Microstructural characteristics and crystallographic evolutions of Ga-doped ZnO films grown on sapphire substrates at high temperatures by RF magnetron sputtering

The microstructural characteristics and crystallographic evolutions of Ga-doped ZnO (GZO) films grown at high temperatures were examined by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The GZO films with various film thicknesses were grown on (0 0 0 1) Al₂O₃ substrates at 750 °C by RF magnetron sputtering using a 2 wt% Ga-doped ZnO single target. The (0 0 0 2) ZnO peaks in the XRD patterns shifted to a higher angle with increasing film thickness and an additional (1 0 1¯ 1) ZnO peak was observed in the final stage of film growth. HRTEM showed the epitaxial growth of GZO films in the initial growth stage and the formation of surface protrusions in the intermediate stage due to elastic relaxation. The surface protrusions consisted of {1 0 1¯ 1}, {1 0 1¯ 3}, and {0 0 0 2} planes. After the surface protrusions had formed, a GZO film with many c-axis tilted grains formed due to plastic relaxation, where the tilted grain boundaries had an angle of 62° to the substrate. The formation of the protrusions and c-axis tilted grains was closely related to the strain status of the film induced by Ga incorporation, high-temperature growth and a high film thickness.     

Growth and microstructural features of laser ablated LiCoO2 thin films

Thin films of LiCoO₂ were prepared by pulsed laser deposition technique and the properties were studied in relation to the deposition parameters. The films deposited from a sintered composite target (LiCoO₂+Li₂O) in an oxygen partial pressure of 100 mTorr and at a substrate temperature of 300 °C exhibited preferred c-axis (0 0 3) orientation perpendicular to the substrate surface. The AFM data demonstrated that the films are composed of uniform distribution of fine grains with an average grain size of 80 nm. The grain size increased with an increase in substrate temperature. The (0 0 3) orientation decreased with increase in (1 0 4) orientation for the films deposited at higher substrate temperatures (>500 °C) indicating that the films’ growth is parallel to the substrate surface. The composition of the experimental films was analyzed using X-ray photoelectron spectroscopy (XPS). The binding energy peaks of Co(2p_3/2) and Co(2p_1/2) are, respectively, observed at 779.3 and 794.4 eV, which can be attributed to the Co³⁺ bonding state of LiCoO₂. The electrochemical measurements were carried out on Li//LiCoO₂ cells with a lithium metal foil as anode and LiCoO₂ film as cathode of 1.5 cm² active area using a Teflon home-made cell hardware. The Li//LiCoO₂ cells were tested in the potential range 2.6-4.2 V. Specific capacity as high as 205 mC/cm² μm was measured for the film grown at 700 °C. The growth of LiCoO₂ films were studied in relation to the deposition parameters for their effective utilization as cathode materials in solid-state microbattery application.     

Effect of substrate temperature on the room-temperature ferromagnetism of Cu-doped ZnO films

Wurtzite structure ZnO films doped with ~2 at% Cu were deposited at substrate temperatures (T_s) from 350 to 600 °C by helicon magnetron sputtering. All the films exhibited room-temperature (RT) ferromagnetism (FM) and the maximum saturation magnetization (M_s) was 1.2 emu/cm³ (~0.15 μ_B/Cu). Cu ions were mainly in a divalent state as identified by X-ray photoelectron spectroscopy. FM tended to increase with decreasing T_s, and vacuum annealing enhanced the M_s. These results suggested that oxygen vacancies and/or zinc interstitials might contribute to the ferromagnetic performance. Thus, the observed FM was explained in terms of the defect related mechanism.     

Crystal growth, characterization and spectroscopic study of europium-doped NaY(PO3)4

Europium-doped NaY(PO₃)₄ single crystals have been synthesized by the flux method with sizes around 1 mm³. The unit cell parameters at room temperature refined by X-ray powder diffraction are a=7.1510(4) Å; b=13.0070(8) Å; c=9.6973(2) Å; β=90.606(3)°, Z=4 with the space group P2₁/n in monoclinic system. The present single crystals have a needle shape, they are elongated along the a crystallographic direction, and their size is in the 500 μm–1 mm range. The linear thermal expansion tensor parameters were determined, being the maximum value along the b direction, 16.1×10⁻⁶ K⁻¹ and the minimum along the a direction being 11.7×10⁻⁶ K⁻¹. The IR vibration modes attributed to the group P–O are consistent with the crystallographic data concerning the chain aspect of the phosphate anion. This material melts incongruently at 1141 K. Intense visible emissions attributed to Eu^{3+ 5}D₀→⁷F₁, ⁵D₀→⁷F₂ and ⁵D₀→⁷F₄, electronic transitions have been observed after pumping at 355 nm at room temperature.     

Heteroepitaxial growth of Cu2O thin film on ZnO by metal organic chemical vapor deposition

Cuprous oxide (Cu₂O) thin films were grown epitaxially on c-axis-oriented polycrystalline zinc oxide (ZnO) thin films by low-pressure metal organic chemical vapor deposition (MOCVD) from Copper(II) hexafluoroacetylacetonate [Cu(C₅HF₆O₂)₂] at various substrate temperatures, between 250 and 400 °C, and pressures, between 0.6 and 2.1 Torr. Polycrystalline thin films of Cu₂O grow as single phase with [1 1 0] axis aligned perpendicular to the ZnO surface and with in-plane rotational alignment due to (2 2 0)_Cu2O(0 0 0 2)_ZnO; [0 0 1]_Cu2O[1 2¯ 1 0]_ZnO epitaxy. The resulting interface is rectifying and may be suitable for oxide-based p–n junction solar cells or diodes.     

Amorphous tungsten-doped In2O3 transparent conductive films deposited at room temperature from metallic target

Amorphous tungsten-doped In₂O₃ (IWO) films were deposited from a metallic target by dc magnetron sputtering at room temperature. Both oxygen partial pressure and sputtering power have significant effects on the electrical and optical properties of the films. The as-deposited IWO films with the optimum resistivity of 5.8 × 10^?4 Ω·cm and the average optical transmittance of 92.3% from 400 to 700 nm were obtained at a W content of 1 wt%. The average transmittance in the near infrared region (700–2500 nm) is 84.6–92.8% for amorphous IWO prepared under varied oxygen partial pressure. The mobility of the IWO films reaches its highest value of 30.3 cm² V^?1 s^?1 with the carrier concentration of 1.6 × 10²⁰ cm^?3, confirming their potential application as transparent conductive oxide films in various flexible devices.     

Effects of oxygen partial pressure during sputtering growth on physical properties of Zn0.93Mn0.07O thin films

We have studied structural, optical, electrical, and magnetic properties of Zn_0.93Mn_0.07O thin films grown by RF magnetron sputtering under ambient gas mixtures of O₂ and Ar. As the oxygen partial pressure increases, the electron concentration systematically decreases and photoluminescence peaks related to oxygen vacancies gradually diminish. These results suggest that oxygen vacancies are majority donors. Smooth surface morphology and electron concentration as low as ∼10¹⁵ cm⁻³ are obtained simultaneously for the film grown in an optimal oxygen partial pressure. This film exhibits ferromagnetism with the Curie temperature of 78 K, while other films grown in higher or lower oxygen partial pressure show paramagnetic behavior down to low temperature. The disappearance of the ferromagnetism can be explained in terms of crystalline quality and surface smoothness rather than electron concentration.     

Structure and growth morphology of Gd2O3-doped CeO2 thin films

Gd₂O₃-doped CeO₂ (Gd_0.1Ce_0.9O_1.95, GDC) thin films were synthesized on (1 0 0) Si single crystal substrates by a reactive radio frequency magnetron sputtering technique. Structures and surface morphologies were characterized by X-ray diffraction (XRD), Atomic Force Microscopy (AFM) and one-dimensional power spectral density (1DPSD) analysis. The XRD patterns indicated that, in the temperature range of 200–700 °C, f.c.c. structured GDC thin films were formed with growth orientations varying with temperature—random growth at 200 °C, (2 2 0) textures at 300–600 °C and (1 1 1) texture at 700 °C. GDC film synthesized at 200 °C had the smoothest surface with roughness of R_rms=0.973 nm. Its 1DPSD plot was characterized with a constant part at the low frequencies and a part at the high frequencies that could be fitted by the f^−2.4 power law decay. Such surface feature and scaling behavior were probably caused by the high deposition rate and random growth in the GDC film at this temperature. At higher temperatures (300–700 °C), however, an intermediate frequency slope (−γ₂≈−2) appeared in the 1DPSD plots between the low frequency constant part and the high frequency part fitted by f⁻⁴ power law decay, which indicated a roughing mechanism dominated by crystallographic orientation growth that caused much rougher surfaces in GDC films (R_rms>4 nm).     

SIMS and Raman characterizations of ZnO:N thin films grown by MOCVD

Nitrogen was incorporated into ZnO films grown by metalorganic chemical vapour deposition (MOCVD) on ZnO substrates using DMZn-TEN, tert-butanol and diallylamine, respectively, as zinc, oxygen and doping sources. The carrier gas was either hydrogen or nitrogen and the partial pressure ratio (R_VI/II) was varied in order to favor the nitrogen incorporation and/or reduce carbon related defects. The ZnO films have been characterized by Micro-Raman scattering and SIMS measurements. SIMS measurements confirm the nitrogen incorporation with concentrations extending from ∼10¹⁹ cm⁻³ to ∼4×10²⁰ cm⁻³. Raman spectra show nitrogen local vibration modes in films grown at low R_VI/II ratio and using H₂ as carrier gas. However, a vibration band attributed to carbon clusters dominates the Raman spectra for films grown with N₂ carrier. The contribution of N complexes was discussed. The strain was calculated for the as-grown and annealed films and it changes from tensile to compressive after annealing.     

Fabrication and characteristics of CeO2 films on Si(1 0 0) substrates by pulsed laser deposition

A detailed investigation about the dependence of film orientation on deposition temperature and ambient oxygen pressure has been carried out for CeO₂ films on Si(1 0 0) substrates using pulsed laser deposition. It has been found that the CeO₂ film orientation varies with increasing oxygen pressure at 750°C deposition temperature. In addition, the recovery of preferential orientation of CeO₂ films grown at 20 Pa ambient oxygen pressure with increasing deposition temperature has also been found for the first time. X-ray photoelectron spectroscopy (XPS) measurements confirm that stoichiometric CeO₂ films can be grown at lower oxygen pressure (5×10⁻³ Pa). HRTEM result also indicates that the CeO₂ films grown at low oxygen pressure are of high crystallinity.     

Structural,electrical and optical properties of SnO2 films deposited on Y-stabilized ZrO2 (1 0 0) substrates by MOCVD

SnO₂ films have been deposited on Y-stabilized ZrO₂ (YSZ) (1 0 0) substrates at different substrate temperatures (500–800 °C) by metalorganic chemical vapor deposition (MOCVD). Structural, electrical and optical properties of the films have been investigated. The films deposited at 500 and 600 °C are epitaxial SnO₂ films with orthorhombic columbite structure, and the HRTEM analysis shows a clear epitaxial relationship of columbite SnO₂(1 0 0)||YSZ(1 0 0). The films deposited at 700 and 800 °C have mixed-phase structures of rutile and columbite SnO₂. The carrier concentration of the films is in the range from 1.15×10¹⁹ to 2.68×10¹⁹ cm⁻³, and the resistivity is from 2.48×10⁻² to 1.16×10⁻² Ω cm. The absolute average transmittance of the films in the visible range exceeds 90%. The band gap of the obtained SnO₂ films is about 3.75–3.87 eV.     

Epitaxial growth of tin oxide film on TiO2(1 1 0) using molecular beam epitaxy

Growth of tin oxide thin films using molecular beam epitaxy in a pyrolyzed nitrogen dioxide atmosphere on a titanium dioxide (1 1 0) substrate was investigated using X-ray photoelectron spectroscopy (XPS), electron diffraction, and atomic force microscopy (AFM). Properties of deposited films were studied for their dependence on substrate temperature and oxidation gas pressure. Analyses using XPS data revealed that tin atoms were fully oxidized to Sn⁴⁺ and SnO₂ films were grown epitaxially in deposition conditions of substrate temperatures of 627 K or higher and NO₂ pressure greater than 3×10⁻³ Pa. At a substrate temperature of 773 K, a smooth surface with atomic steps was visible in the SnO₂ films, but above or below this temperature, fine grains with crystal facets or porous structures appeared. At pressures of 8×10⁻⁴ to 3×10⁻⁴ Pa, the randomly oriented SnO phase was dominantly grown. Further decreasing the pressure, the Sn metal phase, which was epitaxially crystallized at less than 500 K, was also grown.     

Influence of oxygen/argon ratio on structural,electrical and optical properties of Ag-doped ZnO thin films

Ag-doped ZnO (ZnO:Ag) thin films were deposited on quartz substrates by radio frequency magnetron sputtering technique. The influence of oxygen/argon ratio on structural, electrical and optical properties of ZnO:Ag films has been investigated. ZnO:Ag films gradually transform from n-type into p-type conductivity with increasing oxygen/argon ratio. X-ray photoelectron spectroscopy measurement indicates that Ag substitutes Zn site (Ag_Zn) in the ZnO:Ag films, acting as acceptor, and being responsible for the formation of p-type conductivity. The presence of p-type ZnO:Ag under O-rich condition is attributed to the depression of the donor defects and low formation energy of Ag_Zn acceptor. The I–V curve of the p-ZnO:Ag/n-ZnO homojunction shows a rectification characteristic with a turn-on voltage of ∼7 V.     

Oriented polycrystalline α-HgI2 thick films grown by physical vapor deposition

This work investigates the growth of polycrystalline α-HgI₂ thick films from physical vapor deposition. By varying the growth conditions, the as-deposited thick films are characterized by scanning electron microscopy, X-ray diffraction, current–voltage and photoconductivity measurements. The growth mechanism and its effects to the properties of these polycrystalline α-HgI₂ thick films are then discussed. Finally, the best deposition conditions for polycrystalline α-HgI₂ thick films compactly formed by separated columnar monocrystallines with uniform orientation along c-direction and with good crystallinity are reported.     

Synthesis and optical properties of purified translucent,orthorhombic boron nitride films

Large-area (>1 cm²) freestanding translucent orthorhombic boron nitride (oBN) films have been synthesized by magnetron sputtering at a low radio-frequency power of 120 W. The structural characterizations were performed by means of X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. It is demonstrated that oBN is a direct band gap semiconductor (E_g∼3.43 eV). Excited by ultraviolet laser (wavelength at 325 nm), the oBN films emit strong white light, which can be seen by the naked eyes in the dark. In the photoluminescence spectrum, besides the ultraviolet near-band-edge radiative recombination emission, there are three visible emission bands (centered at 400, 538, and 700 nm) arising from the defect-related deep-level centers of oBN, which are mixed to form the white light emission. The hardness and elastic modulus of oBN films are 11.5 and 94 GPa, respectively, examined by nanoindentation measurements.     

Crystalline and electrical properties of pulsed laser deposited BST on platinized silicon substrates

In order to produce thin film capacitors with elevated capacitance and breakdown strength, pulsed laser deposition of the ferroelectric material Ba_0.6Sr_0.4TiO₃ (BST) has been made on (1 1 1)Pt/Ti/SiO₂/Si substrates. The films are in situ crystallized at 700 °C, polycrystalline in nature, and exhibit a single perovskite phase. This paper reports on both the effect of the oxygen pressure during heating and deposition, and the influence of different modes of introduction during the deposition stage, on the crystalline and electrical properties of the BST films. Orientation of films depends on the deposition oxygen pressure, with a (1 1 1) preferential orientation obtained when depositing under vacuum. XRD characterization reveals that the out-of-plane parameter of BST films increases when depositions are made under lower oxygen pressure. This phenomenon is related to a higher concentration of vacancies and defects in the films grown under low-pressure environment. However, a local introduction of oxygen on the substrate improves the annihilation of these defects. The crystalline orientation of the films is also highly dependent on the residual oxygen pressure during heating. A high (1 1 1) preferentially oriented BST film is obtained when heating and depositing under 0.1 mbar oxygen pressure. The heating atmosphere is thought to influence the out-diffusion of titanium on the surface of the Pt layer, thus modifying the nucleation and growth of BST films. Aluminum electrodes have been deposited on top of the BST films by dc sputtering to measure electrical capacitances. The calculated dielectric constant of in situ crystallized films deposited under 0.1 mbar oxygen pressure exceeds 500 at 100 kHz under zero dc bias. This high dielectric constant value obtained without post-deposition treatment appears to be of great technological interest.     

MOCVD growth of GaN on Si(1 1 1) substrates using an ALD-grown Al2O3 interlayer

GaN thin films have been grown on Si(1 1 1) substrates using an atomic layer deposition (ALD)-grown Al₂O₃ interlayer. This thin Al₂O₃ layer reduces strain in the subsequent GaN layer, leading to lower defect densities and improved material quality compared to GaN thin films grown by the same process on bare Si. XRD ω-scans showed a full width at half maximum (FWHM) of 549 arcsec for GaN grown on bare Si and a FWHM as low as 378 arcsec for GaN grown on Si using the ALD-grown Al₂O₃ interlayer. Raman spectroscopy was used to study the strain in these films in more detail, with the shift of the E₂(high) mode showing a clear dependence of strain on Al₂O₃ interlayer thickness. This dependence of strain on Al₂O₃ thickness was also observed via the redshift of the near bandedge emission in room temperature photoluminescence (RT-PL) spectroscopy. The reduction in strain results in a significant reduction in both crack density and screw dislocation density compared to similar films grown on bare Si. Screw dislocation density of the films grown on Al₂O₃/Si substrates approaches that of typical GaN layers on sapphire. This work shows great promise for the use of oxide interlayers for growth of GaN-based LEDs on Si.     

Influence of deposition conditions on nanocrystalline InN layers synthesized on Si(1 1 1) and GaN templates by RF sputtering

We present a detailed investigation on the influence of deposition conditions on morphological, structural and optical properties of InN films deposited on Si(1 1 1) and GaN-on-sapphire templates by reactive radio-frequency (RF) sputtering. The deposition parameters under study are nitrogen content in the sputtering gas, substrate–target distance, substrate temperature and RF power. X-ray diffraction measurements confirm the (0 0 0 1) preferred growth orientation and the wurtzite crystallographic structure of the material. For optimized deposition conditions, InN on Si(1 1 1) substrates presents smooth surface with root-mean-square roughness ∼1 nm. Surface quality of the InN films can be further improved by deposition on GaN-on-sapphire templates, achieving root-mean-square roughness as low as ∼0.4 nm, comparable to that of the underlying substrate. The room-temperature absorption edge is located at 1.70 eV. Intense low-temperature photoluminescence peaking at 1.60 eV is observed.     

Growth, thermal and spectral properties of Nd-doped NaGd(MoO4)2 crystal

Nd³⁺-doped NaGd(MoO₄)₂ crystal with dimensions were grown by Czochralski method. Nd³⁺:NaGd(MoO₄)₂ crystal melts at 1182 °C. The hardness of Nd³⁺:NaGd(MoO₄)₂ crystal is 334 VDH. The specific heat is 72.6 cal/mol K. The thermal expansion coefficients are for c-axis and for a-axis, respectively. The absorption cross-sections of Nd³⁺:NaGd(MoO₄)₂ crystal are with a FWHM of 9 nm at the 804 nm for π-polarization and with a FWHM of 17 nm at 807 nm for σ-polarization, respectively. The emission cross-section σ_em are at 1063 nm for π-polarization and 1.94×10^-20 at 1070 nm cm² for σ-polarization, respectively. The fluorescence lifetime τ_f is 93.9 μs at room temperature.     

Influence of oxygen partial pressure on the properties of undoped InOx films deposited at room temperature by rf-PERTE

Transparent and conductive/semiconductive undoped indium oxide (InO_x) thin films were deposited at room temperature. The deposition technique used is the radio frequency (rf) plasma enhanced reactive thermal evaporation (rf-PERTE) of indium (In) in the presence of oxygen. The influence of oxygen partial pressure on the properties of these films is presented. The oxygen partial pressure varied between 3 × 10^?2 and 1.3 × 10^?1 Pa. Undoped InO_x films, 100 nm thick, deposited at the oxygen partial pressure of 6 × 10^?2 Pa show a conductive behaviour, exhibit an average visible transmittance of 81%, a band gap around 2.7 eV and an electrical conductivity of about 1100 (Ω cm)^?1. For oxygen pressures greater than 6 × 10^?2 Pa, semiconductive films are obtained, maintaining the visible transmittance. Films deposited at lower pressures are conductive but dark. From XPS data, films deposited at an oxygen partial pressure of 6 × 10^?2 Pa show the highest amount of oxygen in the film surface and the lowest ratio between oxygen in the oxide crystalline and amorphous phases.