p-type ZnO thin films grown by RF plasma beam assisted Pulsed Laser Deposition

The high exciton binding energy and band gap energy of ZnO thin films open the prospect of fabricating semiconductor lasers in the ultraviolet spectral range. A prerequisite for laser diode fabrication is highly p-doped ZnO which was not reproducibly obtained up to now. Without intentional doping ZnO exhibits n-type conduction. ZnO thin films have been obtained by radio-frequency assisted pulsed laser deposition. A metallic Zn target was used for ablation in an oxygen and nitrogen RF discharge. The electrical and morphological properties of the films grown on Si were studied by Atomic Force Microscopy (AFM), X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), optical absorption and Hall Effect measurements for different ratios between the nitrogen and oxygen content. The AFM images of the as-grown ZnO films reveal high quality surfaces with low values for the surface roughness and a sharp distribution of grains sizes as an effect of the RF discharge. The XRD patterns for all samples exhibit only (002) and (004) peaks indicating that the c-axis is always oriented normal to the substrate surface. The films present p-type conductivity with different carrier concentration and mobility depending on the nitrogen/oxygen ratio.     

Effect of the annealing environment on the optical properties of ZnO/GaAs grown by MOCVD

The optical properties of ZnO grown on (1 0 0) GaAs substrate using metalorganic chemical vapor deposition are investigated by photoluminescence (PL) spectroscopy. Postgrowth annealing in nitrogen and oxygen was performed for different times and temperatures in order to incorporate As from the substrate into the ZnO thin films. The PL spectra of the samples annealed in different ambients reveal that the effect of As diffusion into the ZnO thin films is more pronounced when the annealing is performed in oxygen at 550 °C. The 11 K PL spectra show the appearance of a transition at ∼3.35 eV after annealing in oxygen at 550 °C for 1 h. A further increase in the annealing temperature leads to the disappearance of this line, while for annealing times longer than 2 h at 550 °C, it is no longer prominent. The increase in intensity of this new transition is also accompanied by the enhancement of radiative centers related to structural defects, such as the stacking fault-related transition at 3.31 eV and the Y-line. Temperature dependent PL illustrates the excitonic nature of the new transition at ∼3.35 eV, which is therefore assigned to (A⁰, X) transition, where the acceptor is possibly the 2V_Zn-As_Zn complex, with an activation energy E_A in the range of 160-240 meV. Furthermore, the enhancement of the radiative centers related to structural defects is regarded as evidence that As atoms tend to segregate in the vicinity of structural defects to relieve local strain.     

High-quality oriented ZnO films grown by sol-gel process assisted with ZnO seed layer

High-quality oriented ZnO films were prepared on silicon and quartz glass by sol-gel, assisted with a ZnO seed layer. The effects of the seed layer on the orientation, morphology and optical properties of ZnO films were investigated. Results show that the seed layer can effectively induce the growth of high-quality oriented ZnO films on two substrates, and the effectiveness of the seed layer strongly depends on preparation conditions, i.e., the spin-coating layer number and the preheating temperature. ZnO films with five layers on the seed layer preheated at 500 °C exhibit the single (0 0 2) orientation, which is much stronger than that on the flat substrate. Additionally, ZnO films on the seed layer show a denser internal structure and higher optical quality than that on the flat substrate. At ten layers, however, ZnO films on the seed layer show the multiple-orientation, which is similar to that on the flat substrate. Finally, the physical mechanism underlying the growth behavior of ZnO films assisted with the seed layer was discussed.     

磁控溅射制备ZnO薄膜及其声表面波特性

通过射频磁控溅射技术在GaAs，Au/GaAs，Si和玻璃基片上成功制备了ZnO多晶薄膜，利用X射线衍射对ZnO薄膜的取向、结晶性进行了表征，结果表明ZnO薄膜呈完全c轴取向，Au缓冲层可以有效地改善ZnO薄膜的晶体质量，X射线摇摆曲线结果表明ZnO(002)衍射峰的半高宽仅为2.41°，同时发现Au缓冲层的结晶质量对ZnO薄膜的c轴取向度有很大影响，通过扫描电子显微镜对ZnO/GaAs和ZnO/Au/GaAs薄膜的表面形貌进行了观测，利用网络分析仪对IDT/ZnO/GaAs薄膜的声表面波特性进行了测量. 关键词： ZnO薄膜 X射线衍射 声表面波     

Effect of intrinsic stress on the optical properties of nanostructured ZnO thin films grown by rf magnetron sputtering

In this paper we report the effect of deposition temperature on the structural and optical properties of ZnO thin films prepared by rf magnetron sputtering. The films grown at lower deposition temperatures were in a state of large compressive stress, whereas the films grown at higher temperature (450 °C) were almost stress free. In the absorption spectra, the ZnO excitonic and the Zn surface plasmon resonance (SPR) peaks have been observed. A redshift in the optical band gap of ZnO films has also been observed with the increase in the deposition temperature. The shift in the band gap calculated from the size effect did not match with the observed shift values and the observed shift has been attributed to the compressive stress present in the films.     

X-ray analysis of ZnO nanorods grown by microwave irradiation heating on ZnO films

Utilizing microwave irradiation heating, 100-nm-diameter ZnO nanorods were grown from aqueous solution on sputtered ZnO films on glass substrates. Its out-of-plane X-ray diffraction (XRD) measurement indicated that the ZnO nanorods were grown with c-axis orientation, similar with the underlying ZnO films. In the in-plane XRD measurement, intensity of the () diffraction was comparable with that of the () one, suggesting their intensity ratio would contain useful information on nanorods density.     

Influence of annealing atmosphere on ZnO thin films grown by MOCVD

ZnO films were deposited on c-plane sapphire substrates by metal-organic chemical vapor deposition (MOCVD). Annealing treatments for as-deposited samples were performed in different atmosphere under various pressures in the same chamber just after growth. The effect of annealing atmosphere on the electrical, structural, and optical properties of the deposited films has been investigated by means of X-ray diffraction (XRD), atomic force microscope (AFM), Hall effect, and optical absorption measurements. The results indicated that the electrical and structural properties of the films were highly influenced by annealing atmosphere, which was more pronounced for the films annealed in oxygen ambient. The most significant improvements for structural and electrical properties were obtained for the film annealed in oxygen under the pressure of 60 Pa. Under the optimum annealing condition, the lowest resistivity of 0.28 Ω cm and the highest mobility of 19.6 cm² v⁻¹ s⁻¹ were obtained. Meanwhile, the absorbance spectra turned steeper and the optical band gap red shifted back to the single-crystal value.     

生长温度对MOCVD外延ZnO纳米结构的影响

为了探究生长温度对外延ZnO纳米结构的影响,得到ZnO纳米结构可控生长的生长温度条件。利用金属有机化学气相沉积（MOCVD）方法,设计并获得了不同生长温度的ZnO外延样品,并对所有样品进行了表面形貌、光学特性、电学特性表征和结晶质量表征。实验结果表明:600℃生长的ZnO纳米柱横向尺寸最小,为65 nm左右,其光学特性也相对较好,晶体衍射峰的半峰宽最小,为0.165°,晶粒尺寸最大,为47.6 nm;电学性质相对最优的为640℃生长的ZnO样品,霍尔迁移率高达23.5 cm²/（V·s）。通过结果分析发现,生长温度能影响外延ZnO的生长模式,从而影响ZnO的形貌、光学、电学和晶体质量等特性。     

Structural and optical properties of ZnO film by plasma-assisted MOCVD

High quality ZnO film was deposited by plasma-assisted metal-organic chemical vapor deposition (MOCVD). We observed a dominant peak at 34.6° due to (0 0 2) ZnO, which indicated that the growth of ZnO film was strongly C-oriented. The full-width at half-maximum (FWHM) of the -rocking curve was 0.56° indicating relatively small mosaicity. Photoluminescence (PL) measurement was performed at both room temperature and low temperature. Ultraviolet (UV) emission at 3.30 eV was found with high intensity at room temperature while the deep level transition was weakly observed at 2.513 eV. The ratio of the intensity of UV emission to that of deep level emission was as high as 193, which implied high quality of ZnO film. From PL spectrum at 10 K, we observed A-exciton emission at 3.377 eV and D°X bound exciton transition at 3.370 eV. The donor–acceptor transition and LO phonon replicas were observed at 3.333 and 3.241 eV respectively. Raman scattering was performed in back scattering at room temperature. The E₂, A_1(LO) and A_1(TO) mode was seen at 437.6, 575.8 and 380 cm^–1 respectively. In comparison with Raman spectrum of ZnO powder, we found that ZnO film was nearly free of strain, which indicated high crystal quality.     

热处理参数对溶胶-凝胶法制备氧化锌薄膜特性的影响

采用溶胶-凝胶旋涂法在Si(111)衬底上生长了ZnO薄膜，并用荧光光谱、原子力显微镜和XRD对ZnO薄膜样品进行了分析.结果表明，溶胶-凝胶旋涂法制备的ZnO薄膜为纤锌矿结构，其c轴取向程度与热处理温度有很大的关系.当热处理温度小于550℃时，氧化锌薄膜在室温下均有较强的紫外带边发射峰，而可见波段的发射很弱；当热处理温度高于550℃时，可见波段发射明显增强.对经过不同时间热处理的ZnO薄膜样品分析表明，氧化锌薄膜的荧光特性及表面形貌与热处理时间也有很大关系，时间过短可见波段的发射较强，但时间过长会导致晶 关键词： ZnO薄膜 光致发光     

MOCVD growth and properties of ZnO films using dimethylzinc and oxygen

The ZnO films were grown by low pressure metal-organic chemical vapor deposition (LP-MOCVD) using dimethylzinc (DMZn) and oxygen. The as-grown film has strong (0002) oriented characteristic, containing the chain-like network grains in small sizes, A well-resolved shoulder emission at 3.03 eV in the photoluminescence (PL) spectra has been ascribed to the interstitial zinc in the crystal, implying a serious oxygen deficiency state of the MOCVD growth, in good agreement with the analysis of XPS results. Post-annealing of the films leads to the remarkable improvement of the structure, morphology, components and optical properties. Large hexagonal columnar grains were then observed by atomic force microscope (AFM). The luminescence efficiency was enhanced greatly due to the reduction of the nonradiative defects. Meanwhile, chemisorbed oxygen gives rise to surface acceptor states, resulting in the different radiative recombination. Photoluminescence excitation measurement shows good agreement with the above conclusions. PACS 68.55.Jk; 78.55.Et; 81.05.Dz; 81.15.Gh     

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.     

Properties of ZnO thin films grown on Si substrates by photo-assisted MOCVD

ZnO thin films were grown on (1 0 0) p-Si substrates by Photo-assisted Metal Organic Chemical Vapor Deposition (PA-MOCVD) using diethylzinc (DEZn) and O₂ as source materials and tungsten-halogen lamp as a light source. The effects of tungsten-halogen lamp irradiation on the surface morphology, structural and optical properties of the deposited ZnO films have been investigated by means of atomic force microscope (AFM), X-ray diffraction and photoluminescence (PL) spectra measurements. Compared with the samples without irradiation, the several characteristics of ZnO films with irradiation are improved, including an improvement in the crystallinity of c-axis orientation, an increase in the grain size and an improvement in optical quality of ZnO films. These results indicated that light irradiation played an important role in the growth of ZnO films by PA-MOCVD.     

Structural and morphological characterizations of ZnO films grown on GaAs substrates by MOCVD

The production of boron carbide (B₄C) nanoparticles was investigated in a conventional high temperature furnace reactor. The reaction was carried out by heating a mixture of amorphous carbon and amorphous boron at 1550 °C to efficiently obtain a quantity of B₄C. Scanning electron microscopy studies showed the average size of B₄C particles was 200 nm, ranging from 50 nm to 350 nm. X-ray diffraction transmission electron microscopy and electron diffraction studies indicated that the prepared nanoparticles were crystalline B₄C with a high density twin structure. High resolution transmission electron microscopy and selected area diffraction were also used to further characterize the structure of the prepared B₄C particles, while energy dispersive spectroscopy and electron energy loss spectroscopy were used to determine the stoichiometry of the product. A solid state diffusion reaction mechanism is proposed.     

工作气压对磁控溅射ZnO薄膜结晶特性及生长行为的影响

采用射频反应磁控溅射方法，在Si(001)基片上制备了具有高c轴择优取向的ZnO薄膜.利用原子力显微镜、X射线衍射、透射电子显微镜和透射光谱分析技术，对不同工作气压下合成的ZnO薄膜的表面形貌、微观结构和光学性能进行表征，研究了工作气压对ZnO薄膜的结晶性能以及生长行为的影响.研究结果显示：对于Ar/O₂流量比例接近1∶1的固定比值下，ZnO薄膜的生长行为主要取决于成膜空间中氧的密度，临界工作气压介于0.5—1.0 Pa之间.当工作气压小于临界值时，ZnO薄膜的成核密度较高，且随工作气压的变化明显，ZnO的生长行为受控于氧的密度，属于氧支配的薄膜生长；当工作气压大于临界值以后，ZnO薄膜的成核密度基本保持不变，Zn原子的数量决定薄膜的生长速率；在0.1—5.0 Pa的工作气压范围内，均可获得高度c轴取向的ZnO薄膜，但工作气压的变化改变着ZnO晶粒之间的界面特征和取向关系.随着工作气压的增加，ZnO晶粒之间的界面失配缺陷减少，但平面织构特征逐渐消失，三叉晶界的空洞逐渐扩大，薄膜的密度下降，折射率减小. 关键词： ZnO薄膜 磁控溅射 表面形貌 微观结构 光学性能     

Optical and electrical properties of aluminum-doped ZnO thin films grown by pulsed laser deposition

Transparent aluminum-doped zinc oxide (AZO) thin films were deposited on quartz glass substrates by pulsed laser deposition (PLD) from ablating Zn-Al metallic targets. The structural, electrical and optical properties of these films were characterized as a function of Al concentration (0-8 wt.%) in the target. Films were deposited at a low substrate temperature of 150 °C under 11 Pa of oxygen pressure. It was observed that 2 wt.% of Al in the target (or 1.37 wt.% of Al doped in the AZO film) is the optimum concentration to achieve the minimum film resistivity and strong ultraviolet emission. The presence of Al in the ZnO film changes the carrier concentration and the intrinsic defects.     

Electrical characterisation of phosphorus-doped ZnO thin films grown by pulsed laser deposition

Phosphorus-doped ZnO films were grown by pulsed laser deposition using a ZnO:P₂O₅-doped target as the phosphorus source with the aim of producing p-type ZnO material. ZnO:P layers (with phosphorus concentrations of between 0.01 to 1 wt%) were grown on a pure ZnO buffer layer. The electrical properties of the films were characterised from temperature dependent Hall-effect measurements. The samples typically showed weak n-type conduction in the dark, with a resistivity of 70 Ω cm, a Hall mobility of μ_n0.5 cm² V ⁻¹ s⁻¹ and a carrier concentration of n3×10¹⁷ cm⁻³ at room temperature. After exposure to an incandescent light source, the samples underwent a change in conduction from n- to p-type, with an increase in mobility and decrease in concentration for temperatures below 300 K.     

Investigation of the vibrational modes of ZnO grown by MOCVD on different orientation planes

Wurtzite ZnO thin films were prepared on sapphire substrate by metal organic chemical vapor deposition (MOCVD). Raman scattering studies on different crystallographic textures were performed in the backscattering geometry, and polarization effect is investigated in different configurations and . ZnO Raman modes are investigated in each texture. In the case of ZnO thin film deposed on r‐() sapphire plane and using backscattering geometry, new Raman line was observed at 390 cm⁻¹ because this mode has not been noticed in this geometry. It is shown that the frequencies of the quasi‐phonon modes of the examined thin film are in good agreement with the theoretical values calculated within the framework of Loudon model. Copyright © 2014 John Wiley & Sons, Ltd.     

Dependences of structural and electrical properties on thickness of polycrystalline Ga-doped ZnO thin films prepared by reactive plasma deposition

Polycrystalline Ga-doped (Ga content: 4 wt%) ZnO (GZO) thin films were deposited on glass substrates at 200 C by a reactive plasma deposition with DC arc discharge technique. The dependences of structural and electrical properties of GZO films on thickness, ranging from 30 to 560 nm, were investigated. Carrier concentration, n, and Hall mobility, μ, increases with increasing film thickness below 100 nm, and then the n remains nearly constant and the μ gradually increases until the thickness reaches 560 nm. The resistivity obtained of the order of 10⁻⁴ Ω cm for these films decreases with increasing film thickness: The highest resistivity achieved is 4.4×10⁻⁴ Ω cm with n of 7.6×10²⁰ cm⁻³ and μ of 18.5 cm²/V s for GZO films with a thickness of 30 nm and the lowest one is 1.8×10⁻⁴ Ω cm with n of 1.1×10²¹ cm⁻³ and μ of 31.7 cm²/V s for the GZO film with a thickness of 560 nm. X-ray diffraction pattern for all the films shows a hexagonal wurtzite structure with its strongly preferred orientation along the c-axis. Full width at half maximum of the (002) preferred orientation diffraction peak of the films decreases with increasing film thickness below 100 nm.     

Room temperature growth and properties of ZnO films by pulsed laser deposition

ZnO thin films were prepared by pulsed laser deposition at room temperature on glass substrates with oxygen pressures of 10-30 Pa. The structural, electrical, and optical properties of ZnO films were studied in detail. ZnO films had an acceptable crystal quality with high c-axis orientation and smooth surface. The resistivity was in the 10² Ω cm order for ZnO films, with the electron concentration of 10¹⁶-10¹⁷ cm⁻³. All the films showed a high visible transmittance ∼90% and a high UV absorption about 90-100%. The UV emission ∼390 nm was observed in the photoluminescence spectra. The oxygen pressures in the 10-30 Pa range were suitable for room temperature growth of high-quality ZnO films.