Growth-Temperature-Controlled Optical Properties of Textured MgxZn1?xO Thin Films

Pulsed laser deposition was used to grow magnesium zinc oxide thin films on amorphous fused silica substrates at several temperatures between room temperature and 750°C. In this study, the effect of growth temperature on the optical properties of textured Mg _x Zn_1−x O thin films was examined. The optical properties of the films were measured using absorption and photoluminescence spectrometry. Absorption spectra revealed that the bandgap values of textured Mg _x Zn_1−x O thin films were enhanced in films grown at higher temperatures. The absorption spectra near the absorption edge were fitted using the Urbach equation in order to investigate the effects of growth temperature on exponential band tail and bandgap. The photoluminescence spectra were measured for magnesium zinc oxide thin films deposited at 250°C, 350°C, 450°C, 550°C, and 650°C. The film grown at 350°C provided the highest excitonic peak intensity. On the other hand, the film grown at 250°C exhibited the lowest excitonic peak intensity. The excitonic peak intensity was considerably reduced in magnesium zinc oxide thin films grown at temperatures greater than 350°C. The ability to perform substrate-temperature-dependent bandgap engineering of Mg _x Zn_1−x O will enable use of this material in next-generation optical and optoelectronic devices.     

Structural and optical properties of Zn<Subscript>1−x</Subscript>Mg<Subscript>x</Subscript>O thin films synthesized with metal organic chemical vapor deposition

We present the structural and optical properties of Zn_1?xMg_xO thin films studied using x-ray diffraction (XRD), extended x-ray absorption fine structure (EXAFS), and photoluminescence (PL) measurements. The Zn_1?xMg_xO films on sapphire [0001] substrates were fabricated with metal organic chemical vapor deposition (MOCVD). The XRD measurements showed that the Zn_1?xMg_xO films (x≤0.05) had a wurtzite structure without any MgO phase and were epitaxially grown along the c-axis of the Al₂O₃ substrate. The lattice constant of the Zn_0.95Mg_0.05O film shrank by 0.023 Å, compared with that of ZnO crystals. From the EXAFS measurements on the Zn_1?xMg_xO films at Zn K-edge, we found a substantial amount of distortion in the bond length of Zn-Zn pairs with a small amount of Mg substitution on the Zn site. The PL measurements showed a gradual increment of the main exciton transitions from 3.36 eV (x=0.0) to 3.57 eV (x=0.05) at 10 K. We also observed a strong deep-level emission near 2.3 eV from the specimen with x=0.05.     

Surface and Interface Properties of Metal-Organic Chemical Vapor Deposition Grown a -Plane Mg x Zn1– x O (0?≤ x ≤?0.3) Films

The a-plane Mg _x Zn_1−x O (0 ≤ x ≤ 0.3) films were grown on r-plane () sapphire substrates using metal-organic chemical vapor deposition (MOCVD). Growth was done at temperatures from 450°C to 500°C, with a typical growth rate of ∼500 nm/h. Field emission scanning electron microscopy (FESEM) images show that the films are smooth and dense. X-ray diffraction (XRD) scans confirm good crystallinity of the films. The interface of Mg _x Zn_1−x O films with r-sapphire was found to be semicoherent as characterized by high-resolution transmission electron microscopy (HRTEM). The Mg _x Zn_1−x O surfaces were characterized using scanning tunneling microscopy (STM) in ultrahigh vacuum (UHV). Low-energy electron diffraction (LEED) shows well-ordered and single-crystalline surfaces. The films have a characteristic wavelike surface morphology with needle-shaped domains running predominantly along the crystallographic c-direction. Photoluminescence (PL) measurements show a strong near-band-edge emission without observable deep level emission, indicating a low defect concentration. In-plane optical anisotropic transmission was observed by polarized transmission measurements.     

Hybrid deposition of piezoelectric (11\bar 20) MgxZn1−xO (0≤x≤0.3) on (01\bar 12) R-sapphire substrates using RF sputtering and MOCVDR-sapphire substrates using RF sputtering and MOCVD

Mg_xZn_1?xO (0≤x≤0.3) films are deposited on R-plane $(01\bar 12)$ sapphire substrates using a hybrid deposition technique: metalorganic chemical vapor deposition and radiofrequency (RF) sputtering. Thick piezoelectric Mg_xZn_1?xO films are deposited by RF sputtering on MOCVD grown thin ZnO buffers on R-sapphire substrate. Molar ratio of ZnO and MgO powders are mixed to form Mg_xZn_1?xO (0≤x≤0.3) sputtering targets with NiO (2–3 wt.%) added for compensation doping to achieve piezoelectricity. Field emission scanning electron microscopy shows that the deposited films are dense and uniform. X-ray diffraction indicates that the sputter-deposited Mg_xZn_1?xO (0≤x≤0.3) films retain the wurtzite crystal structure. The crystallinity of the deposited films is further improved by postannealing at 700°C in oxygen. Compositional analysis of the films is carried out using Rutherford back-scattering. High-frequency and low-loss surface acoustic wave (SAW) testing devices fabricated on these films are demonstrated. The SAW properties are tailored to changing Mg compositions. In the ZnO/R-Al₂O₃ system, two types of wave modes, the Rayleigh-type and the Love-type wave modes, are investigated.     

A study of polycrystalline Cd(Zn,Mn)Te/Cds films and interfaces

Polycrystalline films of Cd_1-x Zn _x Te (x = 0–0.4) and Cd_1-x Mn _x Te (x = 0–0.25) were grown by MBE and MOCVD, respectively, on CdS/SnO₂/glass substrates to investigate their feasibility for solar cell applications. The compositional uniformity and interface quality of the films were analyzed by x-ray diffraction, surface photovoltage, and Auger depth profile measurements to establish a correlation between growth conditions and lattice constant, atomic concentration, and bandgap of the ternary films. MBE-grown polycrystalline Cd_1-x Zn _x Te films showed a linear dependence between Zn/(Cd + Zn) beam flux ratio, Zn concentration in the film, and the bandgap. Polycrystalline Cd_1-x Zn _x Te films grown at 300° C showed good compositional uniformity in contrast to compositionally non-uniform Cd_1-x Mn _x Te films grown by MOCVD in the temperature range of 420–450° C. The MBE-grown Cd_1-x Zn _x Te interface also showed significantly less interdiffusion compared to the MOCVD-grown Cd_1-x Mn _x Te/CdS interface, where preferential exchange between Cd from the CdS layer and Mn from the Cd_1-x Mn _x Te film was observed. The compositional uniformity of MOCVD-grown polycrystalline Cd_1-x Mn _x Te films grown on CdS/SnO₂/glass substrates was found to be a strong function of the growth conditions as well as the Mn source.     

Characterization of ternary MgxZn1−xO thin films deposited by electron beam evaporation

Mg_xZn_1−xO (0≤x≤1) thin films were deposited on glass and quartz substrates by electron beam evaporation and effect of the Mg content of the film on its structural, optical and electrical properties were investigated. The structure, surface morphology, optical transmittance, band gap, refractive index and electrical resistivity were found to depend on the Mg content of the film. XRD data revealed that films were polycrystalline in nature. The structure of the films having Mg content in the range of 1–0.74 was cubic, mixed cubic-hexagonal phases for x=0.47 and hexagonal phase for x=0. The composition analysis showed that Mg content in Mg_xZn_1−xO film is high as compared to the corresponding target alloy. It was observed that the optical band gap increases from 3.3 to 6.09 eV, refractive index at 550 nm decreases from 1.99 to 1.75, transmittance increases from about 70% to 90% and electrical resistivity increases from 0.5 to 1.48×10⁶ Ω cm with the increase of Mg concentration in the film from 0 to 1. The results reported in this work are useful for window layer of solar cells and other optoelectronic devices.     

Electrodepositing ZnxMnyOz alloys from zinc oxide to manganese oxide

Electrodeposition has emerged as a practical and simple method to synthesise semiconductor materials under different forms, thin films or nanostructured layers. This work reports on the cathodic electrodeposition of ZnMnO thin layers using both zinc and manganese chlorides as precursors. The composition of thin films can be varied from binary zinc oxide to manganese oxide varying the Mn/(Mn+Zn) ratio between 0 and 1. The composition of Zn_xMn_yO_z films was obtained by energy dispersive spectroscopy. Zn_1−xMn_xO films with Mn/Zn ratio less than 10% exhibit a crystalline wurtzite structure typical of ZnO fully oriented in the (0 0 2) direction. Higher Mn content leads to deformation of the ZnO lattice and the wurtzite structure is no longer maintained. X-ray photoelectron spectroscopy points out that Mn₃O₄ tends to be deposited when a high Mn/Zn ratio is used in the starting solution. Magnetic measurements on films with Mn/(Zn+Mn) ratio near 1 reveal magnetic characteristics similar to Mn₃O₄ compounds. The transmission spectra of Zn_xMn_yO_z show the typical absorption edge of crystalline ZnO while the wurtzite structure is maintained and it shifts to higher wavelengths when Mn content increases.     

Epitaxial growth and properties of Mg<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript>O films produced by pulsed laser deposition

The Mg _x Zn_1-x O thin films with a Mg content corresponding to x = 0–0.45 are grown by pulsed laser deposition on ablation of ceramic targets. The conditions for epitaxial growth of the films on the single-crystal Al₂O₃ (00.1) substrates are established. The record limit of solubility of Mg in hexagonal ZnO, x = 35 is attained. In this case, the lattice mismatch for the parameter a of the ZnO and Mg_0.35Zn_0.65O films does not exceed 1%, whereas the band gaps of the films differ by 0.78 eV. The surface roughness of the films corresponds to 0.8–1.5 nm in the range of x = 0–0.27.     

The effect of Zn1‐xMgxO buffer layer deposition temperature on Cu(In,Ga)Se2 solar cells: A study of the buffer/absorber interface

The effect of atomic layer deposition temperature of Zn_1‐xMg_xO buffer layers for Cu(In,Ga)Se₂ (CIGS) based solar cell devices is evaluated. The Zn_1‐xMg_xO films are grown using diethyl zinc, bis‐cyclopentadienyl magnesium and water as precursors in a temperature range of 105 to 180°C. High efficiency devices are produced in the region from 105 up to 135°C. At a Zn_1‐xMg_xO deposition temperature of 120°C, a maximum cell efficiency of 15·5% is reached by using a Zn_1‐xMg_xO layer with an x‐value of 0·2 and a thickness of 140 nm. A significant drop in cell efficiency due to large losses in open circuit voltage and fill factor is observed for devices grown at temperatures above 150°C. No differences in chemical composition, structure and morphology of the samples are observed, except for the samples prepared at 105 and 120°C that show elemental selenium present at the buffer/absorber interface. The selenium at the interface does not lead to major degradation of the solar cell device efficiency. Instead, a decrease in Zn_1‐xMg_xO resistivity by more than one order of magnitude at growth temperatures above 150°C may explain the degradation in solar cell performance. From energy filtered transmission electron microscopy, the width of the CIGS/Zn_1‐xMg_xO chemical interface is found to be thinner than 10 nm without any areas of depletion for Cu, Se, Zn and O. Copyright © 2008 John Wiley & Sons, Ltd.     

The Locus of Free Charge‐Carrier Generation in Solution‐Cast Zn1–xMgxO/Poly(3‐hexylthiophene) Bilayers for Photovoltaic Applications

The photoconductivity of solution‐cast Zn_1–xMg_xO (x=0‐0.4) and poly(3‐hexylthiophene) (P3HT) thin films, and Zn_1‐xMg_xO/P3HT bilayers is investigated using Time‐Resolved Microwave Conductivity (TRMC) with the aim of determining the locus of free charge carrier generation in the bilayer system. The photoconductivity of Zn_1–xMg_xO thin films, under illumination with 300 nm laser pulses, is limited by the formation of stable excitons and by scattering of the carriers at grain boundaries. The electron mobility in Zn_1–xMg_xO films decreases exponentially with Mg concentration, up to x=0.4. In agreement with previous work, free carriers are observed in the P3HT film under illumination with 500 nm pulses in the absence of an acceptor. Under illumination with 500 nm pulses, where only the polymer absorbs, the TRMC signal for the Zn_1–xMg_xO/P3HT bilayers for x≥0.2 is the same as that of pure P3HT, indicating that free carrier generation in these bilayers occurs predominately by exciton dissociation in the polymer bulk, and not at the interface between the polymer and the solution‐cast oxide. At lower Mg concentrations (x<0.2) the TRMC signal increases with decreasing x following the dependence of the electron mobility in the oxide but its light intensity dependence remains consistent with free carrier generation in the polymer bulk. To explain these results and previously published photovoltaic device data (Adv. Funct. Mater. 2007 , 17, 264) we propose that free carrier generation in the bilayers predominantly occurs in the bulk of P3HT, and is followed by electron injection to the oxide to yield photocurrent in photovoltaic cells. The dependence of the TRMC signal of the bilayers on Mg concentration is explained in terms of the yield for free carrier generation in the polymer and the relative contributions of electrons in the oxide and holes in the polymer.     

Preparation and characteristics of the wide gap semiconductor Mg0.18Zn0.82O thin film by L-MBE

The high purity ZnO ceramic target and the (MgO)_0.1(ZnO)_0.9 target were fabricated. The wurtzite-phase ZnO thin film and ternary Mg_xZn_1−xO thin film were grown on sapphire (0001) substrates by laser molecular beam epitaxy (L-MBE) from the sintered ceramic targets separately. The films' transmittance spectra at room temperature for the ZnO film and the Mg_xZn_1−xO film were measured and compared while their room temperature photoluminescence spectra were done. The band-gap modulation is realized from 3.31 eV for the ZnO film to 3.64 eV for the Mg_xZn_1−xO alloy film. The Mg content x in the Mg_xZn_1−xO alloy film was determined to be 0.18.     

CuxS背接触层制备及在碲化镉薄膜太阳电池中应用研究

本文采用化学水浴法沉积CuxS薄膜,通过改变Cu元素比例研究其对碲化镉电池效率的影响。研究表明化学水浴法沉积的CuxS是非晶的,采用适当退火条件可以使其晶化,随着退火温度的提高,薄膜变得致密且结晶明显。CuxS薄膜厚度对电池性能有很大的影响,结果表明,随着CuxS薄膜厚度增加,电池性能先增加后减少。薄膜厚度为75nm时,CdS/CdTe电池性能最佳,达到了最高转化效率(η)为12.19%,填充因子(FF)为68.82%,开路电压(Voc)为820mV。     

One‐Step Self‐Assembly Fabrication of High Quality NixMg1‐xO Bowl‐Shaped Array Film and Its Enhanced Photocurrent by Mg,2+ Doping

A series of high quality Ni_xMg_1‐xO bowl‐shaped array films are successfully prepared by a simple one‐step assembly of polystyrene colloidal spheres and metal oxide precursors at oil–water interface, and further used to fabricate nanodevices. The doping of Mg²⁺ can greatly enhance the current and spectrum responsivity of NiO film‐based nanodevice. The maximum R_λ value of these bowl‐shaped Ni_xMg_1‐xO film‐based devices measured in the study shows 4–5 orders of enhancement than the previously reported Ni_xMg_1‐xO film at equal doping.     

Characterization of Zn1?xMgxO Films Prepared by the Sol–Gel Process and Their Application for Thin-Film Transistors

Transparent semiconductor thin films of Zn_1−x Mg _x O (0 ≤ x ≤ 0.36) were prepared using a sol–gel process; the crystallinity levels, microstructures, and optical properties affected by Mg content were studied. The experimental results showed that addition of Mg species in ZnO films markedly decreased the surface roughness and improved transparency in the visible range. A Zn_1−x Mg _x O film with an x-value of 0.2 exhibited the best average transmittance, namely 93.7%, and a root-mean-square (RMS) roughness of 1.63 nm. Therefore, thin-film transistors (TFTs) with a Zn_0.8Mg_0.2O active channel layer were fabricated and found to have n-type enhancement mode. The Zn_0.8Mg_0.2O TFT had a field-effect mobility of 0.1 cm²/V s, threshold voltage of 6.0 V, and drain current on/off ratio of more than 10⁷.     

Optical and electrical properties of crystalline indium tin oxide thin film deposited by vacuum evaporation technique

Indium tin oxide (ITO) thin film was deposited on glass substrate by means of vacuum evaporation technique and annealed at 200 °C, 300 °C and 400 °C in air for 1 h. The characterization and properties of the deposited film samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-VIS-NIR spectroscopy techniques. From the XRD patterns, it was found that the deposited thin film was of crystalline at an annealing temperature of 400 °C. The crystalline phase was indexed as cubic structure with lattice constant and crystallite size of 0.511 nm and 40 nm, respectively. The SEM images showed that the films exhibited uniform surface morphology with well-defined spherical grains. The optical transmittance of ITO thin film annealed at 400 °C was improved from 44% to 84% in the wavelength range from 250 nm to 2 100 nm and an optical band gap was measured as 3.86 eV. Hall effect measurement was used to measure the resistivity and conductivity of the prepared film.     

Band-Gap Engineering in ZnO-MgO Films Prepared by Combustion Flame Pyrolysis of Solution Precursors

MgO-doped ZnO films, metastable in nature, are deposited by combustion flame pyrolysis, as this is one of the suitable methods for fabricating such nonequilibrium films. Experiments to alloy ZnO with MgO have been carried out, aiming to expand the band-gap to the ultraviolet region. Structural and optical studies show that Zn_1−x Mg _x O films with various x values (x = 0.2, 0.3, 0.33, and 0.4) could be obtained and the band-gap of ZnO could be tuned from 3.26 eV to 3.76 eV.     

Effect of processing parameter on structural,optical and electrical properties of photovoltaic chalcogenide nanostructured RF magnetron sputtered thin absorbing films

The aim of this work was to develop high quality of CuIn_1−xGa_xSe₂ thin absorbing films with x (Ga/In+Ga)<0.3 by sputtering without selenization process. CuIn_0.8Ga_0.2Se₂ (CIGS) thin absorbing films were deposited on soda lime glass substrate by RF magnetron sputtering using single quaternary chalcogenide (CIGS) target. The effect of substrate temperature, sputtering power & working pressure on structural, morphological, optical and electrical properties of deposited films were studied. CIGS thin films were characterised by X-ray diffraction (XRD), Field emission scanning electron microscope (FE-SEM), Energy dispersive X-ray spectroscopy (EDAX), Atomic force microscopy (AFM), UV–vis–NIR spectroscopy and four probe methods. It was observed that microstructure, surface morphology, elemental composition, transmittance as well as conductivity of thin films were strongly dependent on deposition parameters. The optimum parameters for CIGS thin films were obtained at a power 100 W, pressure 5 mT and substrate temperature 500 °C. XRD revealed that thin film deposited at above said parameters was polycrystalline in nature with larger crystallite size (32 nm) and low dislocation density (0.97×10¹⁵ lines m⁻²). The deposited film also showed preferred orientation along (112) plane. The morphology of the film depicted by FE-SEM was compact and uniform without any micro cracks and pits. The deposited film exhibited good stoichiometry (Ga/In+Ga=0.19 and In/In+Ga=0.8) with desired Cu/In+Ga ratio (0.92), which is essential for high efficiency solar cells. Transmittance of deposited film was found to be very low (1.09%). The absorption coefficient of film was ~10⁵ cm⁻¹ for high energy photon. The band gap of CIGS thin film evaluated from transmission data was found to be 1.13 eV which is optimum for solar cell application. The electrical conductivity (7.87 Ω⁻¹ cm⁻¹) of deposited CIGS thin film at optimum parameters was also high enough for practical purpose.     

Characterization of UV photodetectors with MgxZn1−xO thin films

In this study the metal-semiconductor-metal (MSM) structure ultraviolet (UV) photodetectors (PDs) based on Mg_xZn_1−xO thin films were fabricated. The Mg_xZn_1−xO thin films were grown on glass substrates by sol-gel method. The results show that the optical absorption has a blue shift and higher transmittance with increasing Mg dopant. The optical band gap were modified by 3.28-3.52 eV, which corresponded to x = 0 and x = 0.16. For a 10 V applied bias, the dark currents of the Mg_xZn_1−xO MSM-PDs were 637 nA (x = 0) to 0.185 nA (x = 0.16) and showed good Schottky contacts. This UV-visible rejection ratio of the Mg_xZn_1−xO UV PDs at x = 0, 0.16, 0.21 and 0.33 were 18.82, 35.36, 40.91 and 42.92, respectively.     

Structural,optical and electrical properties of MgxZn1−xO ternary alloy films

The structural, optical and electrical properties of Mg_xZn_1−xO (x=0.05–0.3) ternary alloy thin films deposited by the sol–gel method on the glass substrate were investigated. The presence of Mg in deposited samples was confirmed through EDAX. XRD spectra revealed that the deposited Mg doped ZnO films were polycrystalline in nature. The optical band gap of the films was tailored between 3.2 and 3.45 eV by varying Mg mole concentration between 0.05 and 0.3. I–V characteristics showed decrease in current with increase in the Mg mole concentration. These results explore the applicability of MgZnO to form effective and efficient heterostructures with ZnO as an active layer for efficient carrier confinement in light emitting devices.     

Evolution of Threading Dislocation Density and Stress in GaN Films Grown on (111) Si Substrates by Metalorganic Chemical Vapor Deposition

We have studied the evolution of threading dislocations (TDs), stress, and cracking of GaN films grown on (111) Si substrates using a variety of buffer layers including thin AlN, compositionally graded Al _x Ga_1-x N (0 ≤ x ≤ 1), and AlN/Al _y Ga_1-y N/Al _x Ga_1-x N (0 ≤ x ≤ 1, y = 0 and 0.25) multilayer buffers. We find a reduction in TD density in GaN films grown on graded Al _x Ga_1-x N buffer layers, in comparison with those grown directly on a thin AlN buffer layer. Threading dislocation bending and annihilation occurs in the region in the graded Al _x Ga_1-x N grown under a compressive stress, which leads to a decrease of TD density in the overgrown GaN films. In addition, growing a thin AlN/Al _y Ga_1-y N bilayer prior to growing the compositionally graded Al _x Ga_1-x N buffer layer significantly reduces the initial TD density in the Al _x Ga_1-x N buffer layer, which subsequently further reduces the TD density in the overgrown GaN film. In-situ stress measurements reveal a delayed compressive-to-tensile stress transition for GaN films grown on graded Al _x Ga_1-x N buffer layers or multilayer buffers, in comparison to the film grown on a thin AlN buffer layer, which subsequently reduces the crack densities in the films.