ZnS薄膜制备和光学性能研究

采用化学水浴法,以硫酸锌、硫脲、联氨、氨水和去离子水为反应前驱物制备ZnS薄膜。采用SEM、EDS、XRD和透射光谱分析方法,研究反应前驱物中氨水以及联氨的浓度对ZnS薄膜形貌、成分、结构和光学性能的影响,同时对ZnS薄膜的形成机理做进一步分析。结果表明:ZnS薄膜由纳米颗粒组成,这些ZnS纳米颗粒为非晶态结构。ZnS薄膜中S与Zn原子比最大为0.79∶1,薄膜中夹杂少量ZnO或Zn(OH)2。ZnS薄膜在可见光波段的透过率大于80%,禁带宽度为3.74～3.84 eV。氨水和联氨浓度对薄膜形貌、成分和光学性能有较大的影响。当反应前驱物中氨水浓度为0.5～0.8 mol/L、联氨浓度为0.5～1.0 mol/L时,溶液中的化学反应以在衬底上发生的离子-离子反应占主导作用,能在衬底上形成致密且颗粒大小分布均匀的ZnS薄膜,S与Zn的原子比接近1∶1。     

Effect of four different zinc salts and annealing treatment on growth,structural, mechanical and optical properties of nanocrystalline ZnS thin films by chemical bath deposition

ZnS thin films were deposited from four different zinc salts on glass substrates by chemical bath deposition method. Different anions of zinc salts affect the deposition mechanism and growth rate, which influence the properties of the films significantly. The ZnS thin film deposited from ZnSO₄ is smoother, thicker, more homogeneous and compact, nearly stoichiometric, comparing with the films deposited from Zn(CH₃COO)₂ and Zn(NO₃)₂, and ZnCl₂. The scratch test of bonding force between ZnS film and substrate shows that the ZnS film deposited from ZnSO₄ has the most excellent adhesion with the substrate. The presence of SO₄²⁻ promotes heterogeneous ZnS thin film growth via ions by ions deposition, and the films deposited from Zn(CH₃COO)₂ and Zn(NO₃)₂ are formed via clusters by clusters deposition. XRD and HRTEM results show that cubic ZnS films are obtained after single deposition, and the grain size of ZnS thin film deposited from ZnSO₄ for 2.5 h is 10 nm. The average transmission of all films is greater than 85% in the wavelength ranging from 600 to 1100 nm, and the transmission of films deposited from ZnSO₄ or Zn(NO₃)₂ for 1.5, 2 and 2.5 h is greater than 85% in the wavelength varying from 340 to 600 nm, which can enhance the blue response. The band gaps of all ZnS thin films are in the range of 3.88–3.99 eV. After annealing treatment, the mechanical and optical properties of the ZnS thin film deposited from ZnSO₄ are improved significantly.     

Influence of Deposition Parameters on the Morphology, Structural, and Optical Properties of ZnSe Nanocrystalline Thin Films

Zinc selenide (ZnSe) nanocrystalline thin films were prepared by using chemical bath deposition at different ammonia concentrations and different deposition temperatures. The structural and optical properties of ZnSe nanocrystalline thin films were investigated as a function of the ammonia concentration in precursors or the deposition temperature using scanning electron microscopy, energy-dispersive spectrometry, x-ray diffraction measurements, and ultraviolet (UV)–visible spectrophotometry measurements. The results reveal that the ZnSe thin films are composed of a large number of uniform spherical particles. Each spherical particle contains several nanocrystals 5 nm to 7 nm in crystallite size. An increase in both the average diameter of the spherical particles and the crystallite size of the nanocrystals occurs with an increase in ammonia concentration and/or deposition temperature. The Se/Zn atom ratios in the ZnSe thin films increase and the optical band gaps, E _g, of the ZnSe thin films decrease with an increase in ammonia concentration or deposition temperature. The kinetics and reaction mechanism of the ZnSe nanocrystalline thin films during deposition are discussed.     

Kinetic Monte Carlo simulation of low-pressure chemical vapor deposition of silicon nitride: Impact of gas flow rate and temperature on silicon cluster size and density

In the present study, the deposition process of SiN_x thin films obtained by a low-pressure chemical vapor deposition technique with a mixture of disilane (Si₂H₆) and ammonia (NH₃) was simulated by using the kinetic Monte Carlo method. A new pattern describing the distribution of ammonia molecules in the simulation matrix was proposed. The influences of the NH₃/Si₂H₆ gas flow ratio and the deposition temperature on the obtained films structure in terms of silicon cluster size and density were analyzed. The simulation results indicate that an increase in the gas flow ratio leads to the deposition of amorphous silicon clusters characterized by small sizes. Nevertheless, an increase in the temperature values of the process provokes an enhancement in the silicon cluster size along with a decrease in their density.     

Atomic Layer Deposition of Aluminum Nitride Using Tris(diethylamido)aluminum and Hydrazine or Ammonia

Aluminum nitride (AlN _x ) films were obtained by atomic layer deposition (ALD) using tris(diethylamido) aluminum(III) (TDEAA) and hydrazine (N₂H₄) or ammonia (NH₃). The quartz crystal microbalance (QCM) data showed that the surface reactions of TDEAA and N2H4 (or NH₃) at temperatures from 150 to 225°C were self-limiting. The rates of deposition of the nitride film at 200°C for systems with N₂H₄ and NH₃ coincided: ~1.1 Å/cycle. The ALD AlN films obtained at 200°C using hydrazine had higher density (2.36 g/cm³, 72.4% of bulk density) than those obtained with ammonia (2.22 g/cm³, 68%). The elemental analysis of the film deposited using TDEAA/N2H4 at 200°C showed the presence of carbon (~1.4 at %), oxygen (~3.2 at %), and hydrogen (22.6 at %) impurities. The N/Al atomic concentration ratio was ~1.3. The residual impurity content in the case of N₂H₄ was lower than for NH₃. In general, it was confirmed that hydrazine has a more preferable surface thermochemistry than ammonia.     

Synthesis and characterization of CdSe nanocrystalline thin films deposited by chemical bath deposition

Cadmium selenide (CdSe) nanocrystalline thin films were prepared by chemical bath deposition (CBD) using ammonia and triethanolamine (TEA) as complexing agents, cadmium chloride and sodium selenosulphate as the sources of Cd²⁺ and Se^2? ions, respectively. The structural and optical properties of CdSe nanocrystalline thin films were investigated as a function of the sodium selenosulphate concentrations or ammonia concentrations in precursors using scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD) measurements, transmission electron microscopy (TEM) and UV–visible spectrophotometer measurements. The results reveal that the CdSe thin films are in the pure cubic phase, which composed of a large number of uniform spherical particles. Each spherical particle contains many nanocrystals 3–10 nm in crystallite size. An increase in both the average diameter of the spherical particles and the crystallite size of the nanocrystals occurs with an increase in ammonia concentrations. The Se/Cd atom ratios of CdSe thin films firstly increase and then decrease with an increase in ammonia concentration or sodium selenosulphate concentration. The optical band gap of CdSe thin films decrease with an increase in ammonia concentrations. The kinetics and reaction mechanism of the CdSe nanocrystalline thin films during deposition are discussed.     

Cu(In,Ga)Se2太阳电池缓冲层ZnS薄膜性质及应用

在含有ZnSO4,SC(NH2)2,NH4OH的水溶液中采用CBD法沉积ZnS薄膜,XRF和热处理前后的XRD测试表明,ZnS沉积薄膜为立方相结构,薄膜含有非晶态的Zn(OH)2.光学透射谱测试表明,制备的薄膜透过率(λ＞500nm)约为90%,薄膜的禁带宽度约为3.51eV.ZnS薄膜沉积时间对Cu(In,Ga)Se2太阳电池影响显著,当薄膜沉积时间在25～35min时,电池的综合性能最好.对比了不同缓冲层的电池性能,采用CBD-CdS为缓冲层的电池转换效率、填充因子、开路电压稍高于CBD-ZnS为缓冲层的无镉电池,但无镉电池的短路电流密度高于前者,两者转换效率相差2%左右.ZnS可以作为CIGS电池的缓冲层,替代CdS,实现电池的无镉化.     

Optimization of SiNX:H films deposited by PECVD for reliability of electronic, microsystems and optical applications

This paper presents the correlation between the optical properties and the chemical and electrical properties of amorphous silicon nitride (SiN_X:H) films prepared by reactor Plasma-Enhanced Chemical Vapor Deposition (PECVD). The effects of temperature and mixture of gases (NH₃/SiH₄/N₂) on these dielectric films are investigated in this study. Silane (SiH₄) and ammonia (NH₃) are used as the reactive species, while nitrogen (N₂) is used as a dilution gas. A particular focus is made on the improvement of the electrical properties that are strongly correlated to the physicochemical bonds films properties. The incorporation of the N₂ dilution leads to the deposition rate and hydrogen content reductions in the film. An optimal gases mixture with N₂ is obtained to improve the breakdown voltage at low temperature, 200 °C. Fundamental properties of these fabricated films are characterized by their elemental composition, chemical specification, residual stress, optical and electrical properties. The results experimentally show that this film can be used to improve some of the key deposition parameters for the reliability of semiconductor, microsystems and optical applications.     

Quantitative Correlation of Perovskite Film Morphology to Light Emitting Diodes Efficiency Parameters

This paper reports quantitative correlation of CH₃NH₃PbBr₃ (MAPbBr₃) thin film morphology to light emitting diode efficiency parameters. Sequential (spin coating) deposition is used for highly reproducible and dense film morphology of MAPbBr₃ thin‐film. In this fabrication process using an orthogonal solvent approach, control of morphology, coverage, thickness, and optical properties in these compact thin‐films is demonstrated. Optical studies show direct correlation between morphology to dynamics of photoluminescence (PL) and absolute PL yield. Perovskite light emitting diodes (PeLEDs) are fabricated from these films to find the best ratio of PbBr₂ versus MABr for optimal performance. This study demonstrates PeLEDs with high brightness, ≈1050 cd m^?2 at 4.7 V (luminance efficiency ≈0.1 cd A^?1), for optimal thin‐film process with state‐of‐the‐art device performance. This quantitative analysis suggests that these state‐of‐the‐art PeLEDs suffer from poor charge carrier balance (≈2%) and out‐coupling efficiency (≈6%). Interestingly, charge carrier balance and PL yield together can explain the change in PeLED efficiency modulation with film morphology. Studies on single carrier devices show that these PeLEDs are electron current dominated and charge carrier balance increases with operating bias voltage.     

Epitaxial Growth and Characterization of p-Type ZnO

N-doped p-type ZnO thin films were grown on c-sapphire substrates, semi-insulating GaN templates, and n-type ZnO substrates by metal organic chemical vapor deposition (MOCVD). Diethylzinc and oxygen were used as precursors for Zn and O, respectively, while ammonia (NH₃) and nitrous oxide (N₂O) were employed as the nitrogen dopant sources. X-ray diffraction (XRD) studies depicted highly oriented N-doped ZnO thin films. Photoluminescence (PL) measurements showed a main emission line around 380 nm, corresponding to an energy gap of 3.26 eV. Nitrogen concentration in the grown films was analyzed by secondary ion mass spectrometry (SIMS) and was found to be on the order of 10¹⁸ cm⁻³. Electrical properties of N-doped ZnO epilayers grown on semi-insulating GaN:Mg templates were measured by the Hall effect and the results indicated p-type with carrier concentration on the order of 10¹⁷ cm⁻³.     

Characterization of n-Type and p-Type ZnS Thin Layers Grown by an Electrochemical Method

Electrodeposition of n-type and p-type thin-film layers of ZnS was carried out using a simple two-electrode system and aqueous solutions of ZnCl₂ and (NH₄)₂S₂O₃ with different Zn²⁺ concentrations. X-ray diffraction measurements show that the ZnS layers deposited from both solutions are amorphous. Optical absorption measurements show low absorbance of the layers with energy bandgap in the range of 3.68 eV to 3.78 eV after postdeposition annealing. Photoelectrochemical cell measurements show that both n-type and p-type ZnS thin layers can be electrodeposited by simply changing the concentrations of the deposition solutions. With higher Zn²⁺ concentration in the bath, n-type ZnS films were deposited, while p-type ZnS films were deposited with lower Zn²⁺ concentration. The estimated resistivity of layers from both solutions using I–V measurements were 3.0 × 10⁴ Ω cm and 2.0 × 10⁴ Ω cm, respectively, for n-ZnS and p-ZnS. Scanning electron microscopy shows that the deposited films consist of particles with good surface coverage of the glass/fluorine-doped tin oxide substrate.     

An evaluation of the deposition parameters for indium sulfide (In2S3) thin films using the grey-based Taguchi method

This paper presents an optimal deposition-parameter design for Indium sulfide (In₂S₃) thin films, using radio frequency (RF) magnetron sputtering for soda-lime glass substrates. The grey relational analysis (GRA), using the Taguchi method with an L₉ (3⁴) orthogonal array, a signal-to-noise (S/N) ratio and an analysis of variance (ANOVA) are used to optimize the multiple performance characteristics (deposition rate and optical transmittance). The effect of the optimization of the In₂S₃ films’ deposition parameters (RF power, sputtering pressure, substrates temperature and deposition time) on the structure, morphology and optical transmittance are studied. The results of the confirmation experiments demonstrate that the deposition rate and optical transmittance of In₂S₃ films is improved by using a deposition process that is optimized using the grey-based Taguchi method.     

CIGS Thin Films for Cd-Free Solar Cells by One-Step Sputtering Process

Cu(In_1?x Ga _x )Se₂ (CIGS) thin films were deposited by a one-step radio frequency (RF) magnetron sputtering process using a quaternary CIGS target. The influence of substrate temperature on the composition, structure, and optical properties of the CIGS films was investigated. All the CIGS films exhibited the chalcopyrite structure with a preferential orientation along the (112) direction. The CIGS film deposited at 623 K showed significant improvement in film crystallinity and surface morphology compared to films deposited at 523 and 573 K. To simplify the manufacturing procedure of solar cells and avoid the use of the toxic element Cd, the properties of ZnS films prepared by RF sputtering were also investigated. The results revealed that the sputtered ZnS film exhibits good lattice matching with the sputtered CIGS film with significantly lower optical absorption loss. Finally, all-sputtered Cd-free CIGS-based heterojunction solar cells with the structure SLG/Mo/CIGS/ZnS/AZO/Al grids were fabricated without post-selenization. Furthermore, the results demonstrated the feasibility of using a full sputtering process for the fabrication of Cd-free CIGS-based solar cell.     

Effects of ammonia concentration on property of Cd1−xZnxS films by chemical bath deposition

Cd_1−xZn_xS thin films were grown on soda–lime glass substrates by chemical-bath deposition (CBD) at 80 °C with stirring. All the samples were annealed at 200 °C for 60 min in the air. The crystal structure, surface morphology, thickness and optical properties of the films were studied with transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), step height measurement instrument and spectrophotometer respectively. The results revealed that Cd_1−xZn_xS thin films had cubic crystal structure and the intensity of the diffraction peak increased gradually as ammonia concentration rose and the grain size varied from 5.1 to 8.3 nm. All of Cd_1−xZn_xS thin films had a granular surface with some smaller pores and the average granule sizes increased from 92 to 163 nm with an increase in ammonia concentration. The Cd_1−xZn_xS thin films had the highest transmittance with ammonia concentration of 0.5 M L⁻¹, whose thickness was 50 nm and band gap was 2.62 eV.     

From Mesostructured Wurtzite ZnS‐Nanowire/Amine Nanocomposites to ZnS Nanowires Exhibiting Quantum Size Effects: A Mild‐Solution Chemistry Approach

Mesostructured wurtzite ZnS‐nanowire‐bundle/amine nanocomposites displaying remarkable quantum size effects are synthesized by using a mild‐solution reaction using different amines, such as n‐butylamine, ethylamine, and tetraethylenepentamine, Zn(NO₃)₂·6 H₂O, and CS(NH₂)₂ or Na₂S·9 H₂O as the precursors at temperatures ranging from room temperature to 180 °C. A possible mechanism for the shape‐controlled growth of ZnS nanowires and nanocomposites is proposed. Increasing the reaction temperature or dispersing the composite in acetic acid or NaOH solution leads to the destruction of the periodic structure and the formation of individual wurtzite nanowires and their aggregates. The nanowire/amine composites and individual wurtzite nanowires both display obvious quantum size effects. Strong band‐edge emission is observed for the wurtzite ZnS nanowires after removal of the amine. The optical properties of these nanocomposites and nanowires are strongly related to the preparation conditions and can be finely tuned. This technique provides a unique approach for fabricating highly oriented wurtzite ZnS semiconductor nanowires, and can potentially be extended to other semiconducting systems.     

Surface morphology dependent tungsten oxide thin films as toxic gas sensor

Tungsten oxide (WO₃) films are of great importance in gas sensing technology due to its selectivity towards toxic gases. In this paper, structural, morphological and compositional properties of spray deposited and chemical vapor deposited WO₃ thin films were investigated using XRD, TEM, SEM, EDAX and Raman spectroscopy. These films have monoclinic crystal structure; and a filamentous network surface for spray deposited films whereas small flake-shaped microstructure was observed on the surface of chemical vapor deposited films. These films were studied for their gas sensing ability towards toxic gases like ammonia (NH₃) and sulphur dioxide (SO₂) as a function of temperature and concentration. Response-recovery characteristics were studied by varying gas concentration. The spray deposited films displayed higher gas response than the chemical vapor deposited films whereas the later exhibited lower optimum operating temperature as well as faster response and recovery. A correlation between the morphological, compositional, electrical and gas sensing properties of these films is also established.     

Role of Zinc Source in Chemical Bath Deposition of Zinc Sulfide Thin Films on Si3N4

Zinc sulfide (ZnS) thin films have been grown by chemical bath deposition (CBD) using different zinc sources on a silicon nitride (Si₃N₄) substrate in an alkaline solution. The zinc precursors used were zinc acetate, zinc nitrate, and zinc sulfate. The structural and optical characteristics of the ZnS thin films obtained were analyzed. The morphology of the surface showed that the films were compact and uniform, with some pinholes in the surface depending on the zinc source. The most homogeneous and compact surfaces were those obtained using zinc nitrate as the zinc source with a root-mean-square (RMS) value of 3 nm. The transmission spectra indicated average transmittance of 80% to 85% in the spectral range from 300 nm to 800 nm, and the optical bandgap calculated for the films was around 3.71 eV to 3.74 eV.     

Synthesis of highly selective and sensitive Cu-doped ZnO thin film sensor for detection of H2S gas

Copper (Cu) doped zinc oxide (ZnO) thin films were successfully prepared by a simple sol-gel spin coating technique. The effect of Cu doping on the structural, morphology, compositional, microstructural, optical, electrical and H₂S gas sensing properties of the films were investigated by using XRD, FESEM, EDS, FTIR, XPS, Raman, HRTEM, and UV–vis techniques. XRD analysis shows that the films are nanocrystalline zinc oxide with the hexagonal wurtzite structure and FESEM result shows a porous structured morphology. The gas response of Cu-doped ZnO thin films was measured by the variation in the electrical resistance of the film, in the absence and presence of H₂S gas. The gas response in relation to operating temperature, Cu doping concentration, and the H₂S gas concentration has been systematically investigated. The maximum H₂S gas response was achieved for 3 at% Cu-doped ZnO thin film for 50 ppm gas concentration, at 250 °C operating temperature.     

Optical,morphological and electrical studies of Zn:PbS thin films

Structural, electrical, and optical properties of undoped and Zn doped lead sulfide (PbS) thin films are benign reported in this paper. The subjected films were grown on glass substrates at 25 °C by a chemical bath deposition (CBD) method. The concentration of Zn in the deposition bath represented by the ratio [Zn²⁺]/[Pb²⁺] was varied from 0% to 5%. It was found that the film׳s grains decreased in size with increasing Zn content in the film. XRD data showed the polycrystalline nature of the film its crystal orientation peak intensities decreased with higher doping concentration of Zn. Atomic force microscopy (AFM) measurements revealed that the surface roughness of the films decreased due to zinc doping as well. However, with increasing of the dopant concentration from 0% to 5%, the average transmittance of the films varied over the range of 35–75%. The estimated optical band (E_g) gaps of undoped and Zn doped PbS thin films were in the range of 0.72–1.46 eV. Hall Effect measurements electrical resistivity, carrier concentration and Hall mobility have been determined for the titled film as functions on the Zn content within the film׳s textures. The overall result of this work suggested that the Zn:PbS film is a good candidate as an absorber layer in the modern solar cell devices.     

Electrical properties of Cu4ZnSnS2/ZnS heterojunction prepared by ultrasonic spray pyrolysis

Cu₂ZnSnS₄ (CZTS)/ZnS heterojunctions have been prepared by a successive deposition of ZnS and CZTS thin films by ultrasonic spray pyrolysis technique on glass substrates. The cupric chloride concentration has been varied in the starting solution in order to investigate its influence on device properties. CZTS/ZnS heterojunctions were characterized by recording their current-voltage characteristics at different temperatures. The obtained results exhibit a good rectifying behavior of the realized heterojunction. Analysis of these results yields saturation current, series resistance and ideality factor determination. From the activation energy of saturation current we inferred that the thermal emission through the barrier height is the dominant mechanism of the reverse current rather than the defects contribution.