Epitaxial Growth and Characterization of p-Type ZnO

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

Optical and Magnetic Properties of ZnO:V Prepared by Ion Implantation

We report on the optical and magnetic properties of the magnetic semiconductor Zn(V)O fabricated by implantation of 195 keV ₅₁V⁺ ions into bulk ZnO:Al grown by a hydrothermal technique. Two sets of the samples, containing N _d –N _a ∼ 10¹⁵ cm⁻³ and 10¹⁸ cm⁻³, were implanted to doses of 1 × 10¹⁵ cm⁻², 3 × 10¹⁵ cm⁻², and 1 × 10¹⁶ cm⁻². The ion implantation was performed at 573 K. To remove irradiation-induced defects, the samples were annealed in air at 1073 K. Photoluminescence (PL) measurements of Zn(V)O films were carried out at temperatures from 10 K to 300 K. The effects of implantation dose and free carrier concentration on the magnetic properties of Zn(V)O were studied using a superconducting quantum interference device magnetometer. Ferromagnetism has been observed in annealed highly conductive samples implanted to 1 × 10¹⁶ cm⁻². The PL studies of ZnO bulk samples implanted with V⁺ have revealed that thermal annealing at 1073 K restores to a large extent the optical quality of the material. A new emission line centered at 3.307 eV has been found in the PL spectrum of the highly conductive samples implanted to the dose of 1 × 10¹⁶ cm⁻², which is most probably due to complexes involving V ions.     

Optimization of N2/Ar gas flow ratio for the realization of nitrogen-doped p-type ZnCdO thin films synthesized by RF magnetron sputtering

Nitrogen doped ZnCdO films [ZCO:N] have been grown on quartz substrates by radio frequency (RF) reactive magnetron sputtering technique, and the effect of the ratio of nitrogen to argon gas flow [N₂:Ar] on their electrical, microstructure and optical properties were investigated by Hall effect, energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscope (TEM), optical absorbance and photoluminescence (PL) measurements. The results indicate that all the ZCO:N films are of hexagonal wurtzite structure with highly (002) preferential orientation. As the N₂:Ar increases from 0:1 to 4:1, the absorption edge for the samples exhibits blue shift. Hall effect measurement results indicate that the N₂:Ar exerts an immense influence on the p-type conduction conversion for ZCO:N film. It is found that ZCO:N film deposited at the N₂:Ar of 1:2 shows the optimal p-type behavior, which has a carrier concentration of 1.10×10¹⁷ cm⁻³, a mobility of 3.28 cm²V⁻¹s⁻¹ and a resistivity of 17.3 Ω cm. Compared with the other samples, ZCO:N film fabricated at the relatively lower N₂:Ar possesses the superior crystal quality, luminescent and electrical properties. Additionally, a possible mechanism of p-type conduction for ZCO:N film was discussed in this work.     

ZnO growth toward optical devices by MOVPE using N2O

Wide bandgap semiconductor zinc oxide (ZnO) layers were grown by metalorganic vapor phase epitaxy (MOVPE) using nitrous oxide (N₂O). Strong ultraviolet (UV) photoluminescence emissions with 1000 times less deep ones at room temperature were observed from ZnO layers grown on sapphire. Alow temperature (500 C)-grown buffer layer of ZnO was effective to enhance the initial nucleation process and to achieve high quality ZnO layers on it at higher growth temperatures (600–700 C). ZnO layers grown on III–V semiconductor substrates showed dominant UV luminescence in spite of low temperature growth. These results imply the abilities of high quality ZnO growth by MOVPE.     

Research of SiO2/InP structure prepared by photo-CVD

The SiO₂ film as an insulator in InP MOS structure was grown by mercury-sensitized photo induced chemical-vapor deposition (photo-CVD) utilizing gaseous mixture of monosilane (SiH₄) and nitrous oxide (N₄O) under 253.7 nm ultraviolet light irradiation. The PHOTOX SiO₂ film (i.e., SiO₂ film prepared by photo-CVD system) deposited at 250° C has a refractive index of 1.46 and breakdown field strength of 7.0 MV/cm. The 1 MHz capacitance-voltage characteristics of the InP MOS diode was measured to study the interface state densities. The minimum value is 1.2 × 10¹¹ cm⁻²eV⁻¹ for the sample prepared at a substrate temperature of 250° C.     

The effect of growth conditions,point defects and hydrogen on the electronic structure and properties of p-type (Al,N) codoped ZnO: A first principles study

The effects of point defects, hydrogen, and growth conditions on the electronic structure and properties of the (Al,N) codoped p-type ZnO have been investigated using the first principles method. The obtained results showed that the Al_Zn–N_O–V_Zn complex is a shallow acceptor that can play an important role in achieving the p-type conductivity in the (Al,N) codoped ZnO films. Our results showed also that the electrical conductivity type in the (Al,N) codoped ZnO films strongly depends on the donor/acceptor concentrations ratio. The codoped ZnO films prepared under both Zn-rich and O-rich growth conditions with a donors/acceptors ratio of 1:2 have a p-type conductivity, while those prepared with a ratio of 1:1 cannot be p-type unless if they are prepared under O-rich conditions. The achieved p-type quality depends also on the used nitrogen doping source. To prepare p-type ZnO film of high quality using the (Al,N) codoping method, the use of NO or NO₂ is recommended. The presence of donor defects such as oxygen vacancies and hydrogen will significantly affect the electronic properties of the (Al,N) codoped ZnO films, and if the concentration of these defects in the sample is high enough, the material can be easily converted to n-type.     

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.     

Ultraviolet Photodetection Properties of a Pt Contact on a Mg<Subscript>0.1</Subscript>Zn<Subscript>0.9</Subscript>O/ZnO Composite Film

We report on the ultraviolet (UV) photodetection properties of a Pt contact on a sol-gel Mg_0.1Zn_0.9O/ZnO composite structure on a glass substrate. In the dark, the current–voltage (I–V) characteristics between the Pt and Ag contacts on the top of the ZnO film were linear while that on the Mg_0.1Zn_0.9O/ZnO composite film were rectifying, suggesting the formation of a Schottky diode on the latter. The ideality factor, n, and the reverse leakage current density, J _R , of the Schottky diode were greater than 2 and 2.36 × 10⁻² A cm⁻² at −5 V, respectively. Under ultraviolet light, the I–V characteristics become linear. The maximum photo-to-dark current ratio observed was about 63. The composite film showed good sensitivity to UV light with wavelengths of less than 400 nm, though the photoresponse process was found to be slow.     

Acceptor and donor doping of AlxGa1−xN thin film alloys grown on 6H-SiC(0001) substrates via metalorganic vapor phase epitaxy

Thin films of Si-doped Al_xGa_1−xN (0.03≤x≤0.58) having smooth surfaces and strong near-band edge cathodoluminescence were deposited at 0.35–0.5 μm/h on on-axis 6H-SiC(0001) substrates at 1100°C using a 0.1 μm AlN buffer layer for electrical isolation. Alloy films having the compositions of Al_0.08Ga_0.92N and Al_0.48Ga_0.52N exhibited mobilities of 110 and 14 cm²/V·s at carrier concentrations of 9.6×10¹⁸ and 5.0×10¹⁷ cm⁻³, respectively. This marked change was due primarily to charge scattering as a result of the increasing Al concentration in these random alloys. Comparably doped GaN films grown under similar conditions had mobilities between 170 and ∼350 cm²/V·s. Acceptor doping of Al_xGa_1−xN for x≤0.13 was achieved for films deposited at 1100°C. No correlation between the O concentration and p-type electrical behavior was observed.     

Properties of thin LPCVD silicon oxynitride films

Thin, uniform silicon oxynitride films with films thicknesses of ≤ 10 nm were successfully deposited by low pressure chemical vapor deposition (LPCVD). The reactant gases were SiH₂Cl₂, N₂O, and NH₃. The compositional uniformity of these films as a function of depth was good. The structure of these oxynitride films was found to be dominated by the mixed matrix of Si, N, and 0, rather than a physical mixture of SiO₂ and Si₃N₄ clusters. N-H bonding was observed and the total amount of hydrogen in the as-deposited film was on the order of 5 x l0²⁰/cm³. No H-OH or Si-OH bonds were detected. Excellent dielectric breakdown distributions were found for oxynitride films with equivalent oxide film thicknesses as low as 7.5 nm. The conduction of Si-N-0 films depended on film composition. A small capacitor-voltage (C-V) window (< 0.1 V) was observed for the Si-N-O/Si structures. The midgap surface state density was on the order of 5 x 10¹⁰/cm² /eV. Either trapping of holes or the generation of positive states were found after high field stressing of the oxynitride films.     

Effect of annealing on the morphology and optoelectrical characteristics of ZnO thin films grown by plasma-assisted molecular beam epitaxy

The dependence of characteristics of plasma-assisted molecular beam epitaxy-grown ZnO thin films on different postgrowth annealing conditions was investigated. It was found that, under oxygen atmosphere, annealing temperature can profoundly affect the morphological, electrical, and optical properties of ZnO thin films. In particular, the surface morphology changed from a relatively smooth surface before annealing to various island morphologies after annealing above 800°C for samples grown directly on sapphire without a buffer layer. It is speculated that intrinsic stress due to lattice mismatch drives the island formation and the high temperature provides the energy needed for this surface rearrangement. Single-field Hall-effect measurement showed that the carrier concentration improved by an order of magnitude and the mobility increased from about 30 cm²/Vs to ∼70 cm²/Vs by annealing at 750°C. Variable-field Hall effect shows that a model with two carriers, one a degenerate low-mobility electron and the other a higher mobility non-degenerate electron, is needed to explain the transport properties of the thin film. Analysis indicates that annealing at 750°C decreased the carrier concentration and increased the mobility for the high-mobility carrier. Annealing also led to a significant improvement in photoluminescence, with temperatures of ∼750–850°C yielding the best results.     

A novel low-temperature method of SiO2 film deposition forMOSFET applications

Silicon dioxide dielectric films were deposited at low temperatures (250–300°) using a novel plasma enhanced MO-CVD process. In this process, the substrate was kept remote from the plasma region and the deposition of the film was achieved at low pressure (0.8-1.0 Torr) and low dc plasma power (0.3 W· cm⁻²). Films deposited using tetraethyloxysilane (TEOS) and nitrous oxide (N₂O) as reactant material had, under optimum deposition conditions, resistivities of ≥ 10¹⁵ ohm-cm, a refractive index of 1.46, a dielectric constant of 3.98 and a breakdown field strength ≥ 5x 10₆ V·cm⁻¹. AES and SIMS analysis indicated that the films were of high purity and were stoichiometric with no metallic silicon present. MOS-capacitors fabricated on Si-substrates showed no hysteresis and no frequency dispersion of capacitance in the accumulation region. An interface state density in the range of 10¹¹ cm⁻²eV⁻¹ was achieved for these MOS devices using our deposited SiO₂dielectric films.     

Frontier of transparent oxide semiconductors

Recent advancements of transparent oxide semiconductors (TOS) toward new frontiers of “oxide electronics” are reviewed based on our efforts, categorized as “novel functional materials”, “heteroepitaxial growth techniques”, and “device fabrications”. Topics focused in this paper are: (1) highly conductive ITO thin film with atomically flat surface, (2) p-type TOS material ZnRh₂O₄, (3) deep-ultraviolet (DUV) transparent conductive oxide β-Ga₂O₃ thin film, (4) electrochromic oxyfuolide NbO₂F, (5) single-crystalline films of InGaO₃(ZnO)_m grown by reactive solid-phase epitaxy, (6) p-type semiconductor LaCuOS/Se epitaxial films capable of emitting UV- and purple-light, (7) p–n homojunction based on bipolar CuInO₂, (8) transparent FET based on single-crystalline InGaO₃(ZnO)₅ films, and (9) UV-light emitting diode based on p–n heterojunction.     

ArF excimer laser induced CVD of aluminum oxide films

The authors have demonstrated photochemical deposition of aluminum oxides from Trimethylaluminum (TMA) and N₂O by using a pulsed ArF excimer laser (193 nm). Both TMA and N₂O are efficiently photodissociated by the 193 nm light. The films are grown on Si and InP wafers contained in a low pressure flowing cell with a heated substrate. The incident laser beam is focused and parallel to the substrate surface. Typical deposition rates are 80–150 A/min. Stripes of aluminum oxide 30 mm wide are uniformly grown on 7.5 cm Si-wafers. The film composition and purity have been investigated using Auger and Infra-red spectroscopy analysis. Surprising results are the relatively low concentration of carbon. Refractive index and thickness have been determined by an ellipsometer. Typical values for the films are 1.54–1.62. Metal-oxide-semiconductor capacitors have been fabricated and characterized. The C-V curves for n-InP/aluminum oxide have clockwise hysteresis, and minimum loop width is less than 0.5 V. The surface state densities are 1 × 10¹¹ cm^-2 eV⁻¹ at the mid band gap.     

Characterization of ZnO and ZnO:Al films deposited by MOCVD on oriented and amorphous substrates

Zinc oxide (ZnO) and ZnO:Al-doped films were deposited by metal organic chemical vapour deposition (MOCVD) using the Zn(tta)₂·tmeda (H-tta=2-thenoyltrifluoroacetone, tmeda=N,N,N′,N′-tetramethylethylendiamine) and Al(acac)₃ (H-acac=acetylacetone) precursors on different substrates. The deposited layers were characterised by X-ray diffraction (XRD) and field-emission scanning electron microscopy (FE-SEM). Film structure is strongly dependent on the substrate nature and deposition conditions. AFM and XRD measurements show a good film texture and a preferential orientation along the c-axis. The Al concentration of ZnO:Al film has been confirmed by energy dispersive X-ray (EDX) analysis. Optical transparency of these ZnO layers has been studied in order to evaluate their applications as a transparent conducting oxide (TCO) material.     

Growth and characterization of OMVPE grown (In,Mn)As diluted magnetic semiconductor

In_1−xMn_xAs diluted magnetic semiconductor (DMS) thin films with x 0.14 have been grown using organometallic vapor phase epitaxy. Tricarbonyl-(methylcyclopentadienyl)manganese was successfully used as the Mn source. Single phase, epitaxial films were achieved for compositions as high as x=0.14 using growth temperatures ≥475°C. For lower growth temperatures or x>0.14, nanometer scale MnAs precipitates were observed within the In_1−xMn_xAs matrix. Transport properties were investigated using the Hall effect. All Mn doped films were p-type with single phase films exhibiting hole concentrations 2≤×10¹⁹ cm⁻³. Magnetization was measured as a function of temperature and applied field for a single phase film with x=0.1. Ferromagnetic ordering was observed at 5 K with a saturation magnetization of M_s=68 emu/cm³, a remnant magnetization, M_r=10 emu/cm³, and a coercive field H_c=400 Oe.     

Fabrication of p-Type ZnO Thin Films via DC Reactive Magnetron Sputtering by Using Na as the Dopant Source

The Na-doped p-type ZnO thin films were prepared by DC reactive magnetron sputtering. Two types of substrates were used for separate testing purposes: silicon wafers for crystallinity measurements and glass slides for electrical and optical transmittance measurements. The lowest room-temperature resistivity under the optimal condition was 59.9 Ω cm, with a Hall mobility of 0.406 cm² V⁻¹s⁻¹ and a carrier concentration of 2.57 × 10¹⁷ cm⁻³. The Na-doped ZnO thin films possessed a good crystallinity with c-axis orientation and a high transmittance (∼85%) in the visible region. The effects of the substrate temperature on the crystallinity and the electrical properties were discussed.     

ZnO TFT Devices Built on Glass Substrates

ZnO thin-film transistors (TFTs) were built on glass substrates. The device with a top gate configuration operates in the depletion mode. The ZnO channel was grown by metalorganic chemical vapor deposition (MOCVD) on glass at low temperature. SiO₂ was used as the gate dielectric. The TFT has an on/off ratio of ∼4.0 × 10⁴ and a channel field-effect mobility of ∼4.0 cm²/V s. The average transmittance of the ZnO film in the visible wavelength is ∼80%. To compare the characteristics of the TFTs prepared by using a poly-ZnO and epitaxial-ZnO channel, an epi-ZnO TFT with the same configuration and dimensions was made on an r-Al₂O₃ substrate. The epi-ZnO TFT shows higher field-effect mobility of ∼35 cm²/V s and on/off ratio of ∼10⁸.     

The properties of Si/Si1-xGex films grown on Si substrates by chemical vapor deposition

A growth parameter study was made to determine the proper of a SiGe superlattice-type configuration grown on Si substrates by chemical vapor deposition (CVD). The study included such variables as growth temperature, layer composition, layer thickness, total film thickness, doping concentrations, and film orientation. Si and SiGe layers were grown using SiH₄ as the Si source and GeH₄ as the Ge source. When intentional doping was desired, diluted diborane for p-type films and phosphine for n-type films were used. The study led to films grown at ∼1000°C with mobilities from ∼20 to 40 percent higher than that of epitaxial Si layers and ∼100 percent higher than that of epitaxial SiGe layers grown on (100) Si in the same deposition system for net carrier concentrations of ∼8x10¹⁵ cm^-3 to ∼2x10¹⁷ cm^-3. Enhanced mobilities were found in multilayer (100)-oriented Si/Si_1-xGe_x films for layer thicknesses ≥400A, for film thicknesses >2μm, and for layers with x = 0.15. No enhanced mobility was found for (111)-oriented films and for B-doped multilayered (100)-orlented films. Supported in part by NASA-Langley Research Center, Hampton, VA, Contract NAS1-16102 (R. Stermer & A. Fripp, Contr. Mon.)     

Growth of Heteroepitaxial ZnO Thin Films on GaN‐Buffered Al2O3 (0001) Substrates by Low‐Temperature Hydrothermal Synthesis at 90 °C

Heteroepitaxial ZnO films are successfully grown on nondoped GaN‐buffered Al₂O₃ (0001) substrates in water at 90 °C using a two‐step process. In the first step, a discontinuous ZnO thin film (ca. 200 nm in thickness) consisting of hexagonal ZnO crystallites is grown in a solution containing Zn(NO₃)·6 H₂O and NH₄NO₃ at ca. pH 7.5 for 24 h. In the second step, a dense and continuous ZnO film (ca. 2.5 μm) is grown on the first ZnO thin film in a solution containing Zn(NO₃)·6 H₂O and sodium citrate at ca. pH 10.9 for 8 h. Scanning electron microscopy, X‐ray diffraction, UV‐vis absorption spectroscopy, photoluminescence spectroscopy, and Hall‐effect measurement are used to investigate the structural, optical, and electrical properties of the ZnO films. X‐ray diffraction analysis shows that ZnO is a monocrystalline wurtzite structure with an epitaxial orientation relationship of (0001)[11 0]_ZnO∥(0001)[11 0]_GaN. Optical transmission spectroscopy of the two‐step grown ZnO film shows a bandgap energy of 3.26 eV at room temperature. A room‐temperature photoluminescence spectrum of the ZnO film reveals only a main peak at ca. 380 nm without any significant defect‐related deep‐level emissions. The electrical property of ZnO film showed n‐type behavior with a carrier concentration of 3.5 × 10¹⁸ cm^–3 and a mobility of 10.3 cm² V^–1 s^–1.