The effects of carrier gas and substrate temperature on ZnO films prepared by ultrasonic spray pyrolysis

ZnO films were deposited on glass substrates in the temperature range of 350–470 °C under an atmosphere of compressed air or nitrogen (N₂) by using ultrasonic spray pyrolysis technique. Structural, electrical and optical properties of the ZnO films were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), electrical two-probe and optical transmittance measurements. The ZnO films deposited in the range of 350–430 °C were polycrystalline with the wurtzite hexagonal structure having preferred orientation depending on the substrate temperature. The ZnO films deposited below 400 °C had a preferred (100) orientation while those deposited above 400 °C mostly had a preferred (002) orientation. The resistivity values of ZnO films depended on the types of carrier gas. The ZnO thin films deposited under N₂ atmosphere in the range of 370–410 °C showed dense surface morphologies and resistivity values of 0.6–1.1 Ω-cm, a few orders of magnitude lower than those deposited under compressed air. Hydrogen substition in ZnO possibly contributed to decreasing resistivity in ZnO thin films deposited under N₂ gas. The Hall measurements showed that the behavior of ZnO films deposited at 410 °C under the N₂ atmosphere was n-type with a carrier density of 8.9–9.2×10¹⁶ cm^-3 and mobility of ～70 cm²/Vs. ZnO thin films showed transmission values at 550 nm wavelength in a range of 70–80%. The values of band gaps extrapolated from the transmission results showed bandgap shrinkage in an order of milli electron volts in ZnO films deposited under N₂ compared to those deposited under compressed air. The calculation showed that the bandgap reduction was possibly a result of carrier–carrier interactions.     

Synthesis and characterization of phosphorus-doped ZnO and (Zn,Mg)O thin films via pulsed laser deposition

The transport and optical properties of phosphorus-doped (Zn,Mg)O thin films grown via pulsed laser deposition (PLD) are studied. The carrier type of as-deposited (Zn,Mg)O:P films converts from n-type to p-type with increasing oxygen partial pressure. All the films exhibit good crystallinity with c-axis orientation. This result indicates the importance of oxidation conditions in realizing p-type (Zn,Mg)O:P films. The as-deposited ZnO:P film properties show a strong dependence on the deposition ambient at different growth temperatures. The resistivity of the samples deposited in O₃/O₂ mixture is two orders of magnitude higher than the films grown in oxygen and O₂/Ar/H₂ mixture. The room-temperature photoluminescence (PL) of the as-deposited films has been shown that growing in the O₂/Ar/H₂ mixture ambient significantly increases the band edge emission while inhibiting the visible emission. The enhanced ultraviolet (UV) emission in the films grown in O₂/Ar/H₂ mixture may result from hydrogen passivation of the deep level emission centers. The annealed ZnO:P films are n-type with nonlinear dependence of resistivity on annealing temperature. The resistivity increases in the films with annealing at 800°C while decreasing with further increasing annealing temperature. Strong visible light emission is observed from the ZnO:P films annealed in oxygen.     

Carrier gas and VI/II ratio effects on carbon clusters incorporation into ZnO films grown by MOCVD

Undoped ZnO films were deposited by atmospheric metal-organic chemical vapor deposition (MOCVD) on (0001) ZnO substrate. The films were grown at various partial pressure ratios of oxygen and zinc precursors (VI/II) using either N₂ or H₂ as carrier gas. Micro-Raman scattering was employed to study the effects of carrier gas, VI/II ratio and annealing on carbon impurity incorporation into the ZnO films. Besides the well known phonon modes of ZnO, Raman spectra of the samples grown with N₂ carrier gas show two additional broad peaks, which are ascribed to carbon sp² clusters related modes, spreading in the frequency range 1300–1600 cm^?1 and dominate the Raman spectrum of the sample grown under oxygen deficiency (VI/II=0.25). In addition, a band centered at ～520 cm^?1, considered as some defects related local vibrations, appears in the samples grown with N₂ as carrier gas and its intensity increases when the VI/II ratio decreases. The average cluster size, estimated from the intensity ratio of D over G bands of the carbon sp² clusters, ranges from 16.5 to 19.4 Å. However, in all the samples grown with H₂ as carrier gas, the bands related to carbon sp² clusters and defects, are largely suppressed and the second-order-Raman scattering band (1050–1200 cm^?1) is clearly observed in addition to the bulk ZnO lattice modes. After annealing the samples at 900 °C in oxygen ambient, the crystal quality has been improved for all the samples but the carbon related bands, formed in the as-deposited films grown with the N₂ carrier gas, were only weakened.     

Thermal stability of sputter-deposited ZnO thin films

This paper describes our investigation on the thermal stability of sputterdeposited, piezoelectric, ZnO thin films, using x-ray photoelectron spectroscopy (XPS), capacitance-voltage (C-V) measurements of metal-insulator-semiconductor structures, and electron microprobe. We focus on out-diffusion of Zn from ZnO thin films at a high temperature (450°C) and the composition change of zinc and oxygen after high temperature annealing (up to 700°C), since these factors are related to reliability and integrated circuits-process-compatibility of the ZnO films which are being used increasingly more in microtransducers and acoustic devices. Our experiments with electron microprobe show that ZnO thin films sputter-deposited from a ZnO target in a reactive environment (i.e., with O₂) are thermally stable (up to 700°C). Additionally, the out-diffusion of zinc atoms from the ZnO films at a high temperature (450°C) is verified to be negligible using the XPS and C-V measurement techniques. The usage of a compound ZnO target, reactive environment with O₂ and optimized deposition parameters (including gas ratio and pressure, substrate temperature, target-substrate distance and rf power, etc.) is critical to deposit thermally stable, high quality ZnO films.     

Resistivity changes of heavily-boron-doped CVD-prepared polycrystalline silicon caused by thermal annealing

Heavily-boron-doped polycrystalline Si films were deposited at 600°C on thermally grown SiO₂ by the thermal decomposition of SiH₄-BCl₃-H₂ mixture. Resistivity changes with isochronal or sequential annealing were systematically examined. Temperature dependence of equilibrium saturation carrier concentration was determined at 800 ～ 1100°C. Since as-deposited polycrystalline Si is in the super-saturated state, carrier concentration decreases from the super-saturated to equilibrium saturation value by annealings over 700°C for poly Si doped with over 2 × 10²⁰ cm^?3 resulting in anomalous resistivity change. Carrier concentration changes reversibly between saturation values with sequential annealing and is determined by the last annealing temperature when the annealing time is long enough. Mobility increases with annealing temperature, however, less increase is found for heavily doped poly Si, which is attributed to the suppression of grain growth caused by electrically inactive Si-B compounds.     

ZnO spintronics and nanowire devices

ZnO is a very promising material for spintronics applications, with many groups reporting room-temperature ferromagnetism in films doped with transition metals during growth or by ion implantation. In films doped with Mn during pulsed laser deposition (PLD), we find an inverse correlation between magnetization and electron density as controlled by Sn-doping. The saturation magnetization and coercivity of the implanted single-phase films were both strong functions of the initial anneal temperature, suggesting that carrier concentration alone cannot account for the magnetic properties of ZnO:Mn and factors such as crystalline quality and residual defects play a role. Plausible mechanisms for ferromagnetism include the bound magnetic polaron model or exchange that is mediated by carriers in a spin-split impurity band derived from extended donor orbitals. The progress in ZnO nanowires is also reviewed. The large surface area of nanorods makes them attractive for gas and chemical sensing, and the ability to control their nucleation sites makes them candidates for microlasers or memory arrays. Single ZnO nanowire depletion-mode metal-oxide semiconductor field effect transistors exhibit good saturation behavior, threshold voltage of ∼−3 V, and a maximum transconductance of 0.3 mS/mm. Under ultraviolet (UV) illumination, the drain-source current increased by approximately a factor of 5 and the maximum transconductance was ∼5 mS/mm. The channel mobility is estimated to be ∼3 cm²/Vss, comparable to that for thin film ZnO enhancement mode metal-oxide semiconductor field effect transistors (MOSFETs), and the on/off ratio was ∼25 in the dark and ∼125 under UV illumination. The Pt Schottky diodes exhibit excellent ideality factors of 1.1 at 25°C, very low reverse currents, and a strong photoresponse, with only a minor component with long decay times thought to originate from surface states. In the temperature range from 25°C to 150°C, the resistivity of nanorods treated in H₂ at 400°C prior to measurement showed an activation energy of 0.089 eV and was insensitive to ambient used. By contrast, the conductivity of nanorods not treated in H₂ was sensitive to trace concentrations of gases in the measurement ambient even at room temperature, demonstrating their potential as gas sensors. Sensitive pH sensors using single ZnO nanowires have also been fabricated.     

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.     

High rate (~7 nm/s), atmospheric pressure deposition of ZnO front electrode for Cu(In,Ga)Se2 thin‐film solar cells with efficiency beyond 15%

Undoped zinc oxide (ZnO) films have been grown on a moving glass substrate by plasma‐enhanced chemical vapor deposition at atmospheric pressure. High deposition rates of ~7 nm/s are achieved at low temperature (200 °C) for a substrate speed from 20 to 60 mm/min. ZnO films are highly transparent in the visible range (90%). By a short (~minute) post‐deposition exposure to near‐ultraviolet light, a very low resistivity value of 1.6·10⁻³ Ω cm for undoped ZnO is achieved, which is independent on the film thickness in the range from 180 to 1200 nm. The photo‐enhanced conductivity is stable in time at room temperature when ZnO is coated by an Al₂O₃ barrier film, deposited by the industrially scalable spatial atomic layer deposition technique. ZnO and Al₂O₃ films have been used as front electrode and barrier, respectively, in Cu(In,Ga)Se2 (CIGS) solar cells. An average efficiency of 15.4 ± 0.2% (15 cells) is obtained that is similar to the efficiency of CIGS reference cells in which sputtered ZnO:Al is used as electrode. Copyright © 2013 John Wiley & Sons, Ltd.     

Enhancement of the hydrogen gas sensitivity by large distribution of c-axis preferred orientation in highly Ga-doped ZnO polycrystalline thin films

The hydrogen gas sensing properties of highly Ga-doped ZnO (GZO) polycrystalline thin films deposited by radio-frequency magnetron sputtering have been studied. The relationship between the microstructural properties of preferred c-axis oriented thin films and the hydrogen gas sensing properties is described. The crystallite size and the preferred orientation distribution were characterized by X-ray diffraction. The crystallite size increased and the preferred orientation distribution decreased with increasing film thickness. In order to control the crystallite size and the c-axis orientation separately, a highly oriented ZnO template layer with different thickness was employed for deposition of 30-nm-thick GZO films. The c-axis orientation of these films were nearly comparable each other, while the crystallite size increased significantly with increasing thickness of the ZnO templates. The hydrogen gas sensitivity at an operating temperature of 330 °C increased slightly with decreasing crystallite size, while the sensitivity was dramatically enhanced by increasing the preferred orientation distribution. It is therefore proposed that the c-axis orientation plays an important role in determining the sensitivity of the hydrogen gas sensor.     

Effects of Growth Temperature on Properties of Nonpolar <Emphasis Type="Italic">a</Emphasis>-Plane ZnO Films on GaN Templates by Pulsed Laser Deposition

In this work, a-plane GaN/r-sapphire templates have been used to grow nonpolar a-plane ZnO films by pulsed laser deposition. The ZnO film growth temperature was varied in the range of 400°C to 600°C, and the effect of growth temperature on the properties of the ZnO thin films was investigated using x-ray diffraction, atomic force microscopy, photoluminescence (PL) spectroscopy, and Raman measurements. The results show that the crystal quality, surface morphology, strain states, and optical properties of a-plane ZnO films are strongly correlated with the deposition temperature. It is found that the crystallinity of the ZnO films gets better and the surface roughness decreases with increasing growth temperature. At a growth temperature of 600°C, the a-ZnO films display the best crystal quality with x-ray (11[`2]0) (11\bar{2}0) omega scan full-width at half-maximum values of 0.28° and 0.41° on axis (11[`2]0) (11\bar{2}0) at azimuth 0° and 90°, respectively. Furthermore, the PL spectrum measured at 83 K is dominated by neutral donor-bound excitons and free-electron-to-bound (e-A ₀) emission, and relatively intense LO-phonon replicas of (e-A ₀) have also been observed in the a-plane ZnO. The dominance of the free exciton and the appearance of its replicas strongly indicate the high quality of the film.     

The effects of process conditions and substrate on copper MOCVD using liquid injection of (hfac)Cu(vtmos)

Copper MOCVD (metalorganic chemical vapor deposition) using liquid injection for effective delivery of the (hfac)Cu(vtmos) [1,1,1,5,5,5-hexafluoro-2,4-pentadionato(vinyltrimethoxysilane) copper(I)] precursor has been performed to clarify growth behavior of copper films onto TiN, <100> Si, and Si₃N₄ substrates. Especially, we have studied the influences of process conditions and the substrate on growth rates, impurities, microstructures, and electrical characteristics of copper films. As the reactor pressure was increased, the growth rate was governed by a pick-up rate of (hfac)Cu(vtmos) in the vaporizer. The apparent activation energy for copper growth over the surface-reaction controlled regime from 155°C to 225°C was in the range 12.7–32.5 kcal/mol depending upon the substrate type. It revealed that H₂ addition at 225°C substrate temperature brought about a maximum increase of about 25% in the growth rate compared to pure Ar as the carrier gas. At moderate deposition temperatures, the degree of a <111> preferred orientation for the deposit was higher on the sequence of <Cu/Si<Cu/TiN<Cu/Si₃N₄. The relative impurity content within the deposit was in the range 1.1 to 1.8 at.%. The electrical resistivity for the Cu films on TiN illustrated three regions of the variation according to the substrate temperature, so the deposit at 165°C had the optimum resistivity value. However, the coarsened microstructures of Cu on TiN prepared above 275°C gave rise to higher electrical resistivities compared to those on Si and Si₃N₄ substrates.     

Preparation of PbTiO3 thin films by plasma enhanced MOCVD and the effect of rapid thermal annealing

Dielectric PbTiO₃-thin films were prepared on p-Si(100) substrate by plasma enhanced metalorganic chemical vapor deposition using high purity Ti(O-i-C₃H₇)₄, Pb(tmhd)₂, and oxygen. As-deposited films were post-treated by rapid thermal annealing method, and the effect of annealing was examined under various conditions. The deposition process was controlled by mixed-control scheme at temperatures lower than 350°C, but controlled by heterogeneous surface reaction at temperatures greater than 350°C. The as-deposited films showed PbO structure at 350∼400°C, but (100) and (101) PbTiO₃ orientations started to appear at 450°C. The deposition rate was increased with rf power due to the enhanced dissociation of Ti and Pb precursors. It was found that the concentration of oxygen plays an important role in crystallization of PbTiO₃ during the rapid thermal annealing. A linear relationship was obtained between the dielectric constant of PbTiO₃ films and the annealing temperature. However, the surface roughness and leakage current density increased mainly due to the defects caused by volatilization of lead and the interface layer formed during the high temperature annealing.     

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.     

Microstructure and properties of aluminum contacts formed on GaAs(100) by low pressure chemical vapor deposition with dimethylethylamine alane source

We report on a low pressure chemical vapor deposition of metallic thin aluminum films on GaAs (001) with a dimethylethylamine alane (DMEAA) source and H₂ as a carrier gas. The deposition temperatures varied in the range 130–360°C. Integrated volumes for Al (111), (100), (110)R, and (110) grains were estimated by the x-ray diffraction technique and the growth temperature values preferred for every type of grains were observed. The experimentally observed dominance of Al(110)R over Al(110), irrespective of the substrate miscut direction, supports the GaAs(100) inner anisotropy effect on the Al grain orientation. Electrical resistivity was 5 ·cm for the best Al films. The Schottky barrier heights were near a 0.7 eV level and the ideality factor n=1.1. Nonalloyed ohmic contacts were fabricated on an n-type GaAs epitaxial layer with an additional set of Si-layers near the Al/GaAs interface. Specific contact resistance, c=7 cm², was measured. Best contacts were obtained at a deposition temperature lower than 250°C.     

Electrical and optical properties of oxygen doped GaN grown by MOCVD using N2O

Oxygen doped GaN has been grown by metalorganic chemical vapor deposition using N₂O as oxygen dopant source. The layers were deposited on 2″ sapphire substrates from trimethylgallium and especially dried ammonia using nitrogen (N₂) as carrier gas. Prior to the growth of the films, an AIN nucleation layer with a thickness of about 300? was grown using trimethylaluminum. The films were deposited at 1085°C at a growth rate of 1.0 μm/h and showed a specular, mirrorlike surface. Not intentionally doped layers have high resistivity (>20 kW/square). The gas phase concentration of the N₂O was varied between 25 and 400 ppm with respect to the total gas volume. The doped layers were n-type with carrier concentrations in the range of 4×10¹⁶ cm⁻³ to 4×10¹⁸ cm⁻³ as measured by Hall effect. The observed carrier concentration increased with increasing N₂O concentration. Low temperature photoluminescence experiments performed on the doped layers revealed besides free A and B exciton emission an exciton bound to a shallow donor. With increasing N₂O concentration in the gas phase, the intensity of the donor bound exciton increased relative to that of the free excitons. These observations indicate that oxygen behaves as a shallow donor in GaN. This interpretation is supported by covalent radius and electronegativity arguments.     

High-Vacuum Evaporation of <Emphasis Type="Italic">n</Emphasis>-CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> Photoabsorber Films for Hybrid PV Structures

Thin films of Cu-In-Se (CISe) photoabsorber with an overall composition of CuIn₃Se₅ were deposited onto glass/indium tin oxide (ITO) substrates from a polycrystalline bulk CuIn₃Se₅ source using the high-vacuum evaporation technique. Thermal conditions for the substrates during the evaporation process and the subsequent annealing in vacuum were selected to prepare polycrystalline n-CuIn₃Se₅ photoabsorber layers for use in hybrid photovoltaic structures based on an inorganic photoabsorber and conductive polymer functional layers. The CISe layers were deposited at a substrate temperature of 200°C and were annealed at temperatures from 300°C to 500°C in vacuum. Part of the as-deposited CISe was annealed twice, in argon and in vacuum at 500°C. These layers exhibited high photosensitivity and photoconductivity when illuminated with white light at an intensity of 100 mW/cm². The results showed that the chalcopyrite structure of the prepared CISe photoabsorber films adhered well to the glass/ITO substrate. The average value of charge carrier concentration and the profile of charge carrier concentration in the annealed CISe photoabsorber layer were calculated using impedance spectroscopy.     

Effect of growth temperature on diode parameters of n-ZnO/p-Si heterojuction diodes grown by atomic layer deposition

n-ZnO/p-Si heterojunctions were grown by atomic layer deposition (ALD) on (100) p-Si substrates at different growth temperatures in the range of ~100–250 °C. The current-voltage characterization of all the heterojunctions showed typical rectifying behavior, a true signature of a p-n junction diode. The diode grown at 100 °C were having significantly lower reverse saturation current (~21 nA) and high rectification factor (~120) compared to those grown at relatively higher temperatures such as 200 or 250 °C. From capacitance-voltage measurements, it was found that the depletion width in the ZnO side of n-ZnO/p-Si diode was maximum (~60 nm) for the diode grown at 100 °C and decreased gradually to ~3 nm for the diodes grown at high temperatures of 250 °C. The electron concentration in ZnO films was found to increase significantly on increasing the growth temperature from ~100 to 250 °C. The junction capacitance also showed an increasing trend with increase in the growth temperature. The variation of diode parameters with growth temperature has been discussed in terms of carrier concentration in ZnO films and associated growth mechanisms of the ALD. Such low temperature grown n-ZnO/p-Si diodes with lower reverse saturation current and large depletion width may be suitable for photo detection applications.     

Investigation of optical and electronic properties in Al–Sn co-doped ZnO thin films

Al-Sn co-doped ZnO thin films were deposited onto quartz substrates by sol-gel processing. The surface morphology and electrical and optical properties were investigated at different annealing temperatures. The surface morphology showed a closely packed arrangement of crystallites in all the doped films. As prepared co-doped films show a preferred orientation along an (0 0 2) plane. This preferred orientation was enhanced by increasing the annealing temperature to between 400 °C and 500 °C, but there was a shift to the (1 0 1) plane when the annealing temperature rose above 500 °C. These samples show, on average, 91.2% optical transmittance in the visible range. In this study, the optical band gap of all the doped films was broadened compared with pure ZnO, regardless of the different annealing temperature. The carrier concentration and carrier mobility of the thin films were also investigated.     

Ultraviolet detectors based on epitaxial ZnO films grown by MOCVD

High-quality zinc oxide (ZnO) films were epitaxially grown on R-plane sapphire substrates by metalorganic chemical vapor deposition at temperatures in the range of 350°C to 600°C. In-situ nitrogen compensation doping was performed using NH₃. Microstructural and optical properties of the films, as well as the N-doping effects, were studied. The metal-semiconductor-metal ultraviolet sensitive photodetectors were fabricated on N-doped epitaxial ZnO films. The detector showed fast photoresponse, with a rise time of 1 μs and a fall time of 1.5 μs. Low-frequency photoresponsivity, on the order of 400 A/W at 5 V bias, was obtained.     

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.