Dynamic scaling and optical properties of Zn（S,O, OH） thin film grown by chemical bath deposition

The scaling behavior and optical properties of Zn(S, O and OH) thin films deposited on soda-lime glass substrates by chemical bath deposition method were studied by combined roughness measurements, scanning electron microscopy and optical properties measurement. From the scaling behaviour, the value of growth scaling exponent β , 0.38±0.06, was determined. This value indicated that the Zn(S, O, OH) film growth in the heterogeneous process was influenced by the surface diffusion and shadowing effect. Results of the optical properties measurements disclosed that the transmittance of the film was in the region of 70%-88% and the optical properties of the film grown for 40 min were better than those grown under other conditions. The energy band gap of the film deposited with 40 min was around 3.63 eV.     

Synthesis and characterization of Zn(O,OH)S and AgInS2 layers to be used in thin film solar cells

In this paper AgInS₂ and Zn(O,OH)S thin films were synthesized and characterized. AgInS₂ layers were grown by co-evaporation from metal precursors in a two-step process, and, Zn(O,OH)S thin films were deposited from chemical bath containing thiourea, zinc acetate, sodium citrate and ammonia. X-ray diffraction measurements indicated that AgInS₂ thin films grown with chalcopyrite structure, and the as-grown Zn(O,OH)S thin films were polycrystalline. It was also found that the AgInS₂ films presented p-type conductivity, a high absorption coefficient (greater than 10⁴ cm⁻¹) and energy band-gap E_g of about 1.95 eV, Zn(O,OH),S thin films presented E_g of about 3.89 eV. Morphological analysis showed that under this synthesis conditions Zn(O,OH),S thin films coated uniformly the absorber layer. Additionally, the Zn(O,OH)S kinetic growth on AgInS₂ layer was studied also. Finally, the results suggest that these layers possibly could be used in one-junction solar cells and/or as top cell in a tandem solar cell.     

Growth of Sn(O,S)2 buffer layers and its application to Cu(In,Ga)Se2 solar cells

Sn-based thin films as new buffer layer for Cd-free Cu(In,Ga)Se₂ (CIGS) solar cells were developed. The Sn(O,S)₂ films were formed on CIGS substrates by chemical bath deposition from an alkaline ammonia solution by reacting tin(IV) chloride with thiourea. Optimization of the growth process allowed the smooth and conformal coverage of the films on the CIGS substrates with a thickness of 20 nm that was a self-limited thickness in the chemical bath deposition process. XPS analysis revealed that the as-deposited films contained Sn–O, Sn–OH, and Sn–S bondings and the ratio of Sn–S bonding to Sn–O bonding was 0.3. The CIGS solar cell fabricated with a 20-nm thick Sn(O,S)₂ buffer layer had the best efficiency of 11.5% without AR coating. The open circuit voltage, short circuit current, and fill factor were 0.55 V, 34.4 mA/cm², and FF = 0.61, respectively. The open circuit voltage and fill factor were low compared to the conventional CIGS solar cell with a 50-nm thick CdS buffer due to too thin Sn(O,S)₂ buffer layer.     

Chemical bonding states and atomic distribution within Zn(S,O) film prepared on CIGS/Mo/glass substrates by chemical bath deposition

Zn(S,O) thin films fabricated on CIGS/Mo/glass substrates by using chemical bath deposition (CBD) in acidic and basic solutions were studied. The Zn(S,O) thin films prepared in acidic solution [A-Zn(S,O) thin film] showed better crystallinity and a more compact surface morphology with larger grains than those prepared in basic solution [B-Zn(S,O) thin film] did. From the analysis of the chemical bonding states, at the initial growth step, the concentration ratio of Zn–O/Zn–S bonds in A-Zn(S,O) thin films was found to be approximately zero, while that in B-Zn(S,O) thin films was approximately equal to 1. The elemental distribution according to depth, determined by secondary ion mass spectroscopy (SIMS), was shown to be uniform throughout both the A- and B-Zn(S,O) thin films. To reduce the number of Zn–O bonds in the B-Zn(S,O) thin films, the samples were post-annealed at up to 300 °C under vacuum, after which the concentration ratio of Zn–O/Zn–S bonds decreased by about 71% without any change in the crystallinity or surface morphology.     

Deposition of copper iodide thin films by chemical bath deposition (CBD) and successive ionic layer adsorption and reaction (SILAR) methods

In this paper, we report structural, morphological, electrical studies of copper iodide (CuI) thin films deposited onto glass substrates by chemical bath deposition (CBD) and successive ionic layer adsorption and reaction (SILAR) methods. CuI thin films were characterized for their structural, morphological and wettability studies by means of X-ray diffraction (XRD), FT-Raman spectroscopy, scanning electron microscopy (SEM), optical absorption, and contact angle measurement methods. Thickness of thin films was 1 ± 0.1 μm measured by gravimetric weight difference method. The CuI thin films were nanocrystalline, with average crystal size of ～60 nm. The FT-IR study confirmed the formation of CuI on the substrate surface. SEM images revealed the compact and cube like structure for CuI thin films deposited by CBD and SILAR methods, respectively. Optical absorption study revealed optical energy gaps as 2.3 and 3.0 eV for CBD and SILAR methods, respectively. Wettability study indicated that CuI thin films deposited by SILAR method are more hydrophobic as compared to CBD method.     

Study of Inx(O,OH,S)y buffer layer effect on CIGSe thin film solar cells

In_x(O,OH,S)_y buffer layer has been applied to Cu(In,Ga)Se₂(CIGSe) solar cell by chemical bath deposition (CBD). The cell efficiency was observed to be dependant on film growth mode of In_x(O,OH,S)_y buffer layer, which was affected by the CBD conditions such as sulfur chemical concentration and deposition time. The fabricated solar cell showing higher conversion efficiency was observed to have non-porous and uniform texture of buffer, whereas the lower conversion efficiency cells were found to have fibrous texture or detached texture of buffer. The fibrous texture and the detached texture induced high series resistance and lower shunt resistance, respectively, which all resulted in lower cell efficiency with reduced fill factor. External quantum efficiency and temperature dependence of open circuit voltage measurements revealed that the lower efficiency cells suffered from higher interface recombination loss due to the related defects.     

Improved growth of solution‐deposited thin films on polycrystalline Cu(In,Ga)Se2

CdS and Zn(O,S) grown by chemical bath deposition (CBD) are well established buffer materials for Cu(In,Ga)Se₂ (CIGS) solar cells. As recently reported, a non‐contiguous coverage of CBD buffers on CIGS grains with {112} surfaces can be detected, which was explained in terms of low surface energies of the {112} facets, leading to deteriorated wetting of the chemical solution on the CIGS surface. In the present contribution, we report on the effect of air annealing of CIGS thin films prior to the CBD of CdS and Zn(O,S) layers. In contrast to the growth on the as‐grown CIGS layers, these buffer lay‐ ers grow densely on the annealed CIGS layer, even on grains with {112} surfaces. We explain the different growth behavior by increased surface energies of CIGS grains due to the annealing step, i.e., due to oxidation of the CIGS surface. Reference solar cells were processed and completed by i‐ZnO/ZnO:Al layers for CdS and by (Zn,Mg)O/ZnO:Al for Zn(O,S) buffers. For solar cells with both, CdS and Zn(O,S) buffers, air‐annealed CIGS films with improved buffer coverage resulted in higher power‐conversion efficiencies, as compared with the devices containing as‐grown CIGS layers. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effect of [Zn]/[S] ratios on the properties of chemical bath deposited zinc sulfide thin films

ZnS thin films have been prepared by chemical bath deposition (CBD) technique onto glass substrates deposited at about 80 °C using aqueous solution of zinc sulfate hepta-hydrate, ammonium sulfate, thiourea, ammonia and hydrazine hydrate. Ammonia and hydrazine hydrate were used as complexing agents. The influence of the ratio of [Zn]/[S] on formation and properties of ZnS thin films has been investigated. The ratio of [Zn]/[S] was changed from 3:1 to 1:9 by varying volumes and/or concentrations of zinc sulfate hepta-hydrate and thiourea in the deposition solution. The structural and morphological characteristics of films have been investigated by X-ray diffraction (XRD), scanning electron microscope and UV-vis spectroscopic analysis. ZnS films were obtained with the [Zn]/[S] ratio ranged from1:1 to 1:6. In the cases of [Zn]/[S] ratio ≥ 3:1 or ≤1:9, no deposition was found. Transparent and polycrystalline ZnS film was obtained with pure-wurtzite structure at the [S]/[Zn] ratio of 1:6. The related formation mechanisms of CBD ZnS are discussed. The deposited ZnS films show good optical transmission (80-90%) in the visible region and the band gap is found to be in the range of 3.65-3.74 eV. The result is useful to further develop the CBD ZnS technology.     

Properties of ITO–AZO bilayer thin films prepared by magnetron sputtering for applications in thin-film silicon solar cells

In this paper we study the electro-optical behavior and the application of indium–tin oxide (ITO) and aluminum-doped zinc oxide (AZO) bilayer thin films for silicon solar cells. ITO–AZO bilayer thin films were deposited on glass substrates using radio-frequency magnetron sputtering. The experimental results show that a decrease in the electrical resistivity of the ITO–AZO bilayer thin films has been achieved without significant degradation of optical properties. In the best case the resistivity of the bilayer films reached a minimum of 5.075×10^?4 Ω?cm when the thickness of the AZO buffer layer was 12 nm. The ITO–AZO bilayer films were applied as the front electrodes of amorphous silicon solar cells and the short-circuit current density of the solar cells was considerably increased.     

Effects of post-thermal treatments on morphological and optical properties of NiO/Ni(OH)2 thin films synthesized by solution growth

Room temperature deposition of PVP capped nanostructured NiO/Ni(OH)₂ thin film, the morphological and optical characterizations by solution growth technique are reported. The nanostructured thin films which were deposited on optical glass substrates were annealed at different temperatures and then subjected to structural, morphological and optical characterizations. X-ray diffraction measurements of the films revealed that higher temperatures during the thermal treatment enhanced the crystallinity of the thin films. The SEM surface micrographs show non-interconnected uniformly deposited fibre-like structures with approximate lengths between 400 and 1200 nm. The optical band gap energy roughly decreased from about 2.7 eV to about 2.2 eV with thermal treatment. The absorbance of the thin films annealed at 300 and 400 °C was as high as 90% in the visible region of the electromagnetic spectrum. These materials could be useful in solar thermal conversion processes.     

Application of multi-buffer layer of (Zn,Mg)O/CdS in Cu2ZnSn(S,Se)4 solar cells

(Zn,Mg)O (ZMO) buffer layer has attracted attention for having the potential to control the conduction band offset of buffer layer and large band-gap (Eg) Cu₂ZnSn(S,Se)₄ (CZTSSe) absorber interface, where the ZMO layer is deposited by the sputtering. However, the solar cell efficiency is decreased with the ZMO layer as compared with the CdS layer. The decrease in conversion efficiency is attributed to the sputtering damage on the absorber and high light reflection from the surfaces of CZTSSe solar cells. To completely suppress the damage, a CdS layer with very thin thickness of 20 nm is inserted between the ZMO layer and the CZTSSe layer. In addition, MgF₂ layers are deposited on CZTSSe solar cells as anti-reflection coating. Ultimately, the solar cell with multi-buffer layer of ZMO/thin-CdS is almost same level as that with the CdS layer. Therefore, the multi-buffer layer can be an appropriate buffer layer of the large-Eg CZTSSe layer.     

AFM, XPS and RBS studies of the growth process of CdS thin films on ITO/glass substrates deposited using an ammonia-free chemical process

This paper deals with a detailed study of the growth stages of CdS thin films on ITO/glass substrates by chemical bath deposition (CBD). The chemical and morphological characterization was done through X-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectrometry (RBS), and atomic force microscopy (AFM) techniques. On the other hand, optical transmission and X-ray diffraction (XRD) measurements were performed in order to study the optical and structural properties of the films. The time, the chemistry, and morphology of the different stages that form the growth process by CBD were identified through these results. Furthermore, clear evidence was obtained of the formation of Cd(OH)₂ as the first chemical species adhered to the substrate surface which forms the first nucleation centers for a good CdS formation and growth. On the other hand, the ITO coating caused growth stages to occur earlier than in just glass substrates, with which we can obtain a determined thickness in a shorter deposition time. We were able to prove that CBD is a good technique for the manufacture of thin films of semiconductor materials, since the CdS film does not have any impurities. Completely formed films were transparent, uniform, with good adherence to the substrate, of a polycrystalline nature with a hexagonal structure. These results indicate that films obtained by CBD are good candidates to be applied in different optoelectronic devices.     

Chemical bath deposition of hausmannite Mn3O4 thin films

A low-temperature chemical bath deposition (CBD) technique has been used for the preparation of Mn₃O₄ thin films onto glass substrates. The kinetic behavior and the formation mechanism of the solid thin films from the aqueous solution have been investigated. Structure (X-ray diffraction and Raman), morphological (atom force microscope), and optical (UV-vis-NIR) characterizations of the deposited films are presented. The results indicated that the deposited Mn₃O₄ thin films of smooth surface with nanosized grains were well crystalline and the optical bandgap of the film was estimated to be 2.54 eV.     

Influence of Ag and Sn incorporation in In_2S_3 thin films

Ag- and Sn-doped In2S3 thin films were deposited on glass substrates using the thermal evaporation technique. The doping was realized by thermal diffusion. The influences of Ag and Sn impurities on the electrical, structural, morphological, and optical properties of the In2S3 films were investigated. In all deposited samples, the x-ray diffraction spectra revealed the formation of cubic In2S3 phase. A significant increase in the crystallite size was observed after Ag doping,while the doping of Sn slightly decreased the crystallite size. The x-ray photoelectron spectroscopy verified the diffusion of Ag and Sn into the In2S3 films after annealing. The optical study illustrated that Ag doping resulted in a reduction of the optical band gap while Sn doping led to a widening of the gap. Optical properties were investigated to determine the optical constants. Besides, it was found that the resistivity decreases significantly either after Ag or Sn incorporation. The study demonstrates that the Sn-doped In2S3 thin films are more suitable for buffer layer application in solar cells than the Ag-doped In2S3 thin films.     

Ellipsometry investigation of the effects of annealing temperature on the optical properties of indium tin oxide thin films studied by Drude-Lorentz model

Float glass substrates covered by high quality ITO thin films (Balzers) were subjected for an hour to single thermal treatments at different temperature between 100 °C and 600 °C. In order to study the electric and optical properties of both annealed and not annealed ITO-covered float glasses, ellipsometry, spectrophotometry, impedance analysis, and X-ray measurements were performed. Moreover, variable angle spectroscopic ellipsometry provides relevant information on the electronic and optical properties of the samples. ITO film is modeled as a dense lower layer and a surface roughness layer. The estimated optical density for ITO and the optical density of the surface roughness ITO layer increases with the annealing temperature. In the near-IR range, the extinction coefficient decreases while the maximum of the absorption in the near UV range shift towards low photon energy as the annealing temperature increases. Spectrophotometry was used to estimate the optical band-gap energy of the samples. The thermal annealing changes strongly the structural and optical properties of ITO thin films, because during the thermal processes, the ITO thin film absorbs oxygen from air. This oxygen absorption decreases the oxygen vacancies therefore the defect densities in the crystalline structure of the ITO thin films also decrease, as confirmed both by ellipsometry and X-ray measurements.     

Green route fast synthesis and characterization of chemical bath deposited nanocrystalline ZnS buffer layers

Zinc sulphide (ZnS) thin films are deposited using chemical bath deposition method on the glass substrates in an aqueous alkaline reaction bath of zinc acetate and thiourea along with non-toxic complexing agent tri-sodium citrate at 95 °C. The results show noteworthy improvement in the growth rate of the deposited ZnS thin films and thickness of the film increases with the deposition time. From X-ray diffraction patterns, it is found that the ZnS thin films exhibit hexagonal polycrystalline phase reflecting from (101) and (0016) planes. The high resolution transmission electron microscopy studies confirmed the formation of hexagonal phase from the d-value calculation which was 0.3108 nm. X-ray photoelectron spectroscopy reveals that the Zn–S bonding energy is at 1022.5 and 162.1 eV for Zn 2p_3/2 and S 2p_1/2 states, respectively. Field emission scanning electron microscopy study shows that deposited thin films are highly uniform, with thin thickness and completely free from large ZnS clusters which usually form in aqueous solutions. Atomic force microscopy investigates that root mean square values of the ZnS thin films are from 3 to 4.5 nm and all the films are morphologically smooth. Energy dispersive spectroscopy shows that the ZnS thin films are relatively stoichiometric having Zn:S atomic ratio of 55:45. It is shown by ultraviolet–visible spectroscopy that ～90% transmittance and ～10% absorbance for the ZnS films in the visible region, which is significantly higher than that reported elsewhere and the band gap energy of the ZnS films is found to be 3.76, 3.74, and 3.71 eV, respectively.     

Effects of copper concentration on electro-optical and structural properties of chemically deposited nanosized (Zn-Cd)S:Cu films

Nanocrystalline (Zn-Cd)S films have been co-deposited on glass slide substrates by chemical bath deposition (CBD) technique at 70 °C for 75 min. Electroluminescent (EL), photoluminescent (PL) and structural characteristics of these films doped with Cu have been investigated. Cu doping has significant effects on the growth, structural and optical properties of the deposited (Zn-Cd)S films. EL studies show the essentiality of copper for EL emission. The effect of Cu concentration is examined on XRD, SEM, UV-vis spectroscopy, etc. The morphology of these films investigated with SEM and XRD is used to determine crystalline nature of the films. The optical absorption coefficient of the films has been found to increase with increase in Cu concentration. Voltage and frequency dependence shows the effectiveness of acceleration-collision mechanism. The trap-depth values are calculated from temperature dependence of EL brightness.     

ZnO薄膜的分子束外延生长及性能

利用分子束外延(MBE)和氧等离子体源辅助MBE方法分别在Si(100)、GaAs(100)和蓝宝石Al2O3(0001)衬底上用Zn、ZnS或以一定Zn-O化学计量比作缓冲层,改变衬底生长温度和氧压,并在氧气氛下,进行原位退火处理,得到ZnO薄膜。依据X射线衍射(XRD)图,表明样品的结晶性能尚好,且呈c轴择优取向;实验结果表明在不同衬底上生长的ZnO薄膜,由于晶格失配度不同,其衍射峰也有区别。用原子力显微镜(AFM)观测薄膜的表面形貌,为晶粒尺寸约几十纳米的ZnO纳米晶,且ZnO晶粒呈六边形柱状垂直于衬底的表面。采用掠入射X射线反射率法测膜厚。在360nm激发下,样品的发光光谱是峰值为410,510nm的双峰谱,是与样品表面氧缺陷有关的深能级发光。     

Studies on Structural,Morphological and Optical Properties of Chemically Deposited CdS<Subscript>1-x</Subscript>Se<Subscript>x</Subscript> Thin Films

The thin films of CdS_1-xSe_x were successfully deposited over glass substrates by chemical bath deposition technique. Cadmium acetate, thiourea and sodium selenosulfate were used as source materials for Cd²⁺, S^2? and Se^2? ions, while 2-mercaptoethanol was used as capping agent. The various deposition conditions such as precursor concentration, deposition temperature, pH and deposition time were optimized for the deposition of CdS_1-xSe_x thin films of good quality and the films were annealed at 200° and 300 °C. The structural, morphological, chemical and optical properties were examined by various characterization techniques and discussed in detail. The optical band gap of CdS_1-xSe_x thin film samples were estimated and found in the range from 2.11 to 1.79 eV for as-deposited and annealed thin films.     

A study of structural, compositional and optical properties of spray-deposited non-stoichiometric (Zn,Fe)S thin films

Non-stoichiometric ternary chalcogenides (Zn,Fe)S were prepared in the film form by pyrolytic spray deposition technique, using air/nitrogen as the carrier gas. The precursor solution comprised of ZnCl₂, FeCl₂ and thiourea. The depositions were carried out under optimum conditions of experimental parameters viz. carrier gas (air/nitrogen) flow rate, concentration of precursor constituents, nozzle substrate distance and temperature of quartz substrate. The deposited thin films were later sintered in argon at 1073 K for 120 min.The structural, compositional and optical properties of the sintered thin films were studied. X-ray diffraction studies of the thin films indicated the presence of (Zn,Fe)S solid solution with prominent cubic sphalerite phase while surface morphology as determined by scanning electron microscopy (SEM) revealed a granular structure.The chemical composition of the resulting thin films as analyzed by energy dispersive X-ray analysis (EDAX) reflected the composition of the precursor solutions from which the depositions were carried out with Fe at% values ranging from 0.4 up to 33.SEM micrographs of thin films reveal that the grain sizes of the thin films prepared using air as carrier gas and N₂ as carrier gas are in the vicinity of 300 and 150 nm, respectively.The diffuse transmittance measurements for thin films, as a function of wavelength reveal the dependence of direct optical band gap on Fe content and type of phase.