Effect of laser incident energy on the structural,morphological and optical properties of Cu2ZnSnS4 (CZTS) thin films

The polycrystalline Cu₂ZnSnS₄ (CZTS) thin films have been prepared by pulsed laser deposition (PLD) method at room temperature. The laser incident energy was varied from 1.0 at the interval of 0.5–3.0 J/cm². The effect of laser incident energy on the structural, morphological and optical properties of CZTS thin films was studied by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and optical absorption. The studies reveal that an improvement in the structural, morphological and optical properties of CZTS thin films with increasing laser incident energy up to 2.5 J/cm². However, when the laser incident energy was further increased to 3.0 J/cm², leads to degrade the structural, morphological and optical properties of the CZTS thin films.     

Effects of hydrogen flow on properties of hydrogen doped ZnO thin films prepared by RF magnetron sputtering

The hydrogen doped ZnO (ZnO:H) thin films were deposited on quartz glass substrates by radio frequency magnetron sputtering. The doping characteristics of ZnO:H thin films with varied hydrogen flow ratio were investigated. At low hydrogen flow ratio (H₂/(H₂+Ar)≤0.02), the ZnO:H thin films exhibited dominant (002) peaks from X-ray diffraction and the lattice constants became smaller. The particles were mainly a columnar structure. The particles’ size became smaller, and the island-like structure appeared on the thin films surface. In addition, the low resistivity properties of ZnO:H thin films was ascribed to the increase of the carriers concentration and carriers mobility; When the hydrogen flow ratio was more than 0.02 (M≥0.02), two absorption bands at 1400–1800 cm^?1 and 3200–3900 cm^?1 were observed from the FT-IR spectra, which indicated that the ZnO:H thin films had typical Zn–H bonding, O–H bonding (hydroxyl), and Zn–H–O bonding (like-hydroxyl). The scanning electron microscope (SEM) results show that a large number of hydroxyl agglomeration formed an island-like structure on the thin films surface. The absorption peak at about 575 cm^?1 in the Raman spectra indicated that oxygen vacancies (V_O) defects were produced in the process of high hydrogen doping. In this condition, the low resistivity properties of ZnO:H thin films were mainly due to the increasing electron concentration resulted from V_O. Meanwhile, the Raman absorption peaks at approximately 98 cm^?1 and 436 cm^?1 became weaker, and the (002) XRD diffraction peak quenched and the lattice constants increased, which shows that the ZnO:H thin films no longer presented a typical ZnO hexagonal wurtzite structure. With the increasing of hydrogen flow ratio, the optical transmittance of ZnO:H thin films in the ultraviolet band show a clear Burstein–Moss shift effect, which further explained that electron concentration was increased due to the increasing V_O with high hydrogen doping concentration. Moreover, the optical reflectance of the thin films decreased, indicating the higher roughness of the films surface. It was noteworthy that etching effect of H plasma was obvious in the process of heavy hydrogen doping.     

连续离子层吸附反应沉积后硫化法制备柔性铜锌锡硫薄膜太阳电池

在柔性钼箔衬底上采用连续离子层吸附反应法(successive ionic layer absorption and reaction)制备ZnS/Cu2SnSx叠层结构的预制层薄膜,预制层薄膜在蒸发硫气氛、550 C温度条件下进行退火得到Cu2ZnSnS4吸收层.分别采用EDS,XRD,Raman,SEM表征吸收层薄膜的成分、物相和表面形貌.结果表明,退火后薄膜结晶质量良好,表面形貌致密.用在普通钠钙玻璃上采用相同工艺制备的CZTS薄膜表征薄膜的光学和电学性能,表明退火后薄膜带隙宽度为1.49 eV,在可见光区光吸收系数大于104cm 1,载流子浓度与电阻率均满足薄膜太阳电池器件对吸收层的要求.用上述柔性衬底上的吸收层制备Mo foil/CZTS/CdS/i-ZnO/ZnO:Al/Ag结构的薄膜太阳电池得到2.42%的效率,是目前报道柔性CZTS太阳电池最高效率.     

Preparation and characterization of Al doped ZnO thin films by PLD

This paper describes the effect of doping on the composition, surface morphology and optical, structural and electrical properties of Al doped ZnO thin films by pulsed laser deposition. SEM analysis shows that the crystalline nature of the deposited films decreases with an increase of Al doping concentration from 1% to 6%. In the AFM analysis, the surface roughness of the deposited films increases by increasing the doping concentration of Al. Al doping strongly influences the optical properties of the ZnO thin films. Optical transmittance spectra show a very good transmittance in the visible region (450–700 nm). The calculated optical band gap was found to be in the range from 3.405 to 3.464 eV. Structural analysis confirms that the increases of Al concentration decrease the crystallinity of the ZnO films and the particle size decreases from 45.7±0.09 to 28.0±0.02 nm. In the Raman analysis, the active mode of Al(=1%) doped ZnO films were observed at 434.81 cm⁻¹. The shifts of the active mode (_E2)$\left(E_2\right)$ show the presence of tensile stress in the deposited films. The electrical properties of the deposited films showed that the values of the Hall mobility was in the range between 2.51 and 10.64 cm²/V s and the carrier concentration between 15.7 and 0.78×10¹⁷ and the resistivity values between 1.59 and 10.97 Ωcm, depending on the doping concentration.     

Study on ferroelectric polarization induced resistive switching characteristics of neodymium-doped bismuth ferrite thin films for random access memory applications

The present work reports on resistive switching (RS) characteristics of Neodymium (Nd)-doped bismuth ferrite (BFO) layers. The Nd (2–10 at%) doped BFO thin film layers were deposited using a spray pyrolysis method. The structural analysis reveals that a higher Nd doping concentration in BFO leads to significant distortion of the prepared Nd:BFO thin films from rhombohedral to tetragonal characteristics. The morphological analysis shows that all the deposited Nd:BFO thin films have regularly arranged grains. The X-ray photoelectron spectroscopy (XPS) analysis reveals that the prepared Nd:BFO thin films have a higher Fe ³⁺/Fe ²⁺ratio and less oxygen vacancy (V_O) defects which enriches the ferroelectric characteristics in Nd:BFO layers. The polarization-electric field (P-E) and RS characteristics of the fabricated Nd:BFO-based RS device were examined. It was observed that the Nd (7 at%) doped BFO RS device shows large remnant polarization (P _r) of 0.21 μC/cm² and stable RS characteristics.     

Significantly reduced leakage currents in organic thin film transistors with Mn‐doped Bi2Ti2O7 high‐k gate dielectrics

We report the fabrication of organic thin‐film transistors (OTFTs) with high‐k gate dielectrics of Mn‐doped Bi₂Ti₂O₇ (BTO) films. 3% Mn‐doped BTO films deposited on polymer substrates by pulsed laser deposition at room temperature exhibit low leakage currents of 2.1 × 10^–8 A/cm² at an applied electric field of 0.3 MV/cm, while undoped BTO films show much higher leakage currents of 4.3 × 10^–4 A/cm². Mn doping effectively reduces the number of oxygen vacancies in the films and improves the electrical properties. Low operation voltage and significantly reduced leakage currents are demonstrated in pentacene‐based OTFTs with the Mn‐doped BTO gate dielectrics. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of bismuth on the electrical properties of Pb0.8Sn0.2Te thin films

D.C. conductivity and Hall coefficient studies were made on bismuth doped Pb_0.8Sn_0.2Te thin films in the temperature range 77–300 K. Hall coefficient and Hall mobility are found to decrease with the increase in doping density of bismuth. Films doped with even 0.3 at.% Bi changed fromp-type ton-type due to the donor action of bismuth in these films. Analysis of mobility-temperature data revealed that the lattice and defect scattering mechanisms are predominant in these films. Defect limited mobility is calculated for all the films and it is found to decrease with increase in doping concentration of bismuth suggesting the increase in defect density.     

Ag掺杂p型ZnO薄膜及其光电性能研究

采用超声喷雾热分解法在石英衬底上以醋酸锌水溶液为前驱体,以硝酸银水溶液为Ag掺杂源生长了Ag掺杂ZnO(ZnO：Ag)薄膜.研究了衬底温度对所得ZnO：Ag薄膜的晶体结构、电学和光学性质的影响规律.所得ZnO：Ag薄膜结构良好,在室温光致发光谱中检测到很强的近带边紫外发光峰,透射光谱中观测到非常陡峭的紫外吸收截止边和较高的可见光区透过率,表明薄膜具有较高的晶体质量与较好的光学特性.霍尔效应测试表明,在500℃下获得了p型导电的ZnO：Ag薄膜,载流子浓度为5.30×10¹⁵cm关键词： ZnO：Ag薄膜 p型掺杂 超声喷雾热分解 霍尔效应     

Effect of indium doping in CdO thin films prepared by spray pyrolysis technique

Preparation of transparent and conducting indium doped CdO thin films by spray pyrolysis on glass substrate is reported for various concentration of indium (2-8 wt%) in the spray solution. The electrical, optical and structural properties of indium doped CdO films were investigated using different techniques such as Hall measurement, optical transmission, X-ray diffraction and scanning electron microscope. X-ray analysis shows that the undoped CdO films are preferentially orientated along (2 0 0) crystallographic direction. Increase of indium doping concentration increases the films packing density and reorient the crystallites along (1 1 1) plane. A minimum resistivity of 4.843×10⁻⁴ Ω cm and carrier concentration of 3.73×10²⁰ cm⁻³ with high transmittance in the range 300-1100 nm were achieved for 6 wt% indium doping. The band gap value increases with doping concentration and reaches a maximum of 2.72 eV for 6 wt% indium doping from 2.36 eV of that of undoped film. The minimum resistivity achieved in the present study is found to be the lowest among the reported values for In-doped CdO films prepared by spray pyrolysis method.     

n-ZnO:Al/i-ZnO/n-CdS/p-Cu2ZnSnS4太阳能电池光伏特性的分析

具有高光吸收系数的半导体Cu₂ZnSnS₄ (CZTS)薄膜是一种新型太阳能电池材料. 本文对n-ZnO:Al/i-ZnO/n-CdS/p-CZTS结构的CZTS薄膜太阳能电池进行分析, 讨论CZTS薄膜的掺杂浓度、厚度、缺陷态和CdS薄膜的掺杂浓度、 厚度对太阳能电池转换效率的影响以及太阳能电池的温度特性. 分析表明, CZTS薄膜作为太阳能电池的主要光吸收层, CZTS薄膜的掺杂浓度和厚度的取值对太阳能电池的转换效率有显著影响, CZTS薄膜结构缺陷态的存在会导致太阳能电池性能的下降. CdS缓冲层的掺杂浓度、厚度对太阳能电池光伏特性的影响较小. 经结构参数优化得到的n-ZnO:Al/i-ZnO/n-CdS/p-CZTS薄膜太阳能电池的最佳光 伏特性为开路电压1.127 V、短路电流密度27.39 mA/cm²、填充因子87.5%、 转换效率27.02%,转换效率温度系数为-0.14%/K.     

Nonlinear optical properties of erbium doped zinc oxide (EZO) thin films

Undoped and Erbium (Er) doped zinc oxide (EZO) thin films were deposited on glass substrate by sol–gel method using spin coating technique with different doping concentration. EZO films were characterized using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), UV–VIS-NIR transmission and single beam z scan method under illumination of frequency doubled Nd:YAG laser. The deposited films were found to be well crystallized with hexagonal wurtzite structure having a preferential growth orientation along the ZnO (002) plane. A blue-shift was observed in the band gap of EZO films with increasing Er concentration. All the films exhibited a negative value of nonlinear refractive index (n₂) at 532 nm which is attributed to the two photon absorption and weak free carrier absorption. Third order nonlinear optical susceptibility, χ⁽³⁾ values of EZO films were observed in the remarkable range of 10^? 6 esu. EZO (0.4 at.%) sample was found to be the best optical limiter with limiting threshold of 1.95 KJ/cm².     

Effects of laser irradiation energy density on the properties of pulsed laser deposited ITO thin films

The properties of indium tin oxide (ITO) thin films, deposited at room temperature by simultaneous pulsed laser deposition (PLD), and laser irradiation of the substrate are reported. The films were fabricated from different Sn-doped In₂O₃ pellets at an oxygen pressure of 10 mTorr. During growth, a laser beam with an energy density of 0, 40 or 70 mJ/cm² was directed at the middle part of the substrate, covering an area of ∼1 cm². The non-irradiated (0 mJ/cm²) films were amorphous; films irradiated with 40 mJ/cm² exhibited microcrystalline phases; and polycrystalline ITO films with a strong 〈111〉> preferred orientation was obtained for a laser irradiation density of 70 mJ/cm². The resistivity, carrier density, and Hall mobility of the ITO films were strongly dependent on the Sn doping concentration and the laser irradiation energy density. The smallest resistivity of ∼1×10^-4 Ω cm was achieved for a 5 wt % Sn doped ITO films grown with a substrate irradiation energy density of 70 mJ/cm². The carrier mobility diminished with increasing Sn doping concentration. Theoretical models show that the decrease in mobility with increasing Sn concentration is due to the scattering of electrons in the films by ionized centers. PACS 81.15.Fg; 73.61.-r; 73.50.-h     

Structural, optical and electrical properties of molybdenum-doped cadmium oxide thin films prepared by spray pyrolysis method

Molybdenum-doped cadmium oxide films were prepared by a spray pyrolysis technique at a substrate temperature of 300?°C. The effect of doping on structural, electrical and optical properties were studied. X-ray analysis shows that the undoped CdO films are preferentially oriented along the (111) crystallographic direction. Molybdenum doping concentration increases the films?? packing density and reorients the crystallites along the (200) plane. A?minimum resistivity of 4.68×10^?4????cm with a maximum mobility of 75?cm²?V^?1?s^?1 is achieved when the CdO film is doped with 0.5?wt.% Mo. The band-gap value is found to increase with doping and reaches a maximum of 2.56?eV for 0.75?wt.% as compared to undoped films of 2.2?eV.     

Multiphonon resonant Raman scattering in N‐doped ZnO

Multiphonon resonant Raman scattering in N‐doped ZnO films was studied, and an enhancement of the resonant Raman scattering process as well as longitudinal optical (LO) phonon overtones up to the sixth order were observed at room temperature. The resonant Raman scattering intensity of the 1LO phonon in N‐doped ZnO appears three times as strong as that of undoped ZnO, which mainly arises from the defect‐induced Raman scattering caused by N‐doping. The nature of the 1LO phonon at 578 cm⁻¹ is interpreted as a quasimode with mixed A₁ and E₁ symmetry because of the defects formed in the ZnO lattice. In addition, the previously neglected impurity‐induced two‐LO‐phonon scattering process was clearly observed in N‐doped ZnO. Copyright © 2009 John Wiley & Sons, Ltd.     

Silicon doping of MBE-grown GaAs films

Two concentration ranges of silicon doping in MBE-grown GaAs films have been investigated in some detail. In lightly doped films, with a free-electron concentration of ≈10¹⁶cm^?3, low-temperature photoluminescence spectra have been analysed to develop a model to account for spectral features previously attributed to Ge and Si acceptor levels. In heavily doped films, a maximum free-electron concentration of ≈7×10¹⁸ cm^?3 has been obtained, which is only rather weakly dependent on growth conditions and the nature of the arsenic species (As₂ or As₄). Transmission electron microscopy has shown that no significant precipitation effects occur when higher Si fluxes are used but there is evidence for autocompensation. The maximum PL intensity (300 K) is found at a lower free electron concentration then with Sn-doped films, and is more sharply peaked, but there is no evidence for an anomalous Moss-Burstein shift.     

Germanium – the superior dopant in n‐type GaN

We present an experimental study about the influence of Si and Ge doping in GaN with focus on the occurring strain levels and overall crystalline quality. Extremely high quality samples were examined by means of Raman spectroscopy, demonstrating effective, n‐type doping concentrations up to the 5 × 10¹⁹ cm^–3 regime. By studying the full width at half maximum (FWHM) of the E₂(high) Raman mode with rising doping concentration, Ge is approved as the by far superior dopant if compared to Si. Even elevated nominal Ge concentrations yield corresponding FWHM values of just 3 cm^–1, a most competitive value even for bare bulk GaN samples. At the same time, the biaxial, compressive stress that is introduced by such high Ge doping amounts to just 0.2 GPa, in clear contrast to the particular case of silicon. Here, even moderate doping levels lead to tensile stress up to 1 GPa and consequently to a serious degeneration of the overall crystal quality as approved by our Raman analysis. Additionally, the examined high doping concentrations enable the observation of longitudinal optical phonon plasmon (LPP) modes in the Raman spectra, which serve as a direct tool for the determination of the effective doping concentration. A careful analysis of the LPP coupling at cryogenic and room temperature yields within the error interval identical free carrier concentrations in all germanium doped samples, pointing towards an energetically shallow nature of the dopant. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Characterization of Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript> Thin Films Prepared by RF Magnetron Sputtering

Zn₂SnO₄ (ZTO) is a stable semiconductor in ZnO–SnO₂ system and important transparent conducting oxide (TCO) predominantly used in optoelectronic devices. ZTO thin films were prepared by RF magnetron sputtering using Zn₂SnO₄ ceramic target in this paper. The effects of annealing temperatures and oxygen contents on characterization of ZTO thin films were studied. The results show that ZTO thin films prepared by RF magnetron sputtering are amorphous with an optical band gap of 3.22 eV. After annealing at 650°C in Ar atmosphere for 40 min, ZTO films possess a spinel structure with an optical band gap of 3.62 eV. The atomic force microscope (AFM) data of morphology reveals that the surface roughness of films is about 2 nm. The results of energy dispersive spectrometer (EDS) show that the concentration ratio of Zn to Sn is in the range from 1.44 to 1.57. The results of Hall-effect-measurement system reveal that the resistivity of films varies from 102 to 10–1 Ωcm, carrier concentration is about 10¹⁷ cm^–3, and mobility ranges from 10⁰ to 10¹ cm² v^–1 s^–1.     

Study on electrical conductivity and phase transition in singly doped BIPBVOX (Bi2V1−xPbxO5.5−x/2) solid electrolyte

Samples of bismuth lead vanadium oxide (BIPBVOX) (Bi₂V_1–xPb_xO_5.5–x/2) singly substituted system in the composition range 0.05 ≤ x ≤ 0.20 were prepared by sol–gel synthesis route. Structural investigations were carried out by using a combination of differential thermal analysis (DTA) and powder X-ray diffraction (PXRD) technique. Energy dispersive X-ray spectroscopy analysis (EDXA) of doped samples was carried out to predict the sample purity and doping concentration. Transitions, α?β, β?γ and γ′?γ were detected by XRD, DTA and variation in the Arrhenius plots of conductivity. The ionic conductivity was measured by AC impedance spectroscopy. The solid solutions with composition x ≤ 0.07 undergo α?β phase transition, at 329 °C and β?γ phase transition at 419 °C. The highly conducting γ′-phase was effectively stabilized at room temperature for compositions with x ≥ 0.17 whose thermal stability increases with Pb content. At 300 °C, the highest value of conductivity 6.234 × 10^?5 S cm^?1 was obtained for composition x = 0.15 and at 600 °C the highest value of conductivity 0.65 S cm^?1 is observed for x = 0.17. AC impedance plots reveal that the conductivity is mainly due to the grain contribution to oxide ion conductivity.     

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.     

Optical characterization of nano-structured Cu2ZnSnS4 thin films deposited by GLAD technique

In this paper, Cu₂ZnSnS₄ (CZTS) thin films were elaborated at room temperature by thermal evaporation method using Glancing Angle Deposition (GLAD) technique at different incident angles γ = 00°, 20°, 40°, 60°, 75° and 85°. XRD, Raman scattering analysis, (SEM) and UV-Visible-NIR spectroscopy were used to characterize the crystalline structure, morphology and optical properties of CZTS samples. The results have showed that the ellipsometric analysis leaded to an optical anisotropy due to the structural anisotropy for CZTS samples deposited at γ = 85°. All Cu₂ZnSnS₄ samples exhibited a high absorption coefficient (α > 10⁴ cm⁻¹) and a direct optical transition varied between 1.48 eV and 2.05 eV for CZTS thin films deposited at γ = 00° and 85°, respectively. The value of the Urbach energy increased with incident angle, indeed, its value increased from 58 meV (γ = 00°) to 604 meV (γ = 75°) and decrease to be 368 meV for γ = 85°. This result is correlated with the Raman analysis. From transmittance data of CZTS thin films deposited at γ = 00°, 20° and 40° Swanepoel's method was used, to estimate the refractive index n. It allows us, using the Wemple-DiDomenico and Spitzer-Fan models, to calculate other optical parameters such as the oscillator energy E₀, dispersion energy E_d, zero frequency refractive index n₀, high frequency dielectric constant ε_∞ and the electric susceptibility χ_e. On the other hand, to have an idea about the evolution of the nonlinear optical character, the nonlinear susceptibility χ⁽³⁾ and the nonlinear refractive index n₂ of CZTS thin films deposited at γ = 00°, 20° and 40° were investigated. Ellipsometric measurements of CZTS thin films has leaded to an optical anisotropy for γ = 85°. In addition, the generalized ellipsometry in Jones formalism have proved this property, which can be related to the nano-columnar slanted structure as revealed by (SEM) analysis.