Layer by layer growth of ZnO on (0001) sapphire substrates by radical-source molecular beam epitaxy

Layer by layer growth of ZnO epilayers on (0001) Al₂O₃ substrates is achieved by radical-source molecular beam epitaxy. A thin MgO buffer, followed by a low-temperature ZnO buffer was used in order to accommodate the lattice mismatch between ZnO and sapphire. Reflection high-energy electron diffraction intensity was employed for the optimization of the ZnO growth. The surface morphology of the samples was studied with atomic force microscopy. Investigation of the nature of the influence of the MgO buffer layer on the formation of ZnO on sapphire substrate was carried out using Transmission Electron Microscopy. For the first time it was shown that a thin spinel (magnesium aluminum oxide) layer is formed on the interface of the sapphire substrate and MgO buffer layer leading to the crystalline quality improvement of the ZnO main layer. X-Ray diffractometry measurements of the obtained ZnO layers show excellent quality of the single crystalline ZnO heteroepitaxially grown on sapphire. The crystalline quality of the ZnO layers is even better than that of our previously reported layers grown employing hydrogen peroxide as an oxidant. The full width at half maximum of the XRD (0002) rocking curve is as low as 25 arc s. The influence of growth parameters (Zn/O flux ratio, temperature, etc.) on the structural properties as well as on the surface morphology of the zinc oxide layers on sapphire is investigated and discussed.     

Time-resolved spectroscopy of excitonic transitions in ZnO/(Zn, Mg)O quantum wells

We report on the optical spectroscopy of a series of ZnO/(Zn, Mg)O quantum wells of different widths, using time-resolved photoluminescence. The samples were grown by molecular beam epitaxy on ZnO templates, themselves deposited on sapphire substrates. The barriers consist of Zn_0.78Mg_0.22O layers. The presence of large internal electric fields in these quantum wells results in a competition between quantum confinement and the quantum confined Stark effect as the quantum well width is varied. A transition energy lying 0.5 eV below the ZnO excitonic gap was observed for the widest of our wells. The PL spectra of the wide quantum wells were obtained using time-integrated photoluminescence, taking a great care with screening effects induced by their very slow dynamics. The effect of the built-in electric field on the excitonic properties was investigated. The excitonic fine structure is shown to depend strongly on the enhancement or suppression of the exchange interaction as a function of the quantum well width.     

Pulsed laser deposition of high-quality ZnO films using a high temperature deposited ZnO buffer layer

High-quality ZnO film growth on sapphire was achieved by pulsed laser deposition using a high temperature deposited ZnO buffer layer. This high temperature deposited buffer layer remarkably improves crystallinity of subsequent films. In particular, the full width at half-maximum of X-ray diffraction ω-rocking curves for ZnO films grown with the buffer layer is 0.0076° (27.36 arcsec) and 0.1242° (447.12 arcsec) for the out-of-plane (002) and in-plane (102) reflections, respectively. In addition, ZnO films grown with this buffer layer showed a carrier mobility of 88 cm²/V s, which is three times higher than that realized for ZnO films grown without the buffer layer. The room temperature photoluminescence spectra showed strong band edge emission with little or no defect-related visible emission. PACS 78.55.Et; 81.05.Dz     

Improved growth of solution‐deposited thin films on polycrystalline Cu(In,Ga)Se2

CdS and Zn(O,S) grown by chemical bath deposition (CBD) are well established buffer materials for Cu(In,Ga)Se₂ (CIGS) solar cells. As recently reported, a non‐contiguous coverage of CBD buffers on CIGS grains with {112} surfaces can be detected, which was explained in terms of low surface energies of the {112} facets, leading to deteriorated wetting of the chemical solution on the CIGS surface. In the present contribution, we report on the effect of air annealing of CIGS thin films prior to the CBD of CdS and Zn(O,S) layers. In contrast to the growth on the as‐grown CIGS layers, these buffer lay‐ ers grow densely on the annealed CIGS layer, even on grains with {112} surfaces. We explain the different growth behavior by increased surface energies of CIGS grains due to the annealing step, i.e., due to oxidation of the CIGS surface. Reference solar cells were processed and completed by i‐ZnO/ZnO:Al layers for CdS and by (Zn,Mg)O/ZnO:Al for Zn(O,S) buffers. For solar cells with both, CdS and Zn(O,S) buffers, air‐annealed CIGS films with improved buffer coverage resulted in higher power‐conversion efficiencies, as compared with the devices containing as‐grown CIGS layers. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Low-temperature MOVPE growth of ZnO thin films by using a buffer layer

ZnO thin films have been grown on a-plane (1,1,−2,0) sapphire substrates by metalorganic vapor phase epitaxy (MOVPE) at low substrate temperature of 350 °C. It is showed that the crystal and electrical quality of the thin films was improved by using a ZnO buffer layer. The photoluminescence (PL) measurements indicate that the ZnO thin films grown at such a low substrate temperature have a strong UV emission.     

Controllable hydrothermal synthesis of ZnO nanowires arrays on Al-doped ZnO seed layer and patterning of ZnO nanowires arrays via surface modification of substrate

ZnO nanowire (NW) arrays are assembled on the Al-doped ZnO (AZO) seed layer by a hydrothermal process. Effects of the temperature and growth time of the hydrothermal process on morphological and photoluminescence properties of the as-assembled ZnO NW arrays are characterized and studied. Results indicate that the length and diameter of the ZnO NWs increase with a lengthening of the growth time at 80 °C and the hydrothermal temperature has a significant effect on the growth rate and the photoluminescence properties of the ZnO NW arrays. The patterned AZO seed layer is fabricated on a silicon substrate by combining a sol-gel process with an electron-beam lithography process, as well as a surface fluorination technique, and then the ZnO NW arrays are selectively grown on those patterned regions of the AZO seed layer by the hydrothermal process. Room-temperature photoluminescence spectra of the patterned ZnO NW arrays shows that only a strong UV emission at about 380 nm is observed, which implies that few crystal defects exist inside the as-grown ZnO NW arrays.     

Growth of nanostructured ZnO thin films on sapphire

Growth of ZnO nanostructures on c-plane sapphire has been investigated using three different methods. Pulsed laser deposition (PLD) at low incident pulse energies can yield nanorods, the majority of which are aligned at an angle of ∼50° to the substrate plane. Selected area electron diffraction reveals that the nanorods display two distinct epitaxial relationships with the sapphire substrate. Those inclined to the surface normal exhibit the relationships (112̄4)_ZnO//(0001)_sap; [101̄0]_ZnO//[112̄0]_sap and (0001)_ZnO//(101̄4)_sap; [101̄0]_ZnO//[112̄0]_sap. Members of the second family are aligned along the surface normal, with (0001)_ZnO//(0001)_sap and [101̄0]_ZnO//[112̄0]_sap; the relative yield of this latter class increases at higher incident pulse energies. Hydrothermal synthesis and chemical vapour deposition on sapphire substrates that have been pre-coated (by PLD) with a thin ZnO layer result, respectively, in well-aligned ZnO microrod and nanorod arrays, both of which satisfy the relationships (0001)_ZnO//(0001)_sap; [101̄0]_ZnO//[112̄0]_sap. In contrast, employing these latter methods with a bare sapphire substrate results in, respectively, poorly aligned structures and localized islands of growth. PACS  81.07.-b; 81.10.-h; 81.15.Aa; 81.15-z; 68.65.-k     

Nanoscale determination of surface orientation and electrostatic properties of ZnO thin films

Scanning force microscopy related techniques are applied to study surface nanoscale properties. We show that nanogoniometry can be combined with local electrostatic measurements – electrostatic force microscopy and Kelvin probe microscopy – to identify surface planes families and to study their local electrical properties. The scanning force microscopy techniques employed are analyzed and the correct way of acquiring and interpreting data is discussed in detail. The experiments performed on ZnO films grown along the nonpolar [112̄0] direction show that these films completely facet into {101̄1} and {101̄1̄} planes, which follow a well defined pattern of surface potential along the [0001] direction. This pattern is explained in terms of the different ionic termination – Zn or O ions – of the exposed facets. Finally, the presence of inversion domain boundaries is discussed. PACS 68.47.Gh; 73.30.+y; 68.37.-d; 73.63.-b     

Epitaxial ZnO films grown on ZnO-buffered c-plane sapphire substrates by hydrothermal method

ZnO films are hydrothermally grown on ZnO-buffered c-plane sapphire substrates at a low temperature of 70 °C. A radio-frequency (RF) reactive magnetron sputtering has been used to grow the ZnO buffer layers. X-ray diffraction, scanning electron microscopy, and room temperature photoluminescence are carried out to characterize the structure, morphology and optical property of the films. It is found that the films are stress-free. The epitaxial relationship between the ZnO film and the c-plane sapphire substrate is found to be ZnO (0 0 0 1)||Al₂O₃ (0 0 0 1) in the surface normal and in plane. Sapphire treatment, as such acid etching, nitridation, and oxidation are found to influence the nucleation of the film growth, and the buffer layers determine the crystalline quality of the ZnO films. The maximum PL quantum efficiency of ZnO films grown with hydrothermal method is found to be about 80% of single-crystal ZnO.     

Annealing effects of sapphire substrate on properties of ZnO films grown by magnetron sputtering

The annealing effects of sapphire substrates on the quality of epitaxial ZnO films grown by dc reactive magnetron sputtering were studied. The atomic steps formed on (0001) sapphire (α-Al₂O₃) substrates surface by annealing at high temperature were analyzed by atomic force microscopy. Their influence on the growth of ZnO films was examined by X-ray diffraction and photoluminescence measurements. Experimental results indicate that the film quality is strongly affected by annealing treatment of the sapphire substrate surface. The optimum annealing temperature of sapphire substrates for ZnO grown by magnetron sputtering is 1400 °C for 1 h in air. PACS 81.40.Ef; 68.55.Jk; 81.05.Dz; 81.15.Cd     

Evidence for barrier-to-well injection of carriers in high quality ZnO/Zn0.9Mg0.1O multiple quantum wells grown on (111) Si

High quality ZnO/Zn_0.9Mg_0.1O multiple quantum wells were grown on (111) Si employing epitaxial Lu₂O₃ buffer layer and a thin ZnO nucleation layer. The linewidth of the low temperature ZnO well emission is only 17 meV. The effective recombination lifetime of emission from ZnO wells is 183 ps. Temperature-dependent photoluminescence is investigated to reveal the behavior of the carriers in the multiple quantum wells. Evidence for the barrier-to-well injection is indicated from the thermal quenching of both the barrier and well emissions. Carrier localization and thermal delocalization are observed in ZnMgO cap/barriers. The depth of the local potential well is determined to be ∼7 meV$\sim 7\text{meV}$.     

Effects of the annealing duration of the ZnO buffer layer on structural and optical properties of ZnO rods grown by a hydrothermal process

In this study, the effects of the annealing duration of a zinc oxide (ZnO) buffer layer on structural and optical properties of ZnO rods grown by a hydrothermal process are discussed. A ZnO buffer layer was deposited on p-type Si (1 1 1) substrates by the metal organic chemical vapor deposition (MOCVD) method. After that, ZnO rods were grown on the ZnO-buffer/Si (1 1 1) substrate by a hydrothermal process. In order to determine the optimum annealing duration of the buffer layer for the growth of ZnO rods, durations ranging from 0.5 to 30 min were tried. The morphology and crystal structure of the ZnO/ZnO-buffer/Si (1 1 1) were measured by field emission scanning electron microscopy (FE-SEM) and x-ray diffraction (XRD). The optical properties were investigated by photoluminescence (PL) measurement.     

Influence of Sb on a controlled-growth of aligned ZnO nanowires in nanoparticle-assisted pulsed-laser deposition

Single-crystalline ZnO nanowires on a sapphire substrate have been synthesized by a nanoparticle-assisted pulsed-laser deposition (NAPLD) using a pure and Sb₂O₃ doped ZnO target. Low density and vertically well-aligned ZnO nanowires were grown on hexagonal cone-shape ZnO cores by introduction of a ZnO buffer layer. More than 90% of the ZnO cores of the Sb-induced ZnO nanowires are formed in the same size of 400 nm. The ZnO nanowires consist of single-crystalline wurtzite ZnO crystal and grow along [0001] direction. The room-temperature photoluminescence spectrum exhibited a strong ultraviolet emission at around 380 nm and a relatively low broad band emission in the visible region, indicating a low concentration of structural defect in the nanowires. Sb can be used as one of the effective additives to control the morphology and alignment of ZnO nanowires synthesized by NAPLD.     

Theoretical study of ZnO adsorption and bonding on Al<Subscript>2</Subscript>O<Subscript>3</Subscript> (0001) surface

ZnO adsorption on sapphire (0001) surface is theoretically calculated by using a plane wave ultrasoft pseudo-potential method based onab initio molecular dynamics. The results reveal that the surface relaxation in the first layer Al-O is reduced, even eliminated after the surface adsorption of ZnO, and the chemical bonding energy is 434.3(±38.6) kJ · mol⁻¹. The chemical bond of ZnO (0.185 ± 0.01 nm) has a 30° angle away from the adjacent, Al-O bond, and the stable chemical adsorption position of the Zn is deflected from the surface O-hexagonal symmetry with an angle of about 30°. The analysis of the atomic populations, density of state and bonding electronic density before and after the adsorption indicates that the chemical bond formed by the O²⁻ of the ZnO and the surface Al³⁺ has a strong ionic bonding characteristic, while the chemical bond formed by the Zn²⁺ and the surface O²⁻ has an obvious covalent characteristic, which comes mainly from the hybridization of the Zn 4s and the O 2p and partially from that of the Zn 3d and the O 2p.     

Effects of sapphire substrate annealing on ZnO epitaxial films grown by MOCVD

The annealing effects of sapphire substrate on the quality of epitaxial ZnO films grown by metalorganic chemical vapor deposition (MOCVD) were studied. The atomic steps formed on (0 0 0 1) sapphire (α-Al₂O₃) substrate surface by annealing at high temperature was analyzed by atomic force microscopy (AFM). The annealing effects of sapphire substrate on the ZnO films were examined by X-ray diffraction (XRD), AFM and photoluminescence (PL) measurements. Experimental results indicate that the film quality is strongly affected by annealing treatment of the sapphire substrate surface. The optimum annealing temperature of sapphire substrates is given.     

Growth,electronic and magnetic properties of doped ZnO epitaxial and nanocrystalline films

We have used oxygen plasma assisted metal organic chemical vapor deposition along with wet chemical synthesis and spin coating to prepare Co_xZn_1-xO and Mn_xZn_1-xO epitaxial and nanoparticle films. Co(II) and Mn(II) substitute for Zn(II) in the wurtzite lattice in materials synthesized by both methods. Room-temperature ferromagnetism in epitaxial Co:ZnO films can be reversibly activated by diffusing in Zn, which occupies interstitial sites and makes the material n-type. O-capped Co:ZnO nanoparticles, which are paramagnetic as grown, become ferromagnetic upon being spin coated in air at elevated temperature. Likewise, spin-coated N-capped Mn:ZnO nanoparticle films also exhibit room-temperature ferromagnetism. However, the inverse systems, N-capped Co:ZnO and O-capped Mn:ZnO, are entirely paramagnetic when spin coated into films in the same way. Analysis of optical absorption spectra reveals that the resonances Co(I)↔Co(II)+e^- _CB and Mn(III)↔Mn(II)+h⁺ _VB are energetically favorable, consistent with strong hybridization of Co (Mn) with the conduction (valence) band of ZnO. In contrast, the resonances Mn(I)↔Mn(II)+e^- _CB and Co(III)↔Co(II)+h⁺ _VB are not energetically favorable. These results strongly suggest that the observed ferromagnetism in Co:ZnO (Mn:ZnO) is mediated by electrons (holes). PACS 75.50.Pp     

Infrared and ultraviolet laser ablation mechanisms of SiO

The growth direction and morphology of ZnO nanostructures synthesized by gas reactions between Zn and O vapor can be modulated by changing the relative gas content of Zn and O in the reaction atmosphere. Dominant nanostructures of ZnO nanotubes and ZnO/Zn nanocables with [112̄0] growth direction were obtained under the oxygen-shortage condition, while mainly ZnO nanowires with [0001] growth direction were obtained under the situation of O abundance. PACS 61.46.+w; 68.70.+w; 81.10.Bk     

The role of a ZnO buffer layer in the growth of ZnO thin film on Al2O3 substrate

A ZnO buffer layer and ZnO thin film have been deposited by the pulsed laser deposition technique at the temperatures of 200 C and 400 C, respectively. Structural, electrical and optical properties of ZnO thin films grown on sapphire (Al₂O₃) substrate with 1, 5, and 9 nm thick ZnO buffer layers were investigated. A minute shift of the (101) peak was observed which indicates that the lattice parameter was changed by varying the thickness of the buffer layer. High resolution transmission electron microscopy (TEM) was used to investigate the thickness of the ZnO buffer layer and the interface involving a thin ZnO buffer between the film and substrate. Selected area electron diffraction (SAED) patterns show high quality hexagonal ZnO thin film with 30 in-plane rotation with respect to the sapphire substrate. The use of the buffer can reduce the lattice mismatch between the ZnO thin film and sapphire substrate; therefore, the lattice constant of ZnO thin film grown on sapphire substrate became similar to that of bulk ZnO with increasing thickness of the buffer layer.     

Control of polarity of heteroepitaxial ZnO films by interface engineering

Control of polarity of heteroepitaxial ZnO films has been examined by interface engineering. ZnO films were grown by plasma-assisted molecular beam epitaxy on Ga-polar GaN template and c-plane sapphire substrates. Polarity of all the samples is determined by coaxial impact collision ion scattering spectroscopy. Zn- and O-polar ZnO films have successfully grown by Zn- and O-plasma pre-exposures on Ga-polar GaN templates prior to ZnO growth. High-resolution transmission electron microscopy revealed formation of a single-crystalline monoclinic Ga₂O₃ interface layer by O-plasma pre-exposure on Ga-polar GaN templates, while no interface layer was observed for Zn pre-exposed ZnO films. The polarity of ZnO films grown under oxygen ambient on c-plane sapphire with MgO buffer is revealed as O-polar. Fabrication of polarity inverted ZnO heterostructure has been studied: polarity of ZnO films on Ga-polar GaN templates was changed from Zn-polar to O-polar by inserting a MgO layer. High-resolution transmission electron microscopy revealed atomically flat interfaces at both lower and upper ZnO/MgO interfaces and no inversion domain boundaries were detected in the upper ZnO layer.     

原子层沉积法 生长ZnO的性质与前驱体源量的关系研究

介绍了新型材料ZnO的各项性能,并采用原子层沉积方法制备新型材料ZnO. 实验中采用二乙基锌(DEZn) 和水作为生长ZnO的前驱体源, 在蓝宝石衬底上生长ZnO; 采用氮气作为载气, 生长温度为180℃. 通过改变在实验中的通入锌源的时间, 探索不同的DEZn的源的量对薄膜的成分(Zn/O)、薄膜的厚度、生长速率、晶型、 表面形貌、三维形貌以及粗糙度的影响. 关键词： 氧化锌 原子层沉积 Zn/O