不同衬底和CdCl2退火对磁控溅射CdS薄膜性能的影响

在科宁7059玻璃, FTO, ITO, AZO四种衬底上磁控溅射CdS薄膜, 并在CdCl₂+干燥空气380 ℃退火, 分别研究了不同衬底和退火工艺对CdS薄膜形貌、结构和光学性能的影响. 扫描电子显微镜形貌表明: 不同衬底原位溅射CdS薄膜的形貌不同, 退火后相应CdS薄膜的晶粒度和表面粗糙度明显增大. XRD衍射图谱表明: 不同衬底原位溅射和退火CdS薄膜均为六角相和立方相的混相结构, 退火前后科宁7059玻璃, FTO, AZO衬底上CdS薄膜有 H(002)/C(111) 最强衍射峰, ITO衬底原位溅射CdS薄膜没有明显的最强衍射峰, 退火后出现 H(002)/(111) 最强衍射峰. 紫外-可见分光光度计分析表明: AZO, FTO, ITO, 科宁7059玻璃衬底CdS薄膜的可见光平均透过率依次减小, 退火后相应衬底CdS薄膜的可见光平均透过率增大, 光学吸收系数降低; 退火显著增大了不同衬底CdS薄膜的光学带隙. 分析得出: 上述结果是由于不同衬底类型和退火工艺对CdS多晶薄膜的形貌、结构和带尾态掺杂浓度改变的结果. 关键词： CdS薄膜 磁控溅射 退火再结晶 带尾态     

Characterization of ZnO thin films grown on various substrates by RF magnetron sputtering

In this study we investigated properties of ZnO thin films deposited on both oxygen-containing substrates and a substrate without oxygen content at various O₂/Ar reactant gas ratios. Deposition of ZnO on indium-tin oxide (ITO) resulted in the best crystallinity, whereas the least degree of crystallization was observed from ZnO deposited on glass. All the films were found to have compressive stress, which was relieved by annealing in O₂ environment. ZnO films deposited on glass revealed p-type conductivity when prepared at O₂/Ar ratio of 0.25 whereas those on SiN_x yielded p-type conductivity when prepared at O₂/Ar ratio of 4. In addition, shallower oxygen interstitial seemed to be found from films with better crystallinity. The largest shift in binding energy of Zn_2p3/2 was observed from ZnO prepared on glass at O₂/Ar ratio of 0.25, whereas that of O_1s was obtained from ZnO deposited on SiN_x at O₂/Ar ratio of 4. A model was proposed in terms of O₂ diffusion and hydrogen desorption in order to account for the observed property variations depending on substrates and O₂/Ar ratios.     

Fabrication of high hole-carrier density p-type ZnO thin films by N-Al co-doping

In order to obtain p-type ZnO thin films, effect of atomic ratio of Zn:N:Al on the electronic and structural characteristic of ZnO thin films was investigated. Hall measurement indicated that with the increase of Al doping, conductive type of as-grown ZnO thin films changed from n-type to p-type and then to n-type again, reasons are discussed in details. Results of X-ray diffraction revealed that co-doped ZnO thin films have similar crystallization characteristic (0 0 2 preferential orientation) like that of un-doping. However, SEM measurement indicated that co-doped ZnO thin films have different surface morphology compared with un-doped ZnO thin films. p-type ZnO thin films with high hole concentration were obtained on glass (4.6 × 10¹⁸ cm⁻³) and n-type silicon (7.51 × 10¹⁹ cm⁻³), respectively.     

Induction of p-type conduction in sputtered deposited Al-N codoped ZnO thin films

Al and N codoped ZnO thin films were grown on n-Si (100) substrate by sputtering technique. Hall effect measurements of as-grown films exhibited n-type conduction, however 500 °C Ar annealed codoped films showed p-type conductivity with a hole concentration of 9.9 × 10¹⁶ cm^− 3, resistivity of 15.95 Ω-cm and hole mobility of 3.95 cm²/Vs, respectively. Codoped ZnO thin films were found to be highly c-axis oriented with good crystal quality. A neutral acceptor-bound exciton and donor-acceptor-pair emissions that appeared at room temperature photoluminescence measurement verify p-type conduction in Al and N codoped ZnO film. The current-voltage characteristics of p-n heterojunction evidently showed a diode like rectifying behaviour.     

High quality p-type Ag-doped ZnO thin films achieved under elevated growth temperatures

By correlating the effects of substrate temperature, oxygen pressure and laser energy on the electrical and microstructural properties of Ag-doped ZnO films grown on a sapphire (0001) substrate, p-type conductivity is achieved under various substrate temperatures in the wide range of 250-750?°C. All of the samples were deposited by pulsed-laser deposition under various designed conditions. Hall measurements indicate that the best conductivity is achieved in Ag-ZnO films under a substrate temperature of 500?°C, a partial oxygen pressure of 250-300?mTorr and laser energy between 330 and 345?mJ. The hole-carrier concentration is 2.29?×?10(18)?cm(-3), the resistivity is 0.9?Ω?cm and the mobility is 3.03?cm(2)?V(-1)?s(-1). Transmission-electron microscopy (TEM) studies on the p-type films reveal similar microstructural properties to one another, but different properties to that of the n-type films deposited at the same temperatures with different deposition parameters.     

Effect of substrate and annealing on the structural and optical properties of ZnO:Al films

ZnO:Al thin films with c-axis preferred orientation were deposited on glass and Si substrates using RF magnetron sputtering technique. The effect of substrate on the structural and optical properties of ZnO:Al films were investigated. The results showed a strong blue peak from glass-substrate ZnO:Al film whose intensity became weak when deposited on Si substrate. However, the full width at half maxima (FWHM) of the Si-substrate ZnO:Al (0 0 2) peaks decreased evidently and the grain size increased. Finally, we discussed the influence of annealing temperature on the structural and optical properties of Si-substrate ZnO:Al films. After annealing, the crystal quality of Si-substrate ZnO:Al thin films was markedly improved and the intensity of blue peak (∼445 nm) increased noticeably. This observation may indicate that the visible emission properties of the ZnO:Al films are dependent more on the film crystallinity than on the film stoichiometry.     

射频反应磁控溅射法退火生长Na-N共掺杂p-ZnO薄膜

采用射频反应磁控溅射法退火生长得到了Na-N共掺杂p-ZnO薄膜。XRD测试结果表明,退火前后均得到c轴择优取向的ZnO薄膜。Hall测试结果表明:退火后薄膜的电学性能明显改善,得到了p-ZnO薄膜,退火温度为450℃时取得最佳电学性能:室温电阻率为139.2Ω.cm,迁移率为0.2cm2.V-1.s-1,空穴浓度为2.5×1017cm-3。XPS分析表明:Na掺入ZnO中作为受主NaZn而存在,N主要以N—H键的形式存在,其受主NO的作用不明显,但是否存在NaZn-NO受主复合体,还需进一步的研究。     

Properties of ZnO thin films deposited on (glass,ITO and ZnO:Al) substrates

ZnO thin films were deposited on glass, ITO (In₂O₃; Sn) and on ZnO:Al coated glass by spray pyrolysis. The substrates were heated at 350 °C. Structural characterization by X-ray diffraction (XRD) measurements shows that films crystallize in hexagonal structure with a preferential orientation along (0 0 2) direction. XRD peak-shift analysis revealed that films deposited on glass substrate (−0.173) were compressive, however, films deposited onto ITO (0.691) and on ZnO:Al (0.345) were tensile. Scanning electron microscopies (SEM) show that the morphologies of surface are porous in the form of nanopillars. The transmittance spectra indicated that the films of ZnO/ITO/glass and ZnO/ZnO:Al/glass exhibit a transmittance around 80% in the visible region. An empirical relationship modeled by theoretical numerical models has been presented for estimating refractive indices (n) relative to energy gap. All models indicate that the refractive index deceases with increasing energy band gap (E_g).     

Van der Pauw Hall Measurement on Intended Doped ZnO Films for p-Type Conductivity

A Van der Pauw Hall measurement is performed on the intended doped ZnO films （Na doped ZnO） grown by using the molecular beam epitaxial method. All as-grown samples show n-type conductivity, whereas the annealed samples （annealing temperature 900℃） show ambiguous carrier conductivity type （n- and p-type） in the automatic Van der Pauw Hall measurement. A similar result has been observed in Li doped ZnO and in as-doped ZnO films by other groups before. However, by tracing the Hall voltage in the Van der Pauw Hall measurement, it is found that this alternative appearance of both n- and p-type conductivity is not intrinsic behavior of the intended doped ZnO films, but is due to the persistent photoconductivity effect in ZnO. The persistent photoconductivity effect would strongly affect the accurate determination of the carrier conductivity type of a highly resistive intended doped ZnO sample.     

Effect of NH4OH concentration on p-type doped ZnO film by solution based process

Highly oriented and large scale p-type ZnO:Al:N films have been successfully synthesized by a simple, solution-based approach. In this approach, p-type doping of zinc oxide was achieved using combination of aqueous ammonia, zinc acetate and aluminium chloride. X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), photoluminescence and Hall measurements indicate that the structure of the ZnO:Al:N films were highly influenced by aqueous ammonia concentration. Excessive aqueous ammonia results in randomly oriented film with excessive precipitation.     

ZnO/Si异质结的光电转换特性研究

利用直流反应溅射方法在p型Si衬底上生长掺Al的n型ZnO薄膜,测量了由n型ZnO薄膜和p型Si衬底组成的异质结在黑暗和光照条件下的I-V特性,结果表明该异质结具有优良的整流特性,而且在光照条件下的反向电流迅速增大并很快趋于饱和.通过测量ZnO薄膜的光电流和异质结的光电压的光谱响应,初步分析了异质结的光电转换机理.测量结果显示,在入射光波长为380nm时光电流强度明显下降,反映出光电流与ZnO薄膜禁带宽度的密切关系;同时还发现,在与ZnO禁带宽度相对应的波长前后所产生的光生电压方向相反.推测这一现象与异质结的能带结构密切相关. 关键词： ZnO薄膜 异质结 光电转换 光谱响应     

Microstructural, optical and electrical studies on sol gel derived ZnO and ZnO:Al films

ZnO and ZnO:Al films were deposited onto glass substrates by the sol gel method using spin coating technique. The effects of aluminum dopant on the crystalline structure and orientation of the ZnO films have been investigated by X-ray diffraction (XRD) study. Surface morphology of the films has also been analyzed by a field emission scanning electron microscope (FESEM) and atomic force microscope (AFM). The average optical transmittance values of all the films is over >83% in the visible region. The optical band gap and Urbach energy values of these films were determined. The absorption edge shifted to the lower energy depending on the Al doping level. The shift of absorption edge is associated with shrinkage effect. The electrical conductivity of the ZnO film enhanced with the Al dopant. From the temperature dependence of conductivity measurements, the activation energy of the films was also calculated.     

NH3气氛处理制备p型ZnO薄膜及性能表征

采用NH₃气氛处理直流/射频共溅射方法制得的ZnO：Al薄膜,从而获得Al+N共掺p型ZnO薄膜.XRD,场发射扫描电子显微镜测试及Hall效应测试发现,处理温度对ZnO薄膜的结构和电学性能具有较大的影响,其中处理温度为700℃时,薄膜具有较好的c轴择优取向,并且薄膜表面平整,结构紧密,晶粒大小均匀,无明显空洞和裂缝,具有良好的表面质量,晶粒尺寸约为40—60nm,薄膜的导电类型由n型转变为p型. 关键词： p型ZnO Al+N共掺杂 直流/射频共溅射     

A comparative study on structural and optical properties of ZnO and Al-doped ZnO thin films obtained by ultrasonic spray method using different solvents

Transparent conducting ZnO and Al doped ZnO thin films were deposited on glass substrate by ultrasonic spray method. The thin films with concentration of 0.1 M were deposited at 350 °C with 2 min of deposition time. The effects of ethanol and methanol solution before and after doping on the structural, optical and electrical properties were examined. The DRX analyses indicated that ZnO films have nanocrystalline nature and hexagonal wurtzite structure with (1 0 0) and (0 0 2) preferential orientation corresponding to ZnO films resulting from methanol and ethanol solution, respectively. The crystallinity of the thin films improved with methanol solution after doping to (0 0 2) oriented. All films exhibit an average optical transparency about 90%, in the visible range. The band gaps values of ZnO thin films are increased after doping from 3.10 to 3.26 eV and 3.27 to 3.30 eV upon Al doping obtained by ethanol and methanol solution, respectively. The electrical conductivity increase from 7.5 to 15.2 (Ω cm)⁻¹ of undoped to Al doped ZnO thin films prepared by using ethanol solution. However, for the methanol solution; the electrical conductivity of the film is stabilized after doping.     

Electro-optical characteristics and field-emission properties of reactive DC-sputtered p-CuAlO2+x thin films

P-type transparent-conducting CuAlO_2+x thin films were deposited on silicon and glass substrates by reactive direct current sputtering of a prefabricated metal powder target having 1:1 atomic ratio of Cu and Al in oxygen-diluted argon atmosphere. XRD spectrum confirmed the proper phase formation of the material. UV-Vis-NIR spectrophotometric measurements showed high transparency of the films in the visible region with direct and indirect band gap values around 3.90 and 1.89 eV, respectively. The room temperature conductivity of the film was of the order of 0.22 S cm⁻¹ and the activation energy was 0.25 eV. Seebeck coefficient at room temperature showed a value of +115 μV/K confirming the p-type nature of the film. Room temperature Hall effect measurement also indicated positive value of Hall coefficient with a carrier concentration 4.4×10¹⁷ cm⁻³. We have also observed the low macroscopic field emission, from the wide band gap p-CuAlO_2+x thin film deposited on glass substrate. The emission properties have been studied for different anode-sample spacing. The threshold field was found to be as low as around 0.5–1.1 V/μm. This low threshold is attributed primarily to the internal nanostructure of the thin film, which causes considerable geometrical field enhancement inside the film as well as at the film/vacuum interface.     

Influence of Al doping on microstructure,morphology, optical and photoluminescence properties of pyrolytic ZnO thin films prepared in an ambient atmosphere

Zinc oxide (ZnO) and aluminium (Al) doped zinc oxide (AZO) thin films have been fabricated by spray pyrolysis technique in normal atmospheric condition. Samples of different Al-concentrations (0–5% Al) were deposited at 350 °C onto glass substrate to study the structural, morphological, optical and photoluminescence properties. X-ray diffraction study confirms that the films are polycrystalline having hexagonal structure. SEM images show that the films have rope and tube like morphology. Optical properties, such as transmittance, optical band gap, extinction coefficient, refractive index, optical conductivity, dielectric constants and electron energy loss functions were analyzed and discussed. Results show that the optical parameters have been changed significantly with Al-doping concentration. The photoluminescence spectra indicate that the PL peaks originated from deep level emissions (DLE) with different intensities for ZnO and Al-doped ZnO films.     

Electrical properties and Raman scattering investigation of Ag doped ZnO thin films

Ag-doped ZnO thin films were deposited on quartz glass substrates by a radio-frequency (RF) magnetron sputtering technique at room temperature (RT). The influence of Ag doping content on the electrical and Raman scattering properties of ZnO films were systematically investigated by Hall measurement system and Raman scattering spectrum. Two additional local vibrational modes (LVMs) at 230.0 and 394.5 cm^?1 induced by Ag dopant in ZnO:Ag films were observed by Raman analyses at RT, corresponding to Ag atoms located at O sites (LV M_Zn?Ag) and Zn sites (LV M_Ag?O) in ZnO lattice. Moreover, we further studied the effect of donor Ag_O and acceptor Ag_Zn defects on the electrical properties of ZnO:Ag films. The results indicate that O-rich condition is preferred to suppress the formation of Ag_O defects and enhance Ag_Zn defects. The p-type ZnO:Ag film was achieved by properly optimizing the annealing conditions under O-rich condition.     

Characterisation of porous doped ZnO thin films deposited by spray pyrolysis technique

Al or Sn doped ZnO films were deposited by spray pyrolysis using aqueous solutions. The films were deposited on either indium tin oxide coated or bare glass substrates. ZnCl₂, AlCl₃ and SnCl₂ were used as precursors. The effect of ZnCl₂ molar concentration (0.1-0.3 M) and doping percentage (2-4% AlCl₃ or SnCl₂) have been investigated. The main goal of this work being to grow porous ZnO thin films, small temperature substrates (200-300 °C) have been used during the spray pyrolysis deposition. It is shown that, if the X-ray diffraction patterns correspond to ZnO, the films deposited onto bare glass substrate are only partly crystallized while those deposited onto ITO coated glass substrate exhibit better crystallization. The homogeneity of the films decreases when the molar concentration of the precursor increases, while the grain size and the porosity decrease when the Al doping increases. The optical study shows that band tails are present in the absorption spectrum of the films deposited onto bare glass substrate, which is typical of disordered materials. Even after annealing 4 h at 400 °C, the longitudinal resistivity of the films is quite high. This result is attributed to the grain boundary effect and the porosity of the films. Effectively, the presence of an important reflection in the IR region in samples annealed testifies of a high free-carriers density in the ZnO crystallites. Finally it is shown that when deposited in the same electrochemical conditions, the transmission of a polymer film onto the rough sprayed ZnO is smaller than that onto smooth sputtered ZnO.     

Pulsed laser deposited ZnO/ZnO:Li multilayer for blue light emitting diodes

Thin films of ZnO, Li doped ZnO (ZLO) and multilayer of ZnO and ZLO (ZnO/ZLO) were grown on silicon and corning glass substrates by pulsed laser deposition technique. Single phase formation and the crystalline qualities of the films were analyzed by X-ray diffraction and Li composition in the film was investigated to be 15 wt% by X-ray photoelectron spectroscopy. Raman spectrum reveals the hexagonal wurtzite structure of ZnO, ZLO and ZnO/ZLO multilayer and confirms the single phase formation. Films grown on corning glass shows more than 80% transmittance in the visible region and the optical band gaps were calculated to be 3.245, 3.26 and 3.22 eV for ZnO, ZLO and ZnO/ZLO, respectively. An efficient blue emission was observed in all films which were grown on silicon (1 0 0) substrate by photoluminescence (PL). PL measurements at different temperatures reveal that the PL emission intensity of ZnO/ZLO multilayer was weakly dependent on temperature as compared to the single layers of ZnO and ZLO and the wavelength of emission was independent of temperature. Our results indicate that ZnO/ZLO multilayer can be used for the fabrication of blue light emitting diodes.