Fabrication of Ag nanoparticle/ZnO thin films using dual-plasma-enhanced metal-organic chemical vapor deposition (DPEMOCVD) system incorporated with photoreduction method and its application

We report a novel method to grow silver nanoparticle/zinc oxide (Ag NP/ZnO) thin films using a dual-plasma-enhanced metal-organic chemical vapor deposition (DPEMOCVD) system incorporated with a photoreduction method. The crystalline quality, optical properties, and electrical characteristics of Ag NP/ZnO thin films depend on the AgNO₃ concentration or Ag content and annealing temperature. Optimal Ag NP/ZnO thin films have been grown with a AgNO₃ concentration of 0.12 M or 2.54 at%- Ag content and 500 °C- rapid thermal annealing (RTA); these films show orientation peaks of hexagonal-wurtzite-structured ZnO (002) and face-center-cubic-crystalline Ag (111), respectively. The transmittance and resistivity for optimal Ag NP/ZnO thin films are 85% and 6.9×10⁻⁴ Ω cm. Some Ag NP/ZnO transparent conducting oxide (TCO) films were applied to InGaN/GaN LEDs as transparent conductive layers. The InGaN/GaN LEDs with optimal Ag NP/ZnO TCO films showed electric and optical performance levels similar to those of devices fabricated with indium tin oxide.     

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.     

Pendeo-epitaxial growth of gallium nitride on silicon substrates

Pendeo-epitaxy (PE)¹ from raised, [0001] oriented GaN stripes covered with silicon nitride masks has been employed for the growth of coalesced films of GaN(0001) with markedly reduced densities of line and planar defects on Si(111)-based substrates. Each substrate contained previously deposited 3C-SiC(111) and AlN(0001) transition layers and a GaN seed layer from which the stripes were etched. The 3C-SiC transition layer eliminated chemical reactions between the Si and the NH₃ and the Ga metal from the decomposition of triethylgallium. The 3C-SiC and the GaN seed layers, each 0.5 μm thick, were also used to minimize the cracking and warping of the GaN/SiC/silicon assembly caused primarily by the stresses generated on cooling due to the mismatches in the coefficients of thermal expansion. Tilting in the coalesced GaN epilayers of 0.2° was confined to areas of lateral overgrowth over the masks; no tilting was observed in the material suspended above the trenches. The strong, low-temperature PL band-edge peak at 3.456 eV with a FWHM of 17 meV was comparable to that observed in PE GaN films grown on AlN/6H-SiC(0001) substrates.     

Cathodoluminescence of ZnO/GaN/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> heteroepitaxial structures grown by chemical vapor deposition

The cathodoluminescent properties of ZnO films in ZnO/GaN/α-Al₂O₃ and ZnO/α-Al₂O₃ heteroepitaxial structures grown by chemical vapor deposition in a low-pressure flowing-gas reactor were studied and compared. A superlinear dependence of the excitonic-band intensity in the cathodoluminescence spectrum of the ZnO/GaN/α-Al₂O₃ structures on the electron-beam current is ascertained, which indicates that the emission is stimulated for relatively low thresholds of the excitation intensity. It is shown that the ZnO films grown on the GaN substrates exhibit a much more effective cathodoluminescence compared to the cathodoluminescence in the films grown on α-Al₂O₃. It was observed that the luminescent properties of ZnO layers in the ZnO/GaN/α-Al₂O₃ structures subjected to long-term heat treatment at 750°C in an oxygen atmosphere exhibit a high thermal stability.     

Hybrid Solar Cells Using a Zinc Oxide Precursor and a Conjugated Polymer

We describe a new method towards bulk‐heterojunction hybrid polymer solar cells based on composite films of zinc oxide (ZnO) and a conjugated polymer poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV). Spin‐coating diethylzinc as a ZnO precursor and MDMO‐PPV from a common solvent at 40 % humidity and annealing at 110 °C provides films in which crystalline ZnO is found to be intimately mixed with MDMO‐PPV. Photoluminescence and photoinduced spectroscopy demonstrate that photoexcitation of these hybrid composite films results in a fast and long‐lived charge transfer from the polymer as a donor to ZnO as ato be obtained n acceptor. Using the ZnO‐precursor method, hybrid polymer solar cells have been made with an estimated air‐mass of 1.5 (AM 1.5) energy conversion efficiency of 1.1 %. This new method represents a fivefold improved performance compared to similar hybrid polymer solar cells based on amorphous TiO₂.     

Effects of humidity during formation of zinc oxide electron contact layers from a diethylzinc precursor solution

This work focuses on the role of humidity in the formation of ZnO thin films from a reactive diethylzinc precursor solution for use as the electron contact layer (ECL) in organic photovoltaic (OPV) devices. This method is well suited for flexible devices because the films are annealed at 120 °C, making the process compatible with polymer substrates. ZnO films were prepared by spin coating and annealing at different relative humidity (RH) levels. It is found that RH during coating and annealing affects the chemical and physical properties of the ZnO films. Using x-ray photoelectron spectroscopy it is found that increasing RH during the formation steps produces a more stoichiometric oxide and a higher Zn/O ratio. Spectroscopic ellipsometry data shows a small decrease in the optical band gap with increased humidity, consistent with a more stoichiometric oxide. Kelvin probe measurements show that increased RH during formation results in a larger work function (i.e. further from vacuum). Consistent with these data, but counter to what might be expected, when these ZnO films are used as ECLs in OPV devices those with ZnO ECLs processed in low RH (less stoichiometric) had higher power conversion efficiency than those with high-RH processed ZnO due to improved open-circuit voltage. The increase in open-circuit voltage with decreasing humidity was observed with two different donor polymers and fullerene acceptors, which shows the trend is due to changes in ZnO. The observed changes in open-circuit voltage follow the same trend as the ZnO work function indicating that the increase in open-circuit voltage with decreasing humidity is the result of improved energetics at the interface between the bulk-heterojunction and the ZnO layer due to a vacuum level shift.     

Correlation of biaxial strains, bound exciton energies, and defect microstructures in gan films grown on AlN/6H-SiC(0001) substrates

Biaxial strains resulting from mismatches in thermal expansion coefficients and lattice parameters in 22 GaN films grown on A1N buffer layers previously deposited on vicinal and on-axis 6H-SiC(0001) substrates were measured via changes in the c-axis lattice parameter. A Poisson’s ratio of ν = 0.18 was calculated. The bound exciton energy (E_BX) was a linear function of these strains. The shift in E_BX with film stress was 23 meV/GPa. Threading dislocations densities of ~10¹⁰/cm² and ~10⁸/em² were determined for GaN films grown on vicinal and on-axis SiC, respectively. A 0.9% residual compressive strain at the GaN/AIN interface was observed by high resolution transmission electron microscopy (HRTEM).     

Valence band discontinuity of the (0001) 2H-GaN / (111) 3C-SiC interface

X-ray and UV photoelectron spectroscopies were used to measure the valence band discontinuity at the interface between (0001) 2H-GaN films and 3C-SiC (111) substrates. For GaN films grown by NH₃ gas source molecular beam epitaxy on (1×1) 3C-SiC on-axis surfaces, a type I band alignment was observed with a valence band discontinuity of 0.5±0.1 eV. A type I band alignment was also determined for GaN films grown on (3×3) 3C-SiC, but with a larger valence band discontinuity of 0.8±0.1 eV.     

Correlation between nitrogen and carbon incorporation into MOVPE ZnO at various oxidizing conditions

Nitrogen-doped ZnO films with preferential (0 0 0 1) orientation were synthesized on c-Al₂O₃ and Si substrates by metal organic vapor phase epitaxy (MOVPE) using tertiary butanol (t-BuOH) and/or N₂O as oxidizers for diethylzinc (DEZ). A striking correlation between nitrogen and carbon incorporation into ZnO was revealed by concentration versus depth profiling employing secondary ion mass spectrometry (SIMS), consistently with recently reported simulations of nitrogen-carbon complexing.     

Analysis of reactor geometry and diluent gas flow effects on the metalorganic vapor phase epitaxy of AIN and GaN thin films on α(6H)-SiC substrates

The influence of diluent gas on the metalorganic vapor phase epitaxy of AlN and GaN thin films has been investigated. A computational fluid dynamics model using the finite element method was employed to improve film uniformity and to analyze transport phenomena. The properties of AlN and GaN thin films grown on α(6H)-SiC(0001) substrates in H₂ and N₂ diluent gas environments were evaluated. Thin films of AlN grown in H₂ and N₂ had root mean square (rms) roughness values of 1.5 and 1.8 nm, respectively. The surface and defect microstructures of the GaN thin films, observed by scanning and transmission electron microscopy, respectively, were very similar for both diluents. Low temperature (12K) photoluminescence measurements of GaN films grown in N₂ had peak intensities and full widths at half maximum equal to or better than those films grown in H₂. A room temperature Hall mobility of 275 cm²/V·s was measured on 1 μm thick, Si-doped, n-type (1×10¹⁷ cm⁻³) GaN films grown in N₂. Acceptor-type behavior of Mg-doped GaN films deposited in N₂ was repeatably obtained without post-growth annealing, in contrast to similar films grown in H₂. The GaN growth rates were ∼30% higher when H₂ was used as the diluent. The measured differences in the growth rates of AlN and GaN films in H₂ and N₂ was attributed to the different transport properties of these mixtures, and agreed well with the computer model predictions. Nitrogen is shown to be a feasible alternative diluent to hydrogen for the growth of AlN and GaN thin films.     

Intensity of emission from intracenter 4f-transitions in a-Si:H, ZnO, and GaN films doped with rare-earth ions

It is shown that the intensity of emission from intracenter 4f-transitions in amorphous a-Si:H films and crystalline (GaN, ZnO) films doped with rare-earth ions is governed by the local environment of doping impurity ions. In the case of a-Si:H, a pseudo-octahedron with the C _4V point group is present due to nanocrystallites, which provides a local environment for rare-earth ions. In the case of a hexagonal crystal lattice in crystalline GaN and ZnO films, the local symmetry of rare-earth ions introduced into the semiconductor matrix by diffusion, with a pseudo-octahedron with the C _4V point group, is formed by stresses due to rare-earth ion-oxygen complexes with a radius exceeding that of host ions incorporated at crystal lattice sites. In contrast to GaN films, ZnO films exhibit, on being doped with Tm, Sm, and Yb, both high-intensity emission in the long-wavelength spectral region, characteristic of intracenter 4f transitions in rare-earth ions, and a substantial increase in intensity in the short-wavelength spectral region (?? = 368?C370 nm). GaN films doped with rare-earth ions exhibit in this spectral range only an inhomogeneously broadened emission spectrum due to the presence of an emission band characteristic of donor-acceptor recombination.     

Morphology and growth mechanism of aligned ZnO nanorods grown by catalyst-free MOCVD

We report on ZnO nanorods grown by catalyst-free metal-organic chemical vapour deposition (MOCVD) in a commercial Epigress reactor using diethylzinc and N₂O as precursors. Well-aligned ZnO nanorods with uniform diameter, length and density have been grown perpendicularly to the sapphire (0 0 0 1) surface. Scanning electron microscopy (SEM) has been used to observe the morphology of the ZnO nanorods and X-ray diffraction and transmission electron microscopy (TEM) to investigate the crystalline structure of the nanorods. TEM observation as well as photoluminescence measurements confirm the very good crystalline quality of the nanorods. SEM observation on samples that have been prepared with various deposition times has been used in order to investigate the growth mechanism. Three types of ZnO morphologies have been identified: a thin two-dimensional ZnO layer formed at the sapphire surface, covered by three-dimensional hexagonal-shaped islands and hexagonal nanorods on top of them.     

Lateral Epitaxial Overgrowth of ZnO in Water at 90 °C

Lateral epitaxial overgrowth (LEO) of ZnO has been demonstrated in water at 90 °C. The process starts with hydrothermal epitaxial growth of ZnO(0001) on MgAl₂O₄(111), followed by channel stamping of photoresist to define “growth windows”. LEO films grow in zinc‐precursor solutions at pH 10.9; sodium citrate addition controls out‐of‐plane growth. Transmission electron microscopy indicates threading dislocation reductions from ～ 2 × 10¹⁰ to < 2 × 10⁸ cm^–2 from the window to the wing regions. Microphotoluminescence and Hall‐effect measurements indicate improved material quality. Wing tilt was observed. Double LEO demonstrates the possibility of complete dislocation reduction.     

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.     

Growth of Polarity-Controlled ZnO Films on (0001) Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

The polarity control of ZnO films grown on (0001) Al₂O₃ substrates by plasma-assisted molecular-beam epitaxy (P-MBE) was achieved by using a novel CrN buffer layer. Zn-polar ZnO films were obtained by using a Zn-terminated CrN buffer layer, while O-polar ZnO films were achieved by using a Cr₂O₃ layer formed by O-plasma exposure of a CrN layer. The mechanism of polarity control was proposed. Optical and structural quality of ZnO films was characterized by high-resolution X-ray diffraction and photoluminescence (PL) spectroscopy. Low-temperature PL spectra of Zn-polar and O-polar samples show dominant bound exciton (I₈) and strong free exciton emissions. Finally, one-dimensional periodic structures consisting of Zn-polar and O-polar ZnO films were simultaneously grown on the same substrate. The periodic inversion of polarity was confirmed in terms of growth rate, surface morphology, and piezo response microscopy (PRM) measurement.     

Surface etching of 6H-SiC (0001) and surface morphology of the subsequently grown GaN via MOCVD

The correlation between surface morphological properties of the GaN epilayers and the surface conditions of 6H-SiC (0001) substrates etched in H₂, C₂H₄/H₂, and HCl/H₂ was studied. Etching 6H-SiC in H₂ produced a high quality surface with steps and terraces, while etching in HCl/H₂ produced either a rough surface with many pits and hillocks or a smooth surface similar to that etched in H₂, depending on the HCl concentration and temperature. The GaN epilayers were subsequently deposited on these etched substrates using either a low temperature GaN or a high temperature AlN buffer layer via MOCVD. The substrate surface defects increased the density and size of the “giant” pinholes (2–4 μm) on GaN epilayers grown on a LT-GaN buffer layer. Small pinholes (<100 nm) were frequently observed on the samples grown on a HT-AlN buffer layer, and their density decreased with the improved surface quality. The non-uniform GaN nucleation caused by substrate surface defects and the slow growth rate of planes of the islands were responsible for the formation of “giant” pinholes, while the small pinholes were believed to be caused by misfit dislocations.     

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.     

TEM structural studies of undoped and Si-doped GaN grown on Al2O3 substrate

Transmission electron microscopy was used to study the microstructure of GaN films undoped or Si-doped to 10¹⁷ or 10¹⁸ cm^?3 and grown by molecular-beam epitaxy on (0001) Al₂O₃ substrate without nitridation or a buffer layer. Defect structures including inversion domains, nanopipes, and (0001) stacking faults were studied. The influence of Si doping on the threading dislocation density and the dimensions of GaN grains bounded by inversion domains was assessed. Smoothing of the steplike morphology of the GaN film surface occurs at a Si concentration of 10¹⁷ cm^?3.     

Investigation of ZnO nanopillars fabrication in a new Thomas Swan close coupled showerhead MOCVD reactor

Self-organized ZnO nanopillars were grown on a-plane Al₂O₃ in a vertical MOCVD reactor using diethylzinc and N₂O as precursors. This is the very first Thomas Swan reactor that is specially designed for the growth of ZnO and GaN. The influence of different growth parameters including growth time, VI/II-ratio, substrate temperature and reactor pressure on the shape of the nanostructures is investigated by field emission scanning electron microscopy. An explanation for the formation of nanopillars is given resulting in high substrate temperatures and low VI/II-ratios for the best results. It is shown that the density, length and diameter can be controlled choosing appropriate growth parameters.     

氮化Si基ZnO/Ga_2O_3制备GaN薄膜

利用射频磁控溅射法在Si衬底上先溅射ZnO缓冲层,接着溅射Ga2O3薄膜,然后ZnO/Ga2O3膜在管式炉中常压下通氨气进行氮化,反应自组生成GaN薄膜。XRD测量结果表明,利用该方法制备的GaN薄膜是沿c轴方向择优生长的六角纤锌矿多晶结构的薄膜,利用SEM观测了其表面形貌,PL测量结果发现了位于351nm处的室温光致发光峰。