Wet-chemical etching of (11 $$\bar 2$$ 0) ZnO films0) ZnO films

This paper describes the optimized process of wet-chemical etching of a ZnO film grown on an r-plane sapphire. Different etchants and solution ratios have been used to achieve controllable etching rate and steep etching profile. With selected etching solutions, the etching profiles of epitaxially grown ZnO films (>1.3 μm) are improved. Using Al instead of photoresist as the mask generates a steeper etching slope. Maximal 1:1 vertical/horizontal ratio (45°) has been achieved. X-ray photoelectron spectroscopy (XPS) and sheet resistance measurements show that this wet-chemical etching process has negligible influence on the modification of the physical and chemical properties of the etched surface.     

Ultraviolet detectors based on epitaxial ZnO films grown by MOCVD

High-quality zinc oxide (ZnO) films were epitaxially grown on R-plane sapphire substrates by metalorganic chemical vapor deposition at temperatures in the range of 350°C to 600°C. In-situ nitrogen compensation doping was performed using NH₃. Microstructural and optical properties of the films, as well as the N-doping effects, were studied. The metal-semiconductor-metal ultraviolet sensitive photodetectors were fabricated on N-doped epitaxial ZnO films. The detector showed fast photoresponse, with a rise time of 1 μs and a fall time of 1.5 μs. Low-frequency photoresponsivity, on the order of 400 A/W at 5 V bias, was obtained.     

Fast and Reversible Wettability Transitions on ZnO Nanostructures

Surface wettability is an important property of solid/liquid interfaces. Recently, the control of contact angle (CA) has been used to drive liquid droplets in micro- or nanosize channels on biochemical and environmental sensing chips, where a faster CA transition rate is desirable for the prompt control of liquid movement. We studied the CA between water droplet and zinc oxide (ZnO) nanotips grown by metalorganic chemical vapor deposition (MOCVD). ZnO was grown as epitaxial films on r-plane sapphire, or as vertically aligned nanotips on various substrates, including silicon, c-plane sapphire, and glass. It is demonstrated that by using ultraviolet (UV) illumination and oxygen annealing, the CA on ZnO nanotips can be changed between 0° and 130°, whereas the CA on the ZnO films only varies between 37° and 100°. The fast transition rates also have been observed. (Received October 16, 2006; accepted January 23, 2007)     

ZnO nanotips grown on Si substrates by metal-organic chemical-vapor deposition

The ZnO nanotips are grown on silicon and silicon-on-sapphire (SOS) substrates using the metal-organic chemical-vapor deposition (MOCVD) technique. The ZnO nanotips are found to be single crystal and vertically aligned along the c-axis. In-situ Ga doping is carried out during the MOCVD growth. The ZnO nanotips display strong near-band edge photoluminescence (PL) emission with negligible deep-level emission. Free excitonic emission dominates the 77-K PL spectrum of the as-grown, undoped ZnO nanotips, indicating good optical properties and a low defect concentration of the nanotips. The increase of PL intensity from Ga doping is attributed to Ga-related impurity band emission. Photoluminescence quenching is also observed because of heavy Ga doping. ZnO nanotips grown on Si can be patterned through photolithography and etching processes, providing the potential for integrating ZnO nanotip arrays with Si devices.     

Realization of intrinsic p-type ZnO thin films by metal organic chemical vapor deposition

P-type ZnO thin films were grown on sapphire substrates with and without nitrous oxide (N₂O) by metal organic chemical vapor deposition (MOCVD). The intrinsic p-type ZnO films were achieved by controlling the Zn:O ratio in the range of 0.05–0.2 without N₂O flow. Secondary ion mass spectroscopy (SIMS) showed that the films contained little or no nitrogen (N) impurities for all samples. The p-type behavior of the samples should be due to the intrinsic acceptor-like defects V_Zn, for ZnO film grown without nitrous oxide, and N, occupying O sites as acceptors for ZnO film grown with nitrous oxide. The best p-type ZnO film has low resistivity of 0.369 Ω-cm, high carrier density of 1.62×10¹⁹ cm⁻³, and mobility of 3.14 cm²/V-s. The obtained p-type ZnO films possess a transmittance of nearly 100% in the visible region and strong near-band-edge emission.     

Photoluminescent properties of ZnO thin films grown on SiO2/Si(100) by metal-organic chemical vapor deposition

We report on the photoluminescent (PL) properties of ZnO thin films grown on SiO₂/Si(100) substrates using low pressure metal-organic chemical vapor deposition. The growth temperature of the films was as low as 400°C. From the PL spectra of the films at 10–300 K, strong PL peaks due to free and bound excitons were observed. The origin of the near bandedge emission peaks was investigated measuring temperature-dependent PL spectra. In addition, the Zn O films demonstrated a stimulated emission peak at room temperature. Upon illumination with an excitation density of 1 MW/cm², a strong, sharp peak was observed at 3.181 eV.     

Growth of phosphorus-doped p-type ZnO thin films by MOCVD

Phosphorus-doped p-type ZnO thin films are prepared on glass substrates by metalorganic chemical vapor deposition (MOCVD). DEZn, O2, and P2O5 powders are used as reactant and dopant sources. The p-type ZnO films are grown at a temperature between 673 K and 723 K. The best p-type sample has a low resistivity of A strong emission peak at 3.354 eV corresponding to neutral acceptor bound excitons is observed at 77 K in the photoluminescence spectra, which further verifies the p-type characteristics of the films.     

Structural and Optical Properties of ZnO Nanotips Grown on GaN Using Metalorganic Chemical Vapor Deposition

ZnO nanotips are grown on epitaxial GaN/c-sapphire templates by metalorganic chemical vapor deposition. X-ray diffraction (XRD) studies indicate that the epitaxial relationship between ZnO nanotips and the GaN layer is (0002)ZnO||(0002)GaN and (101̄0)ZnO||(101̄0)GaN. Temperature-dependent photoluminescence (PL) spectra have been measured. Sharp free exciton and donor-bound exciton peaks are observed at 4.4 K with photon energies of 3.380 eV, 3.369 eV, and 3.364 eV, confirming high optical quality of ZnO nanotips. Free exciton emission dominates at temperatures above 50 K. The thermal dissociation of these bound excitons forms free excitons and neutral donors. The thermal activation energies of the bound excitons at 3.369 eV and 3.364 eV are 11 meV and 16 meV, respectively. Temperature-dependent free A exciton peak emission is fitted to the Varshni’s equation to study the variation of energy bandgap versus temperature.     

Determination of the direction of piezoelectric field in InGaN/GaN multiple quantum-well structures grown by metal-organic chemical vapor deposition

The direction of the piezoelectric field in InGaN/GaN multiple quantum-well (MQW) structures grown by metal-organic vapor deposition (MOCVD) was determined using excitation-power-density variable photoluminescence (PL). By comparing the excitation-power-density dependence of the shift of the PL peak and the change of the full-width at half-maximum (FWHM) of the peak from an InGaN/GaN MQW structure and an InGaN MQW-based light-emitting diode (LED), the piezoelectric field in the InGaN/GaN MQW structures was unambiguously determined to be pointing toward the substrate. This result helps to identify the surface polarity of the LED wafer as Ga-faced.     

适用SAW器件的ZnO/Ti/Si薄膜制备及缺陷分析

在Si(100)衬底和Ti/Si(100)衬底上分别制备了ZnO薄膜,探讨了Ti缓冲层对ZnO薄膜结构和缺陷的影响,利用X射线衍射(XRD)测试了ZnO薄膜的晶体结构及择优取向,利用原子力显微镜(AFM)观察ZnO薄膜的表面粗糙度(RMS),利用光致发光(PL)光谱检测了ZnO薄膜的缺陷,利用四探针法测试了ZnO薄膜的电阻率。结果表明,在Ti/Si(100)衬底上、衬底温度350℃的条件下,制备的ZnO薄膜表面光滑、缺陷少、电阻率高且具有高C轴取向。本文这一工作对于压电薄膜缺陷分析及高性能ZnO的声表面波(SAW)器件研制有重要意义。     

Optical properties of InN films grown by MOCVD

By means of optical absorption, photolumines-cence (PL), Raman scattering and ellipsometry, optical properties of indium nitride (InN) films grown by metal organic chemical vapor deposition (MOCVD) are investigated. Through absorption and PL measurements, it is proven that the band gap of high quality InN is 0.68 eV, which agrees with the recently reported value, 0.7 eV. By analysis of the Raman scattering spectrum, the comparatively low background concentration of electron results in a smaller band gap value. The transition energy of wurtzite InN at critical point is determined by ellipsometric spectra. In addition, the complex refractive index of InN at energy ranging from 0.65 to 4.0 eV is obtained for the first time.     

Structural and optical properties of Zn<Subscript>1−x</Subscript>Mg<Subscript>x</Subscript>O thin films synthesized with metal organic chemical vapor deposition

We present the structural and optical properties of Zn_1?xMg_xO thin films studied using x-ray diffraction (XRD), extended x-ray absorption fine structure (EXAFS), and photoluminescence (PL) measurements. The Zn_1?xMg_xO films on sapphire [0001] substrates were fabricated with metal organic chemical vapor deposition (MOCVD). The XRD measurements showed that the Zn_1?xMg_xO films (x≤0.05) had a wurtzite structure without any MgO phase and were epitaxially grown along the c-axis of the Al₂O₃ substrate. The lattice constant of the Zn_0.95Mg_0.05O film shrank by 0.023 Å, compared with that of ZnO crystals. From the EXAFS measurements on the Zn_1?xMg_xO films at Zn K-edge, we found a substantial amount of distortion in the bond length of Zn-Zn pairs with a small amount of Mg substitution on the Zn site. The PL measurements showed a gradual increment of the main exciton transitions from 3.36 eV (x=0.0) to 3.57 eV (x=0.05) at 10 K. We also observed a strong deep-level emission near 2.3 eV from the specimen with x=0.05.     

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.     

基于PLD法制备ZnO:Eu3+,Li+薄膜的发光性质研究

采用脉冲激光沉积(PLD)技术在Si(111)衬底上生长了Eu3+、Li+共掺杂的ZnO薄膜。分别对样品进行了X射线衍射(XRD)谱测试和光致发光(PL)谱分析,重点研究了退火处理对样品结构和发射光谱的影响。XRD谱测试表明,样品具有很好的C轴择优取向。PL谱研究表明,当用325nm光激发样品时,样品的发射光谱仅由ZnO基质的紫外发射和蓝光发射组成,并没有发现稀土Eu3+的特征发光峰;样品的蓝光发射源于电子从Zn填隙形成的浅施主能级到Zn空位形成的浅受主能级跃迁;和真空中退火的样品相比,O2中制备的样品的蓝光发射减弱,紫外发光增强。用395nm的光激发时,退火前样品分别在594nm和613nm处存在两个明显的Eu3+特征发光峰,退火后的样品仅发现Eu3+位于594nm的特征发光峰,这表明,退火处理不利于稀土离子的特征发射,但O2中退火的样品ZnO基质红绿波段发射光谱明显增强。     

Deposition of tantalum oxide films by dual spectral source assisted metalorganic chemical vapor deposition (MOCVD)

Dual spectral source assisted metalorganic chemical vapor deposition (MOCVD) is an ideal technique for the deposition of high dielectric constant materials. Tungsten halogen lamps and a deuterium lamp are used as the sources of optical and thermal energy. In this paper, we have reported the deposition and characterization of tantalum penta oxide films. Ta₂O₅ films were deposited at 660°C for 15 min and annealed at 400°C for 1 h. The leakage current densities of 10.6 nm thick films are as low as 10₋₁₀ A/cm² for gate voltage under 4V. To the best of our knowledge, these are the best results reported to date by any researcher. The high energy photons used in the in-situ cleaning and deposition process play an important role in obtaining high quality films of Ta₂O₅.     

Electrical and optical properties of oxygen doped GaN grown by MOCVD using N2O

Oxygen doped GaN has been grown by metalorganic chemical vapor deposition using N₂O as oxygen dopant source. The layers were deposited on 2″ sapphire substrates from trimethylgallium and especially dried ammonia using nitrogen (N₂) as carrier gas. Prior to the growth of the films, an AIN nucleation layer with a thickness of about 300? was grown using trimethylaluminum. The films were deposited at 1085°C at a growth rate of 1.0 μm/h and showed a specular, mirrorlike surface. Not intentionally doped layers have high resistivity (>20 kW/square). The gas phase concentration of the N₂O was varied between 25 and 400 ppm with respect to the total gas volume. The doped layers were n-type with carrier concentrations in the range of 4×10¹⁶ cm⁻³ to 4×10¹⁸ cm⁻³ as measured by Hall effect. The observed carrier concentration increased with increasing N₂O concentration. Low temperature photoluminescence experiments performed on the doped layers revealed besides free A and B exciton emission an exciton bound to a shallow donor. With increasing N₂O concentration in the gas phase, the intensity of the donor bound exciton increased relative to that of the free excitons. These observations indicate that oxygen behaves as a shallow donor in GaN. This interpretation is supported by covalent radius and electronegativity arguments.     

InP-based multiple quantum well structures grown with tertiarybutylarsine (TBA) and tertiarybutylphosphine (TBP): Effects of growth interruptions on structural and optical properties

In this paper, we investigate the effect of interfacial layers on GalnAs(P)/GalnAsP and GalnAs/InP multiple quantum well structures with x-ray diffraction and photoluminescence. We observe a decrease in the room temperature and low temperature photoluminescence intensity as the number of periods is increased which we attribute to the interfaces. Furthermore, different growth interruption schemes show that decomposed As species from TBA have an effect on the structural and optical quality of these structures at both the lower and upper interfaces due to As carry-over. The effect of this carry-over is shown in structural measurements and laser diode results.     

Al薄膜对(002)ZnO/Al/Si结构基片中ZnO薄膜特性影响的实验研究

采用射频磁控溅射法沉积制备了(002)ZnO/A l/Si复合结构。研究了Al薄膜对(002) ZnO/Al/Si复合结构的声表面波器件(SAWD)基片性能影响以及当ZnO 薄膜厚度一定时的Al膜最佳厚度。采用X射线衍射(XRD)对Al和ZnO薄膜进行了结构表征 ,采用 扫描电镜(SEM)对ZnO薄膜进行表面形貌表征,并从薄膜生长机理角度进行了分析。结果 表明,加Al薄膜有利于ZnO薄膜按(002)择优取向生长,并且ZnO 薄膜的结晶性能提高;与(002)ZnO/Si结构基片相比,当Al薄膜 厚为100nm时,(002)ZnO/Al/Si结构中ZnO薄 膜的机电耦合系数提高 了65%。     

磁激励RF-PECVD法低温制备类金刚石薄膜及其特性

采用磁激励射频等离子体增强化学气相沉积(M-RF-PECVD)方法,室温下分别在玻璃和Si(100)衬底上制备类金刚石(DLC)薄膜,通过扫描电镜(SEM)、傅里叶红外光谱(FTIR)和Raman光谱对不同沉积条件下制备的薄膜进行表征。结果表明,在反应压强为30 Pa、入射功率为50 W、CH4/Ar=5/90、衬底温度为40℃的实验条件下,制备的含氢DLC薄膜表面平整、结构致密,膜基结合度良好,薄膜中以sp3键为主。     

The impact of nitridation and nucleation layer process conditions on morphology and electron transport in GaN epitaxial films

A systematic study has been performed to determine the characteristics of an optimized nucleation layer for GaN growth on sapphire. The films were grown during GaN process development in a vertical close-spaced showerhead metalorganic chemical vapor deposition reactor. The relationship between growth process parameters and the resultant properties of low temperature GaN nucleation layers and high temperature epitaxial GaN films is detailed. In particular, we discuss the combined influence of nitridation conditions, V/III ratio, temperature and pressure on optimized nucleation layer formation required to achieve reproducible high mobility GaN epitaxy in this reactor geometry. Atomic force microscopy and transmission electron microscopy have been used to study improvements in grain size and orientation of initial epitaxial film growth as a function of varied nitridation and nucleation layer process parameters. Improvements in film morphology and structure are directly related to Hall transport measurements of silicon-doped GaN films. Reproducible growth of silicon-doped GaN films having mobilities of 550 cm²/Vs with electron concentrations of 3 × 10¹⁷ cm⁻³, and defect densities less than 10⁸ cm⁻² is reported. These represent the best reported results to date for GaN growth using a standard two-step process in this reactor geometry.