Influences of ZnO buffer layers on the quality of ZnO films synthesized by the metal-organic chemical vapor deposition process

High-quality ZnO thin films were prepared by metal-organic chemical vapor deposition (MOCVD) on a sapphire (a-Al₂O₃) substrate. The synthesis of ZnO films was performed over a substrate temperature of 400–700°C and at chamber pressures of 0.1–10 torr. The structural and optical properties of ZnO films were investigated in terms of deposition conditions, such as substrate temperature, working pressure, and the ratio of Zn precursor (Diethylzinc (DEZn)) to oxygen. The ZnO films, preferentially oriented to 34.42° diffraction because of the (002) plane, were obtained under processing conditions of 700°C and 3 torr. This film shows a full-width at half-maximum (FWHM) of 0.4–0.6°. The results of photoluminescence (PL) spectroscopy also show a strong near band-edge emission at 3.36 eV at 10 K as well as a very weak emission at deep levels around 2.5 eV at room temperature. In addition, we are interested in the introduction of ZnO buffer-layer growth by the sputtering process to reduce lattice mismatch stress. This paper addresses how to advance the crystalline and optical properties of film. The ZnO film grown with the aid of a buffer layer shows a FWHM of 0.06–0.1° in the x-ray diffraction (XRD) pattern. This result indicates that crystalline properties were highly improved by the ZnO buffer layers. The PL spectroscopy data of ZnO film also shows a strong near band-edge emission and very weak deep-level emission similar to films synthesized without a buffer layer. Accordingly, synthesized ZnO films with buffer layers indicate fairly good optical properties and low defect density as well as excellent crystallinity.     

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.     

Room-temperature ferromagnetic ordering in Mn-doped ZnO thin films grown by pulsed laser deposition

The ferromagnetic ordering in Mn-doped ZnO thin films grown by pulsed laser deposition (PLD) as a function of oxygen pressure and substrate temperature has been investigated. Room-temperature ferromagnetic behaviors in the Mn-doped ZnO films grown at 700°C and 800°C under 10⁻¹ torr in oxygen pressure were found, whereas ferromagnetic ordering in the films grown under 10⁻³ torr disappeared at 300 K. The large positive magnetoresistance (MR), ∼10%, was observed at 5 K at low fields and small negative MR was observed at high fields, irrespective of oxygen pressure. In particular, anomalous Hall effect (AHE) in the Mn-doped ZnO film grown at 700°C under 10⁻¹ Torr has been observed up to 210 K. In this work, the observed AHE is believed to be further direct evidence demonstrating that the Mn-doped ZnO thin films are ferromagnetic.     

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.     

Thermo-Sensitive Ba0.64Sr0.36TiO3 Thin Film Capacitors for Dielectric Type Uncooled Infrared Sensors

Ba_0.64Sr_0.36TiO₃ (BST) thin films are prepared on Pt/Ti/SiO₂/Si₃N₄/SiO₂/Si substrates by a sol-gel method. Thermo-sensitive BST thin film capacitors with a Metal-Ferroelectrics-Metal (M-F(BST)-M) structure are fabricated as the active elements of dielectric type uncooled infrared sensors. XRD are employed to analyze the crystallographic structures of the films. AFM observations reveal a smooth and dense surface of the films with an average grain size of about 35 nm. Rapid temperature annealing (RTA) process is a very efficient way to improve crystallization quality. The preferable annealing temperature is 800°C for 1 min. The butterfly shaped C-V curves of the capacitors indicate the films have a ferroelectric nature. The dielectric constant and dielectric loss of the films at 100 kHz are 450 and 0.038, respectively. At 25°C, where the thermo-sensitive capacitors work, the temperature coefficient of dielectric constant (TCD) is about 5.9 %/°C. These results indicate that the capacitors with sol-gel derived BST thin films are promising to develop dielectric type uncooled infrared sensors.     

Spontaneous growth by sol-gel process of low temperature ZnO as cathode buffer layer in flexible inverted organic solar cells

In this study, the sol–gel method was employed to prepare zinc oxide (ZnO) thin films as cathode buffer layers for inverted organic solar cells (IOSCs). We used a low temperature sol-gel process for the synthesis of ZnO thin films, in which the molar ratio of zinc acetate dihydrate (ZAD) to ethanolamine (MEA) was varied; subsequently, using the thin films, we successfully fabricated inverted solar cells on flexible plastic substrates. A ZnO sol–gel was first prepared by dissolving ZAD and MEA in ethylene glycol monomethyl ether (EGME). The molar ratios of ZAD to MEA were set as 1:1.2, 1:1, and 1:0.8, and we investigated the characteristics of the resulting ZnO thin films. We investigated the optical transmittance, surface roughness, and surface morphology of the films. Then, we discussed the reasons about the improvement of the device efficiency. The devices were fabricated using the ZnO thin films as cathode buffer layers. The results indicated that the morphology of the thin films prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 changed to a rippled nanostructure after two-step annealing. The PCE was enhanced because of the higher light absorption in the active layer caused by the nanostructure. The structure of the inverted device was ITO/ZnO/P3HT:PC₆₁BM/MoO₃/Ag. The short-circuit current densities (8.59 mA/cm² and 8.34 mA/cm²) of the devices with films prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 ratios, respectively, and annealed at 125 °C were higher than that of the device containing the ZnO thin film that was annealed at 150 °C. Inverted solar cells with ZnO films that were prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 and annealed at 125 °C exhibited PCEs of 3.38% and 3.30%, respectively. More than that, PCEs of the flexible device can reach up to 1.53%.     

衬底温度对PLD法制备的ZnO:Ga薄膜结构和性能的影响

利用脉冲激光沉积法在石英衬底上制备了镓掺杂氧化锌(ZnO:Ga)透明导电薄膜,研究了衬底温度对薄膜的结构、表面形貌和光电性能的影响.研究表明:制备的ZnO:Ga薄膜是具有六角纤锌矿结构的多晶薄膜.随着衬底温度的增加,衍射峰明显增强,晶粒尺寸增大.当衬底温度为450℃时,薄膜的最低电阻率为8.5×10<'-4>Ω·cm,...     

Structural,Optical and Electrical Properties of Polycrystalline CuO Thin Films Prepared by Magnetron Sputtering

Cupric oxide thin films were deposited on silicon and sapphire substrates by reactive radio frequency magnetron sputtering at different substrate temperatures. The results showed that the CuO films were composed of different sizes of CuO nano-grains and the CuO films deposited on Si substrates showed a more dense and uniform surface than that deposited on Al₂O₃ substrates. It was noted that both the CuO films deposited on Si and Al₂O₃ substrates revealed only CuO related diffractions and the preferred orientation of the CuO films changed from (002) to (111) as the substrate temperature increased. Moreover, the carrier concentration was 1.141?×?10¹⁸ cm^?3 and the mobility was 0.401 cm²/v s at 450°C substrate temperature. The controllable electrical properties of the films can be achieved by the variation of crystal quality arising from the substrate temperature.     

Transformation process of laser ablated PZT thin films

Transformation behavior of piezoelectric lead zirconate titanate (PZT) thin films prepared by laser ablation on unheated Al₂O₃ substrates was investigated within a broad temperature region. As-deposited films were mainly amorphous containing some microcrystalline perovskite and pyrochlore phases. The rhombohedral perovskite was the main phase in the films annealed between 500 and 800°C. These films also contained some pyrochIore, PbTiO₃, PbO, and ZrO₂. The PbO and ZrO₂ disappeared in the optimal annealing temperature interval of 700 to 800°C. Decomposition reactions took place above 800°C due to evaporation of lead and diffusion reactions occurred between substrate and film so that the films annealed at 1100°C consisted of ZrO₂, TiO₂, and PbO.     

Influence of Substrate Temperature and Post-Deposition Annealing on Material Properties of Ga-Doped ZnO Prepared by Pulsed Laser Deposition

Ga-doped ZnO films were prepared at 10 mTorr of oxygen over a broad temperature range using pulsed laser deposition. The carrier concentration of as-deposited films decreased monotonically with deposition temperature over a temperature range of 25°C to 450°C. Post-deposition annealing of as-deposited films in forming gas (5% H₂ in argon) or vacuum resulted in a substantial increase in both carrier concentration and electron mobility. The figure of merit was highest for films deposited at 250°C then annealed in forming gas at 400°C. The optical transmittance was near 90% throughout the visible and near-infrared spectral regions. These results indicate that Ga-doped ZnO is a viable alternative to transparent indium-based conductive oxides.     

Effect of Temperature on Structural and Morphologic Properties of ZnO Films Annealed in Ammonia Ambient

ZnO thin films were prepared on Si(111) substrates by pulsed laser deposition (PLD). Then, the samples were annealed at different temperatures in NH₃ ambient and their properties were investigated particularly as a function of annealing temperature. The structure, morphology, and optical properties of ZnO films were studied by x-ray diffraction (XRD), Fourier transform infrared spectroscope (FTIR), scanning electron microscope (SEM), and photoluminescence (PL). The results show that the increase of annealing temperature makes for the improvement in the crystal quality and surface morphology below the temperature of 650°C. However, when the annealing temperature is above 650°C, the ZnO films will volatilize and, especially at 750°C, ZnO will volatilize completely.     

Epitaxial growth of (11\bar 20) ZnO on (01\bar 12) Al2O3 by metalorganic chemical vapor deposition2) Al2O3 by metalorganic chemical vapor deposition

There has been increased interest in high quality ZnO films for use in a diverse range of applications such as in high frequency surface acoustic wave filters, buffer layers for GaN growth, transparent and conductive electrodes, and solid state lasers. In the present paper, ZnO films were epitaxially grown on R-plane sapphire substrates by metalorganic chemical vapor deposition at temperatures in the range 350–450°C. X-ray diffraction and electron microscopy results indicate that the ZnO films are epitaxially grown on ( $01\bar 12$ ) Al₂O₃ surface with the ( $11\bar 20$ ) plane parallel to the surface. Cross-sectional high resolution-transmission electron microscopy imaging of the as-grown film shows that the interface is semi-coherent and atomically sharp, with misfit dislocations relieving the misfit strain between ZnO and sapphire. In order to check the thermal stability of the as-grown ZnO films, annealing in an O₂+N₂ ambience at 850°C for 30 min was performed. The annealed films showed improved crystallinity. At the same time, limited reaction between ZnO and sapphire occurred, resulting in the formation of a 15–20 nm thick spinel layer at the interface.     

Properties of antimony doped ZnO thin films deposited by spray pyrolysis technique

Antimony (Sb) doped zinc oxide (ZnO) thin films were deposited on the glass substrate at 450°C using spray pyrolysis technique. Effect of Sb doping on surface morphology structural, optical and electrical properties were studied. X-ray diffraction (XRD) analysis showed that both the undoped and doped ZnO thin films are polycrystalline in nature with (101) preferred orientation. SEM analysis showed a change in surface morphology of Sb doped ZnO thin films. Doping results in a marked increase in conductivity without affecting the transmittance of the films. ZnO films prepared with 3 at % Sb shows the lowest resistivity of 0.185 Ohm cm with a Hall mobility of 54.05 cm² V^–1 s^–1, and a hole concentration of 6.25 × 10¹⁷ cm^–3.     

Effect of Rapid Thermal Annealing on Sputtered CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> Thin Films

Calcium copper titanium oxide (CaCu₃Ti₄O₁₂, abbreviated to CCTO) films were deposited on Pt/Ti/SiO₂/Si substrates at room temperature (RT) by radiofrequency magnetron sputtering. As-deposited CCTO films were treated by rapid thermal annealing (RTA) at various temperatures and in various atmospheres. X-ray diffraction patterns and scanning electron microscope (SEM) images demonstrated that the crystalline structures and surface morphologies of CCTO thin films were sensitive to the annealing temperature and ambient atmosphere. Polycrystalline CCTO films could be obtained when the annealing temperature was 700°C in air, and the grain size increased signifi- cantly with annealing in O₂. The 0.8-μm CCTO thin film that was deposited at RT for 2 h and then annealed at 700°C in O₂ exhibited a high dielectric constant (ε′) of 410, a dielectric loss (tan δ) of 0.17 (at 10 kHz), and a leakage current density (J) of 1.28 × 10⁻⁵ A/cm² (at 25 kV/cm).     

Investigation of the blue–green emission and UV photosensitivity of Cu-doped ZnO films

Cu-doped zinc oxide (ZnO:Cu) films were deposited on p-Si (100) substrates using radio-frequency reactive magnetron sputtering. The structure and optical properties of the films were characterized by X-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and fluorescence spectroscopy. XRD and SEM results revealed that ZnO:Cu film had a better preferential orientation along the c-axis compared with pure ZnO film. The chemical state of copper and oxygen in ZnO:Cu films was investigated by XPS. The results suggest that the Cu ion has a mixed univalent and bivalent state. The integrated Cu²⁺/Cu⁺ intensity ratio increased with the O₂ partial pressure. Photoluminescence measurements at room temperature revealed a double peak in the blue regions and a green emission peak. The close relationship between the valence state of Cu ions and the blue–green emission is discussed in detail. A higher photocurrent was observed for ZnO:Cu films under UV illumination. UV photodetectors based on ZnO:Cu films have high sensitivity and fast response and recovery times. Under periodic UV illumination at 380 nm the ZnO:Cu films showed stable photocurrent growth and decay, so the films are potential candidate materials for UV photodetectors.     

Effect of thermal annealing on physical properties of vacuum evaporated In2S3 buffer layer for eco-friendly photovoltaic applications

The present communication reports the effect of thermal annealing on the physical properties of In₂S₃ thin films for eco-friendly buffer layer photovoltaic applications. The thin films of thickness 150 nm were deposited on glass and indium tin oxide (ITO) coated glass substrates employing thermal vacuum evaporation technique followed by post-deposition thermal annealing in air atmosphere within a low temperature range 150–450 °C. These as-deposited and annealed films were subjected to the X-ray diffraction (XRD), UV–vis spectrophotometer, current–voltage tests and scanning electron microscopy (SEM) for structural, optical, electrical and surface morphological analysis respectively. The compositional analysis of as-deposited film is also carried out using energy dispersive spectroscopy (EDS). The XRD patterns reveal that the as-deposited and annealed films (≤300 °C) have amorphous nature while films annealed at 450 °C show tetragonal phase of β-In₂S₃ with preferred orientation (109) and polycrystalline in nature. The crystallographic parameters like lattice constant, inter-planner spacing, grain size, internal strain, dislocation density and number of crystallites per unit area are calculated for thermally annealed (450 °C) thin films. The optical band gap was found in the range 2.84–3.04 eV and observed to increase with annealing temperature. The current–voltage characteristics show that the as-deposited and annealed films exhibit linear ohmic behavior. The SEM studies show that the as-deposited and annealed films are uniform, homogeneous and free from crystal defects and voids. The grains in the thin films are similar in size and densely packed and observed to increase with thermal annealing. The experimental results reveal that the thermal annealing play significant role in the structural, optical, electrical and morphological properties of deposited In₂S₃ thin films and may be used as cadmium-free eco-friendly buffer layer for thin films solar cells applications.     

Zinc Oxysulfide Thin Films Grown by Pulsed Laser Deposition

Pulsed laser deposition was used to produce thin films of zinc oxysulfide (ZnO _x S_1−x ) on quartz substrates. The target was a sintered pellet (ZnO_0.39S_0.61) made of a solution precipitate. The film composition obtained by electron probe microanalysis (EPMA) was ZnO_0.41S_0.59, ZnO_0.44S_0.56, and ZnO_0.37S_0.63 for substrate temperatures of 450°C, 540°C, and 630°C, respectively. X-ray diffraction (XRD) showed that samples deposited at 450°C and at 540°C had a prominent cubic sphalerite phase, whereas samples deposited at 630°C consisted of three phases, viz. hexagonal wurtzite and cubic sphalerite (ZnS), and hexagonal zincite (ZnO). With respect to the tabulated lattice spacings for sphalerite (cell constant 0.5406 nm), distinct shifts were observed for the low temperature samples, yielding cell constants around 0.533 nm. Transmission electron microscopy (TEM)–selected area electron diffraction studies support the XRD data. Patterns of films deposited at 540°C could be indexed as sphalerite, with similar lattice shifts as in XRD, resulting in a cell constant of 0.53. Locally highly resolved chemical analysis by TEM–energy dispersive x-ray analysis revealed a stoichiometry that was consistent with the EPMA results. Ultraviolet (UV)–visible transmission measurements of the films led to bandgap energies around 3.3 eV, which is well below the reported bandgap energies of ZnS.     

Nanostructured thin films of the La0.7Sr0.3MnO3 manganite obtained using the extraction pyrolytic method

The extraction pyrolytic method is used to fabricate thin (100–300 nm) films of the lanthanum manganites La_0.7Sr_0.3MnO₃ on fused silica substrates. The films are deposited on the substrate using the alternate sessions of the centrifuging of solution and pyrolysis. The annealing of thin films at temperatures of greater than 650°C yields the single-phase La_0.7Sr_0.3MnO₃ material. It is demonstrated that the annealing temperature substantially affects the magnetic properties of the resulting films: the films exhibit the properties of spin glasses and ferromagnetic properties at temperatures of less than 700°C and greater than 700°C, respectively.     

Dielectric properties of low loss Ba<Subscript>6−3x</Subscript>Nd<Subscript>8+2x</Subscript>Ti<Subscript>18</Subscript>O<Subscript>54</Subscript> thin films prepared by pulsed laser deposition for microwave applications

Ba_6−3xNd_8+2xTi₁₈O₅₄ with x=0.25 (BNT-0.25, or simply, BNT) dielectric thin films with a thickness of 320 nm have been prepared on Pt-coated silicon substrates by pulsed laser deposition (PLD) at the substrate temperature of 650°C in 20 Pa oxygen ambient. X-ray analysis showed that the as-deposited films are amorphous and the films remain amorphous after a postannealing at 750°C for 30 min. The dielectric constant of the BNT films has been determined to be about 80 with a low loss tan δ of about 0.006 at 1 MHz. The capacitance-voltage (C-V), capacitance-frequency, and capacitance-temperature characteristics of a BNT capacitor with Pt top electrode were measured. A low leakage-current density of 4×10⁻⁶ A/cm² at 6 V was measured, and a preliminary discussion of the leakage-current mechanism is also given. It is proposed that amorphous BNT-0.25 thin films will be a potential dielectric material for microwave applications.     

Amorphous metal-semiconductor contacts for high temperature electronics—I Materials and characterisation

In this and a companion paper, we summarise the achievement of a metal-semiconductor contact whose electrical characteristics degrade only over tens of hours at 500°C. Although initially conceived as a barrier to Au diffusion, the thin amorphous metal film now fails because of out-diffusion of elements of the semiconductor. In this paper we summarise the rationale for using amorphous metal films, the choice of alloys, the fabrication of test structures, and the characterisation of these structures before and after exposure to temperatures as high as 700°C for 24 hr. The companion paper describes the thermal degradation of Schottky barrier characteristics of metal films on both Si and GaAs.