thin films were prepared by single-step D.C. sputtering at 100-400 °C for 3 h using targets composed of Cu₂Se and SnSe₂ in three different ratios of 2/1 (target A), 1.8/1 (target B), and 1.6/1 (target C). The advantages of self-synthesized SnSe₂ instead of commercially available SnSe for depositing Cu₂SnSe₃ thin films were demonstrated. Effects of target composition and substrate temperature on the properties of Cu₂SnSe₃ thin films were investigated. Structure, surface morphology, composition, electrical and optical properties at different process conditions were measured. The 400 °C-sputtered films obtained from target B display with direct band gap of 0.76 eV, electrical resistivity of 0.12 Ω cm, absorption coefficient of 10⁴-10⁵ cm^− 1, carrier concentration of ∼ 1.8 × 10¹⁹ cm^− 3, and electrical mobility of 2.9 cm²/V s.     

Annealing effect on crystallization behavior of cubic MgxZn1−xO films on A-plane and M-plane sapphire

Cubic Mg_xZn_1−xO thin films with Mg composition around 70% were deposited on A-plane and M-plane sapphire substrates by rf-reactive magnetron sputtering. Measured structural and optical properties of these thin films indicated an optimal annealing temperature of 700 °C which produced high quality cubic MgZnO thin films on both substrates. Moreover, when the annealing temperature exceeded 750 °C, a much rougher surface resulted, and several large mosaic particles on the surface of the annealed films appeared. From EDX results, the Mg composition was lower than that found in other sections of the annealed films. We attributed this to thermally induced reconstruction of the crystallites. This phenomenon was more obvious for annealed MgZnO films on A-plane sapphire than that on M-plane sapphire. Thermal expansion mismatch with the substrate is the principal reason.     

AC conductivity and dielectric properties of Sb2Te3 thin films

Sb₂Te₃ films of different thicknesses, in the thickness range 300-620 nm, were prepared by thermal evaporation. X-ray analysis showed that the as-deposited Sb₂Te₃ films are amorphous while the source powder and annealed films showed a polycrystalline nature. The AC conductivity and dielectric properties of Sb₂Te₃ films have been investigated in the frequency range 0.4-100 kHz and temperature range 303-373 K. The AC conductivity σ_AC(ω) was found to obey the power law ω^s where s?1 independent of film thickness. The temperature dependence of both AC conductivity and the exponent s can be reasonably well interpreted by the correlated barrier hopping (CBH) model. The experimental results of the dielectric constant ε₁ and the dielectric loss ε₂ are frequency and temperature dependent and thickness independent. The maximum barrier height W_M calculated from dielectric measurements according to the Guintini equation agrees with that proposed by the theory of hopping of charge carriers over a potential barrier as suggested by Elliott for chalcogenide glasses. The effect of annealing at different temperatures on the AC conductivity and dielectric properties was also investigated. Values of σ_AC, ε₁ and ε₂ were found to increase with annealing treatment due to the increase of the degree of ordering of the investigated films. The Cole-Cole plots for the as-deposited and annealed Sb₂Te₃ films have been used to determined the molecular relaxation time τ. The temperature dependence of τ indicates a thermally activated process.     

Spray pyrolyzed β-In2S3 thin films: Effect of postdeposition annealing

Indium sulfide thin films prepared using spray pyrolysis, with In/S ratio 2/3 in the solution, were annealed in vacuum at 300 and 400 °C. The effect of this treatment on properties of the films was studied using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, optical absorption, transmission and electrical measurements. Optical constants of the films were calculated using the envelope method. Annealing did not affect the optical properties of the film much, but the resistivity of the films showed a drastic decrease and the grain size increased. In₂S₃ thin films have potential use as buffer layer in photovoltaic heterojunction devices.     

SiO2 layer thickness effects on the (001) texture of FePtCu:SiO2 nanocomposite films

The influence of SiO₂ layer thickness of (Fe₅₂Pt₄₈)₈₈Cu₁₂:SiO₂ multilayer nanocomposite films on their structural and magnetic properties were investigated. The films were deposited on (001) textured FePt films, and then annealed at 873 K. The crystalline texture of (Fe₅₂Pt₄₈)₈₈Cu₁₂:SiO₂ films changes drastically with respect to the thickness of the SiO₂ layers. In the film with 50-Å thick SiO₂ layers, the (111) peak was strong although the (001) orientation is dominant, and self-organized spherical FePtCu particles were formed in the SiO₂ matrix. However, in the film with 19-Å thick SiO₂ layers, flat FePt grains with perfect (001) orientation were obtained. In addition, twins with different crystalline orientations were seen in the above films with different thicknesses of the SiO₂ layers. Accordingly, different perpendicular hysteresis loops were obtained.     

Electrochemical reduction of CO2 by Cu2O-catalyzed carbon clothes

Cu₂O cubes with average edge lengths of 640 nm were prepared by a chemical reduction approach. The as-synthesized Cu₂O particles were deposited on carbon clothes for electrochemical characterizations in cyclic voltammetry (CV) and potentiostatic measurements. In 0.5 M NaOH electrolytes saturated with N₂ or CO₂, both the Cu₂O and carbon clothes were stable at the potential range of 0 to − 1.7 V. Comparisons in the current responses from the CV and potentiostatic measurements suggested the Cu₂O with notable catalytic abilities for the CO₂ reduction. The mass activity was estimated at 0.94 mA/mg. Chemical analysis from gas chromatography confirmed the methanol to be the predominant product.     

Effects of hydrogen annealing on the microstructure and optical properties of single-phased Ag2O film deposited using direct-current reactive magnetron sputtering

Single-phased and (111)-oriented Ag₂O film deposited using direct-current reactive magnetron sputtering is annealed using different annealing temperatures (T_a) for 1 h in Ar and H₂ mixture. After hydrogen annealing, a very weak but clear Ag(200) diffraction peak begins to appear, and the Ag₂O diffraction peak weakens at T_a = 175 °C. However, the Ag diffraction peak becomes discernable at T_a = 190 °C. No Ag₂O diffraction peaks but rather Ag diffraction peaks are discerned at T_a = 200 °C. The hydrogen reduction effect can reduce the film's critical thermal decomposition temperature to 175 °C. After hydrogen annealing, the surface of the film evolutes from compact and uniform to osteoporosis, and then to a porous structure. Moreover, the optical properties of the film obviously change at T_a over 190 °C, indicating that the hydrogen reduction can significantly enhance the decomposition of Ag₂O due to H₂ dissociation on the surface followed by gaseous H₂O molecule formation and desorption.     

The properties of transparent semiconductor Zn1 − xTixO thin films prepared by the sol-gel method

Transparent semiconductor thin films of Zn_1 − xTi_xO (0 ≦ x ≦ 0.12) were deposited on alkali-free glass substrates by the sol-gel method. The effects of Ti addition on the crystallization, microstructure, optical properties and resistivity of ZnO thin films were investigated. The as-coated films were preheated at 300 °C, and then annealed at 500 °C in air ambiance. X-ray diffraction results showed all polycrystalline Zn_1 − xTi_xO thin films with preferred orientation along the (002) plane. Ti incorporated within the ZnO thin films not only decreased surface roughness but also increased optical transmittance and electrical resistivity. In the present study, the Zn_0.88Ti_0.12O film exhibited the best properties, namely an average transmittance of 91.0% (an increase of ~ 12% over the pure ZnO film) and an RMS roughness value of 1.04 nm.     

Degradation of thin films of YBa2Cu3O7 by annealing in air and in vacuum

The degradation of epitaxial thin films of YBa₂Cu₃O₇ has been studied as a function of annealing temperature in air and in vacuum; some samples had an evaporated overlayer of CaF₂. Degradation was monitored by the measurement of electrical properties after consecutive 30-min annealing treatments. The room-temperature resistance registered significant increases for all samples after annealing at temperatures above about 200°C; the critical current density at 77 K was degraded for annealing temperatures 400°C in air, and 200–250°C in vacuum. By annealing in oxygen at 550°C, electrical properties were restored in degraded bare YBCO samples annealed in vacuum, but not for those annealed in air.     

Multi-stage evaporation of Cu2ZnSnS4 thin films

Multi-stage evaporation is a well-established method for the controlled growth of chalcopyrite thin films. To apply this technique to the deposition of Cu₂ZnSnS₄ thin films we investigated two different stage sequences: (A) using Cu₂SnS₃ as precursor to react with Zn-S and (B) using ZnS as precursor to react with Cu-Sn-S. Both Cu₂SnS₃ and ZnS are structurally related to Cu₂ZnSnS₄. In case (A) the formation of copper tin sulphide in the first stage was realized by depositing Mo/SnS_x/CuS (1 < x < 2) and subsequent annealing. In the second stage ZnS was evaporated in excess at different substrate temperatures. We assign a significant drop of ZnS incorporation at elevated temperatures to a decrease of ZnS surface adhesion, which indicates a self-limited process with solely reactive adsorption of ZnS at high temperatures. In case (B) firstly ZnS was deposited at a substrate temperature of 150 °C. In the second stage Cu, Sn and S were evaporated simultaneously at varying substrate temperatures. At temperatures above 400 °C we find a strong decrease of Sn-incorporation and also a Zn-loss in the layers. The re-evaporation of elemental Zn has to be assumed. XRD measurements after KCN-etch on the layers prepared at 380 °C show for both sample types clearly kesterite, though an additional share of ZnS and Cu₂SnS₃ can not be excluded. SEM micrographs reveal that films of sample type B are denser and have larger crystallites than for sample type A, where the porous morphology of the tin sulphide precursor is still observable. Solar cells of these absorbers reached conversion efficiencies of 1.1% and open circuit voltages of up to 500 mV.     

Preparation, dielectric and ferroelectric properties of Pb5Ge3O11 and Pb5Ge2.85Si0.15O11 thin films fabricated by sol-gel process

Lead germanate-silicate (Pb₅Ge_2.85Si_0.15O₁₁) ferroelectric thin films were successfully fabricated on Pt/Ti/SiO₂/(100)Si substrates by the sol-gel process. The thin films were fabricated by multi-coating at preheating temperatures of 350 and 450 °C. After annealing the thin films at 600 °C, the films exhibited c-axis preferred orientation. The degree of c-axis preferred orientation of the thin films preheated at 350 °C was higher than that of films preheated at 450 °C. Grain growth was influenced by the annealing time. The thin films exhibited a well-saturated ferroelectric P-E hysteresis loop when preheated at 350 °C and annealed at 600 °C for 1.5 h. The values of the remanent polarization (Pr) and the coercive field (Ec) were approximately 2.1 μC/cm² and 100 kV/cm, respectively.     

Growth and structure characterization of epitaxial Bi2Sr2Co2Oy thermoelectric thin films on LaAlO3 (001)

Epitaxial Bi₂Sr₂Co₂O_y thin films with excellent c-axis and ab-plane alignments have been grown on (001) LaAlO₃ substrates by chemical solution deposition using metal acetates as starting materials. Microstructure studies show that the resulting Bi₂Sr₂Co₂O_y films have a well-ordered layer structure with a flat and clear interface with the substrate. Scanning electron microscopy of the films reveals a step-terrace surface structure without any microcracks and pores. At room temperature, the epitaxial Bi₂Sr₂Co₂O_y films exhibit a resistivity of about 2 mΩ cm and a seebeck coefficient of about 115 μV/K comparable to those of single crystals.     

Effect of H2S treatment on properties of CuInS2 thin films deposited by chemical spray pyrolysis at low temperature

CuInS₂ thin films were deposited by chemical spray of aqueous solutions containing CuCl₂, InCl₃ and thiourea at substrate temperature of 250 °C in air and subjected to annealing at 530 °C in H₂S atmosphere. Structure and composition before and after annealing were studied by XRD, EDS, XPS and Raman spectroscopy. As-sprayed films were low-crystalline, showed uniform distribution of elements in film thickness and no oxygen content. For the CuInS₂ films deposited from the solutions with [Cu²⁺] / [In³⁺] = 1.0 and 1.1, H₂S treatment for 30 min increased the chalcopyrite content up to 73% and 51%, respectively. Cu_XS phase in sprayed CIS films promotes the crystallite growth but retards the formation of chalcopyrite phase during H₂S treatment.     

Spray-pyrolysis Cd2SnO4 films for electrochemical applications

Conductive cadmium stannate (Cd₂SnO₄,) films were grown by a simple spray-pyrolysis technique using aerosols ultrasonically generated from solutions containing Cd(thd)₂(TMEDA) and ⁿBu₂Sn(AcAc)₂, and monoglyme as solvent (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate, TMEDA = N,N,N′,N′-tetramethylethylenediamine, AcAc = acethylacetonate). The overall film growing procedure was carried out at or below 400 °C thus allowing low-melting temperature materials like glass to be used as film substrates. Typical resistivity values of Cd₂SnO₄ films were found to be ∼ 2 · 10 ⁻³ Ωcm. The films exhibit excellent electrochemical activity with comparable or higher electron transfer rates than cadmium stannate films obtained via sol-gel methods at high annealing temperature.