Al和Sb共掺对ZnO有序阵列薄膜的结构和光学性能的影响

采用水热合成法在预先生长的ZnO种子层的玻璃衬底上制备出Al和Sb共掺ZnO纳米棒有序阵列薄膜. 通过X射线衍射、扫描电镜、透射电镜和选区电子衍射分析表明:所制备的薄膜由垂直于ZnO种子层的纳米棒组成, 呈单晶六角纤锌矿ZnO结构, 且沿[001]方向择优生长, 纳米棒的平均直径和长度分别为27.8 nm和1.02 μm. Al和Sb共掺ZnO纳米棒有序阵列薄膜的拉曼散射分析表明:相对于未掺杂ZnO薄膜的拉曼振动峰(580 cm^-1), Al和Sb共掺ZnO阵列薄膜的E₁(LO)振动模式存在拉曼位移. 当Al和Sb的掺杂量为3.0at%,4.0at%,5.0at%,6.0at%时, Al和Sb共掺ZnO阵列薄膜的拉曼振动峰的位移量分别为3,10,14,12 cm^-1. E₁ (LO) 振动模式位移是由Al和Sb掺杂ZnO产生的缺陷引起的. 室温光致发光结果表明:掺杂Al和Sb后, ZnO薄膜在545 nm处的发光强度减小,在414 nm处的发光强度增加. 这是由于掺杂Al和Sb后, ZnO薄膜中Zn_i缺陷增加, O_i缺陷减少引起的. 关键词： Al和Sb共掺ZnO薄膜 纳米棒有序阵列 结构表征 拉曼散射     

带隙可调的Al，Mg掺杂ZnO薄膜的制备

利用射频磁控溅射（RF-MS）方法,固定Al₂O₃掺杂量2 wt%,Mg掺杂量分别为1 wt%,3 wt%和5 wt%,在玻璃基底上制备了Al掺杂和Al,Mg共掺杂的ZnO薄膜,在500 ℃空气中退火2 h后,测量并比较了它们的光学和电学性质．结果表明,Al,Mg共掺杂的ZnO薄膜结晶质量良好,具有ZnO纤锌矿结构,具有较强的（002）面衍射峰,表明薄膜晶体沿c轴优先生长;与Al掺杂ZnO薄膜相比蓝端光透射率增加,1 wt%和3 wt% Mg掺杂薄 关键词： 射频磁控溅射 ZnO薄膜 Al Mg共掺杂     

Structural,electrical and optical studies on spray-deposited aluminium-doped ZnO thin films

Thin films of zinc oxide (ZnO) were deposited on cleaned glass substrates by chemical spray pyrolysis technique using Zn(CH₃COO)₂ as precursor solution. Also, aluminium-doped thin films of ZnO were prepared by using AlCl₃ as doping solution for aluminium. The dopant concentration [Al/Zn atomic percentage (at%)] was varied from 0 to 1.5 at% in thin films of ZnO prepared in different depositions. Structural characterization of the deposited films was performed with X-ray diffraction (XRD) studies. It confirmed that all the films were of zinc oxide having polycrystalline nature and possessing typical hexagonal wurtzite structure with crystallite size varying between 100.7 and 268.6 nm. The films exhibited changes in relative intensities and crystallite size with changes in the doping concentration of Al. The electrical studies established that 1 at% of Al-doping was the optimum for enhancing electrical conduction in ZnO thin films and beyond that the distortion caused in the lattice lowered the conductivity. The films also exhibited distinct changes in their optical properties at different doping concentrations, including a blue shift and slight widening of bandgap with increasing Al dopant concentration.     

Spray pyrolised Al/ZnO: Al heterojunction: Effect of Al on junction properties

Al/ZnO: Al heterojunction was fabricated by depositing ZnO: Al film on Al substrate by spray pyrolysis technique at 220 °C substrate temperature. XRD, SEM and EDAX techniques were used to study the properties of thin films. Heterojunction properties were studied by I–V and C–V measurements. The fabricated Al/ZnO: Al junctions were rectifying in character. The room temperature ideality factors of Al/ZnO: Al junctions are found to vary from 2.56 to 5.45. The reverse saturation currents are 5.21 × 10⁻⁹, 1.35 × 10⁻⁶, 1.99 × 10⁻⁶, 9.99 × 10⁻⁷ and 1.02 × 10⁻⁷ A for Al/ZnO: Al junctions. Junction forward current depends on doping concentrations and temperature, whereas reverse saturation current remains independent for Al concentration. The built-in-potential calculated from capacitance for Al/ZnO: Al junctions are 2.74, 2.60, 2.0, 2.50 and 2.43 V corresponding to 1, 2, 3, 4 and 5 mol% of Al. X-ray diffraction study confirmed that the films are polycrystalline, orientated in (0 0 2) plane. Scanning electron microscopy study confirmed circular ring patterns with inside ribbon type structure for Al doped ZnO films.     

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.     

High quality nitrogen-doped zinc oxide thin films grown on ITO by sol–gel method

Highly transparent N-doped ZnO thin films were deposited on ITO coated corning glass substrate by sol–gel method. Ammonium nitrate was used as a dopant source of N with varying the doping concentration 0, 0.5, 1.0, 2.0 and 3.0 at%. The DSC analysis of prepared NZO sols is observed a phase transition at 150 °C. X-ray diffraction pattern showed the preferred (002) peak of ZnO, which was deteriorated with increased N concentrations. The transmittance of NZO thin films was observed to be ~88%. The bandgap of NZO thin films increased from 3.28 to 3.70 eV with increased N concentration from 0 to 3 at%. The maximum carrier concentration 8.36×10¹⁷ cm⁻³ and minimum resistivity 1.64 Ω cm was observed for 3 at% N doped ZnO thin films deposited on glass substrate. These highly transparent ZnO thin films can be used as a window layer in solar cells and optoelectronic devices.     

Structure distortion,optical and electrical properties of ZnO thin films co-doped with Al and Sb by sol-gel spin coating

ZnO thin films co-doped with Al and Sb with different concentrations and a fixed molar ratio of AlCl 3 to SbCl 3 at 1:2, are prepared by a sol-gel spin-coating method on glass annealed at 550°C for 2 h in air. The x-ray diffraction results confirm that the ZnO thin films co-doped with Al and Sb are of wurtzite hexagonal ZnO with a very small distortion, and the biaxial stresses are 1.03×10 8 , 3.26×10 8 , 5.23×10 8 , and 6.97×10 8 Pa, corresponding to those of the ZnO thin films co-doped with Al and Sb in concentrations of 1.5, 3.0, 4.5, 6.0 at% respectively. The optical properties reveal that the ZnO thin films co-doped with Al and Sb have obviously enhanced transmittance in the visible region. The electrical properties show that ZnO thin film co-doped with Al and Sb in a concentration of 1.5 at% has a lowest resistivity of 2.5Ω·cm.     

Structural and optical properties of La-doped BaSnO3 thin films grown by PLD

In this study the structural and optical properties of lanthanum-doped BaSnO₃ powder samples and thin films deposited on fused silica were investigaed using laser ablation. Under an oxygen pressure of 5×10⁻⁴ mbar, phase pure BaSnO₃ films with a lattice constant of 0.417 nm and grain size of 21 nm were prepared at 630 °C. The band gap of BaSnO3 powder sample and thin films was calculated to be 3.36 eV and 3.67 eV, respectively. There was a progressive increase in conductivity for thin films of BaSnO₃ doped with 0~7 at% of La. The highest conductivity, 9 Scm⁻¹, was obtained for 7 at% La-doped BaSnO₃. Carrier concentration, obtained from Burstein-Moss (B-M) shift, nearly matches the measured values except for 3 at% and 10 at% La-doped BaSnO₃ thin films.     

Growth of high-quality ZnO thin films on (11\bar{2}0) a-plane sapphire substrates by plasma-assisted molecular beam epitaxy

High-quality ZnO thin films were grown on a-plane sapphire substrates by plasma-assisted molecular beam epitaxy. X-ray diffraction and transmission electron microscopy reveal that the ZnO films have high structural quality and an atomically sharp ZnO/Al₂O₃ interface. The full width at half maximum values of the 0002 and $30\bar{3}2$ ZnO ω-rocking curves are 467.8 and 813.5 arc sec for a 600 nm thick ZnO film. A screw dislocation density of 4.35×10⁸ cm^?2 and an edge dislocation density of 3.38×10⁹ cm^?2 are estimated by X-ray diffraction. The surface of the ZnO epilayers contains hexagonal pits, which can be observed in the Zn-polar ZnO. The films have a resistivity of 0.119 Ω?cm, an electron concentration of 6.85×10¹⁷ cm^?3, and a mobility of 76.5 cm²?V^?1?s^?1 at room temperature. Low temperature photoluminescence measurements show good optical properties comparable to ZnO single crystals.     

Influence of Al concentration on electrical, structural and optical properties of Al-As codoped p-ZnO thin films

We report the influence of Al concentration on electrical, structural, optical and morphological properties of Al-As codoped p-ZnO thin films using RF magnetron sputtering. Al-As codoped p-ZnO films with different Al concentrations were fabricated using As back diffusion from the GaAs substrate and sputtering Al₂O₃ mixed ZnO targets (1, 2 and 4 at%). The grown films were investigated by Hall effect measurement, X-ray diffraction (XRD), electron probe microanalysis (EPMA), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and atomic force microscopy (AFM) to study the electrical, structural, optical and morphological properties of the films. From the XRD, it was observed that both full-width at half-maximum (FWHM) and c-axis lattice constant have similar trends with respect to Al concentration. Hall measurements showed that the hole concentration increases as the Al concentration increases from 10¹⁵ to 10²⁰ cm⁻³. The increase in hole concentration upon codoping was supported by the red shift in the near-band-edge (NBE) emission observed from room temperature PL spectra. The proposed p-type mechanism due to As_Zn-2V_Zn complex was confirmed by low temperature PL and XPS analysis. The low FWHM, resistivity and peak-to-valley roughness observed by XRD, Hall measurement and AFM, respectively, suggest that 1 at% Al-doped ZnO:As film is the best codoped film.     

室温制备低电阻率高透过率H,W共掺杂ZnO薄膜

采用脉冲直流磁控溅射法,以WO3:ZnO陶瓷靶为溅射靶材,通过在溅射气氛中引入H2的方式,在室温条件下制备了低电阻率、高可见和近红外光区透过率的H,W共掺杂ZnO (HWZO)薄膜.系统地研究了H2流量对所制备的HWZO薄膜的结构、组分、元素价态、光电特性的影响.结果表明:掺入的H可促进Zn的氧化,改善薄膜的结晶质量,提高薄膜透过率.H引入之后薄膜的载流子浓度增加,电阻率降低.在H2流量为6mL/min时制备的HWZO薄膜性能最优,电阻率为7.71×10-4 Ω·m,光学带隙为3.58 eV,400-1100 nm的平均透过率为82.4％.     

Electrical properties of Sb-doped epitaxial SnO2 thin films prepared using excimer-laser-assisted metal–organic deposition

Excimer-laser-assisted metal–organic deposition (ELAMOD) was used to prepare Sb-doped epitaxial (001) SnO₂ thin films on (001) TiO₂ substrates at room temperature. The effects of laser fluence, the number of shots with the laser, and Sb content on the electrical properties such as resistivity, carrier concentration, and carrier mobility of the films were investigated. The resistivity of the Sb-doped epitaxial (001) SnO₂ thin film prepared using an ArF laser was lower than that of the film prepared using a KrF laser. The van der Pauw method was used to measure the resistivity, carrier concentration, and carrier mobility of the Sb-doped epitaxial (001) SnO₂ thin films in order to determine the effect of Sb content on the electrical resistivity of the films. The lowest resistivity obtained for the Sb-doped epitaxial (001) SnO₂ thin films prepared using ELAMOD with the ArF laser and 2 % Sb content was 2.5 × 10^?3 Ω cm. The difference between the optimal Sb concentrations and resistivities of the films produced using either ELAMOD or conventional thermal MOD was discussed.     

Towards a thin films electrochromic device using NASICON electrolyte

The optimisation of the morphology of WO₃ thin films allowed a more efficient electrochromic colouring using Na⁺ ions than H⁺ ones. Therefore, sodium superionic conductor (Na₃Zr₂Si₂PO₁₂, NASICON) films may be used as electrolyte in inorganic electrochromic devices. In this paper, the structure, chemical composition, morphology and electrochromic properties of WO₃, ZnO:Al and Na₃Zr₂Si₂PO₁₂ thin films were studied to develop a novel type of electrochromic device. WO₃, ZnO:Al and Na₃Zr₂Si₂PO₁₂ thin films were deposited using reactive magnetron sputtering of tungsten, zinc and aluminium and Zr–Si and Na₃PO₄ targets, respectively. For transparent conductive oxide coatings, a correlation was established between the deposition parametres and the film’s structure, transmittance and electrical resistivity. Classical sputtering methods were not suitable for the deposition of NASICON films on large surface with homogenous composition. On the other hand, the use of high-frequency pulsed direct current generators allowed the deposition of amorphous films that crystallised after thermal annealing upon 700 °C in the Na₃Zr₂Si₂PO₁₂ structure. Amorphous films exhibited ionic conductivity close to 2 × 10⁻³ S cm⁻¹. Finally, preliminary results related to the electrochromic performance of NASICON, WO₃ and indium tin oxide devices were given. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, France, Sept. 9–15, 2007.     

Effect of growth time on the structure, Raman shift and photoluminescence of Al and Sb codoped ZnO nanorod ordered array thin films

Al and Sb codoped ZnO nanorod ordered array thin films have been deposited on glass substrate with a ZnO seed layer by hydrothermal method at different growth time. The effect of growth time on structure, Raman shift, and photoluminescence (PL) was studied. The thin films at growth time of 5 h consist of nanorods growth vertically oriented with ZnO seed layer, and the nanorods with an average diameter of 27.8 nm and a length of 1.02 μm consist of single crystalline wurtzite ZnO crystal and grow along [0 0 1] direction. Raman scattering analysis demonstrates that the thin films at the growth time of 5 h have great Raman shift of 15 cm⁻¹ to lower wavenumber and have low asymmetrical factor Г_a/Г_b of 1.17. Room temperature photoluminescence reveals that there is more donor-related PL in films with growth time of 5 h.     

Surface microstructure and morphology study of thin films produced from volatile fluorine-containing rare-earth β-diketonate complexes and their adducts

We present the results of a surface microstructure and morphology study of thin films produced from volatile fluorine-containing rare-earth β-diketonate complexes and their adducts. Films 0.2–0.4 μm in thickness were synthesized in vacuum by means of thermal deposition of the parent substances at a pressure of 5 × 10^?4?1 × 10^?3 Pa and a deposition rate of 3 × 10^?3 μm s^?1 (for NaNd(FOD)₄ films, the deposition rate was 8 × 10^?2 μm s^?1). The microstructure of films depends on the deposition conditions. The films of [NaNd(PTFA)₄] and [NaNd(FOD)₄] complexes and Ln(PTFA)₃ · S₁ adducts have an amorphous structure. The [NaNd(PTFA)₄(Phen)] and Nd(PTFA)₃ · S₂ films are characterized by a more ordered polycrystalline structure with the grain size ranging from 0.2 to 1.5 μm.     

溶胶-凝胶法制备Li-N双掺p型ZnO薄膜的结构、光学和电学性能

采用溶胶-凝胶法在n型Si(100)衬底上沉积Li-N双掺杂ZnO薄膜,经X射线衍射和扫描电镜图片分析,所制备薄膜具有多晶纤锌矿结构和高的c轴择优取向.室温下霍尔效应测试结果显示Li-N双掺杂ZnO薄膜具有p型导电特性.在Li掺杂量为15.0at%,Li/N（摩尔比）为1∶1,700℃退火等优化条件下得到的最佳电学性能结果是：电阻率为0.34 Ω·cm,霍尔迁移率为16.43 cm²/V·s,载流子浓度为2.79×10¹⁹ cm^{-3关键词： Li-N双掺 p型ZnO薄膜 溶胶-凝胶 性能}     

Preparation and electrical conductivity of LISICON thin films

LISICON thin films have been prepared with RF sputtering and subsequent heat-treatment. The crystal phases of sputtered films depend on the sputtering conditions, especially the target composition and ambient gas atmosphere. Though the as-sputtered films in Ar-O₂ mixed gas (target composition: Li₃Zn_0.5GeO₄+0.5 ZnO, gas pressure: 9×10^-2 Torr, oxygen gas content: 74.6%) were amorphous; LISICON single phase thin films were obtained after annealing at 600°C for 6 h. The conductivity of the film at 500°C is 5×10^-3ω^-1cm^-1 which is slightly lower than that for ceramic Li₃Zn_0.5GeO₄.     

MnBiAl薄膜的磁光及磁性能研究

用真空电子束蒸发制备了MnBi_xAl_0.15薄膜.当0.4≤x≤0.7时,MnBi_xAl_0.15薄膜的Kerr角与MnBi_x薄膜相比有显著增大;而当x＞0.7时,MnBi_xAl_0.15的Kerr角则比MnBi_x的要不,633nm波长测量时,MnBi_{0.5Al0.15的Kerr角为2.75°,而相对应的MnBi0.5薄膜只有1.56°.MnBi05Al0.15薄膜的室温饱和磁化强度Ms为3×10⁵A/m,比MnBi0.5薄膜的Ms(4×10⁵A/m)要小.推测当0.4≤x≤0.7时,Al可能部分占据Bi空位和部分取代Mn位,由于晶格收缩使得Mn 3d电子与Bi 6p电子的杂化概率增大,从而导致其Kerr效应增强. 关键词：}     

Effect of Si ion irradiation on polycrystalline CdS thin film grown from novel photochemical deposition technique

CdS thin films have been deposited from aqueous solution by photochemical reactions. The solution contains Cd(CH₃COO)₂ and Na₂S₂O₃, and pH is controlled in an acidic region by adding H₂SO₄. The solution is illuminated with light from a high-pressure mercury-arc lamp. CdS thin films are formed on a glass substrate by the heterogeneous nucleation and the deposited thin films have been subjected to high-energy Si ion irradiations. Si ion irradiation has been performed with an energy of 80 MeV at fluences of 1×10¹¹, 1×10¹², 1×10¹³ and 1×10¹⁴ ions/cm² using tandem pelletron accelerator. The irradiation-induced changes in CdS thin films are studied using XRD, Raman spectroscopy and photoluminescence. Broadening of the PL emission peak were observed with increasing irradiation fluence, which could be attributed to the band tailing effect of the Si ion irradiation. The lattice disorder takes place at high Si ion fluences.     

氢气引入对宽光谱Mg和Ga共掺杂ZnO透明导电薄膜的特性影响

为适应宽光谱高效率硅基薄膜太阳电池的应用需求,本文尝试采用直流磁控溅射技术在553 K衬底温度下生长氢化Mg和Ga共掺杂ZnO(HMGZO)透明导电氧化物(TCO)薄膜.通过对薄膜微观结构、表面形貌、电学以及光学性能的测试和分析,详细地研究了氢气(H2)流量(0—16.0 sccm)对HMGZO薄膜结晶特性及光电性能的影响.实验结果表明:生长获得的HMGZO薄膜均为六角纤锌矿结构的多晶薄膜,择优取向为(002)晶面生长方向.薄膜的生长速率随着氢气流量的增加呈现逐渐减小趋势,主要归因于溅射产额的减小.适当的氢气引入会引起晶粒尺寸的增加.随着氢气流量由0增加至4.0 sccm,ZnO薄膜电阻率从177?·cm急剧减小至7.2×10-3?·cm,主要是由于H施主的引入显著地增加了载流子浓度;然而进一步增加氢气流量(4.0—16.0 sccm)造成电阻率的轻微增加,主要归因于载流子浓度的减小以及过多氢杂质引入造成杂质散射的增加.所有生长获得的HMGZO薄膜平均光学透过率在波长λ～320—1100 nm范围内可达87%以上.由于Mg的作用及Burstein-Moss效应的影响造成了带隙展宽,带隙变化范围～3.49—3.70 eV,其中最大光学带隙Eg可达～3.70 eV.