ZnO薄膜材料的发光特性

回顾了最近几年对 Zn O薄膜材料发光特性的研究进展 ,介绍了用不同方法制备 Zn O薄膜的自发辐射和受激辐射发光特性。     

Growth-temperature-dependent optical and acetone detection properties of ZnO thin films

Zinc oxide (ZnO) thin films were prepared onto glass substrates at moderately low growth temperature by two-stage spray pyrolysis technique. The effects of growth temperature on structural, optical and acetone detection properties were investigated with X-ray diffractometry, a UV-visible spectrophotometer, photoluminescence (PL) spectroscopy and a homemade gas sensor testing unit, respectively. All the films are polycrystalline with a hexagonal wurtzite phase and exhibit a preferential orientation along [002] direction. The film crystallinity is gradually enhanced with an increase in growth temperature. The optical measurements show that all the films are physically highly transparent with a transmittance greater than 82% in the visible range. The band gap of the film is observed to exhibit a slight red shift with an increasing growth temperature. The PL studies on the films show UV/violet PL band at ～ 395 nm. Among all the films investigated, the film deposited at 250 ℃ demonstrates a maximum sensitivity of 13% towards 20 ppm of acetone vapors at 300 ℃ operating temperature.     

ZnO缓冲层和退火处理对MgO薄膜结构的影响

采用直流反应磁控溅射法在Si衬底上引入ZnO缓冲层制备了沿(200)晶面择优取向生长的MgO薄膜,然后分别采用快速退火和常规退火两种不同的方式对MgO薄膜进行晶化处理。利用X射线衍射仪(XRD)以及原子力显微镜(AFM)研究了ZnO缓冲层以及两种不同的退火方式对MgO薄膜的结构和形貌的影响。结果表明:具有合适厚度的ZnO缓冲层可以显著地提高MgO薄膜的结晶质量。另外,与快速退火相比,常规退火处理后得到的MgO晶粒均匀圆润,有着较大的(200)衍射峰强度以及较小的表面粗糙度。     

梯度掺杂生长绒面结构ZnO:B-TCO薄膜及其特性研究

采用新的金属有机化学气相淀积(MOCVD)-ZnO镀膜工艺技术-梯度掺杂技术生长绒面结构。研究ZnO:B-TCO薄膜。结果表明,梯度掺杂技术可有效增加薄膜晶粒尺寸和提高光散射作用。并且,梯度掺杂技术有效地提高了薄膜在近红外区域的光学透过率,有利于应用于宽谱域薄膜太阳电池。生长获得的MOCVD-ZnO薄膜,其薄膜电子迁移率为24 cm2/V,电阻率为2.17×10-3Ω.cm,载流子浓度为1.20×1020cm-3,且在小于1 000 nm波长范围内的平均透过率大于85%。     

Low substrate temperature deposition of transparent and conducting ZnO: Al thin films by RF magnetron sputtering

Transparent and conducting Al-doped ZnO(ZnO:Al) films were prepared on glass substrate using the RF sputtering method at different substrate temperatures from room temperature(RT) to 200 ℃. The structural,morphological, electrical and optical properties of these films were investigated using a variety of characterization techniques such as low angle XRD, Raman spectroscopy, X-ray photoelectron spectroscopy(XPS), field-emission scanning electron microscopy(FE-SEM), Hall measurement and UV–visible spectroscopy. The electrical properties showed that films deposited at RT have the lowest resistivity and it increases with an increase in the substrate temperature whereas carrier mobility and concentration decrease with an increase in substrate temperature. Low angle XRD and Raman spectroscopy analysis reavealed that films are highly crystalline with a hexagonal wurtzite structure and a preferred orientation along the c-axis. The FE-SEM analysis showed that the surface morphology of films is strongly dependent on the substrate temperature. The band gap decreases from 3.36 to 3.29 e V as the substrate temperature is increased from RT to 200 ℃. The fundamental absorption edge in the UV region shifts towards a longer wavelength with an increase in substrate temperature and be attributed to the Burstein-Moss shift. The synthesized films showed an average transmission(> 85%) in the visible region, which signifies that synthesized ZnO:Al films can be suitable for display devices and solar cells as transparent electrodes.     

制备工艺对ZnO薄膜的结构与光学性质的影响

利用射频磁控反应溅射技术生长出具有高度晶面(0002)取向的ZnO外延薄膜。通过AFM、XRD、吸收光谱和荧光光谱等测试手段,分别研究分析了不同衬底、不同溅射气氛和退火对ZnO薄膜结构及光学性质的影响。研究表明,在200℃低温生长的硅基ZnO薄膜具有几百纳米的氧化锌准六角结构外形;当氧氩比为4:1(质量流量比)时,吸收谱激子峰最佳;退火后,激子峰(363 nm)加强,同时出现了402 nm的本征氧空位紫光发射。     

Influence of growth time on crystalline structure, conductivity and optical properties of ZnO thin films

This paper examines the growth of ZnO thin films on glass substrate at 350 ℃ using an ultrasonic spray technique. We have investigated the influence of growth time ranging from 1 to 4 min on structural, optical and electrical properties of ZnO thin films. The as-grown films exhibit a hexagonal structure wurtzite and are (002) oriented. The maximum value of grain size G = 63.99 nm is attained for ZnO films grown at 2 min. The average transmittance is about 80%, thus the films are transparent in the visible region. The optical gap energy is found to increase from 3.26 to 3.37 eV with growth time increased from 1 to 2 min. The minimum value of electrical resistivity of the films is 0.13 Ω·cm obtained at 2 min. A systematic study on the influence of growth time on the properties of ZnO thin films deposited by ultrasonic spray at 350 ℃ has been reported.     

The study on mechanism of ultraviolet laser emission at room temperature from nanocrystal thin ZnO films grown on sapphire substrate by L-MBE

ZnO nanocrystal thin films were fabricated on sapphire substrates by laser molecular beam epitaxy. The structure and optical properties of the films were investigated experimentally. The film having small nanocrystal size of about 50-200 nm shows optically pumped ultraviolet laser emission at room temperature. This paper discussed the theoretical mechanism of excitonic radiative recombination in relation with the nanocrystal structure on ZnO film ultraviolet laser research. It is concluded that the experimental results are consistent with the theoretical analysis.     

退火气氛对稀土Eu3+掺杂ZnO薄膜结构和发光性质的影响

采用脉冲激光沉积(PLD)法在Si(111)衬底上制备稀土Eu3+掺杂ZnO薄膜材料,分别在纯氧和真空气氛中进行退火处理。XRD图谱中仅观察到尖锐的ZnO(002)衍射峰,表明ZnO:Eu3+,Li+薄膜具有良好的c轴取向。薄膜的结构参数显示：在纯氧气氛中退火的样品具有较大的晶粒尺寸且应力较小,表明在纯氧中退火的样品具有较好的结晶质量。通过光致发光谱发现,在纯氧中退火的样品的IUV/IDL比值较大,说明在纯氧中退火的样品缺陷去除更充分,结晶质量更好。当用395nm光激发样品时,仅发现Eu3+位于595nm附近的5D0→7F1磁偶极跃迁峰。并没有发现Eu3+在613 nm附近的特征波长发射,表明掺杂的Eu3+占据了ZnO基质反演对称中心格位。     

ZnO薄膜的激光光声效应

本文分析了ZnO薄膜的光声效应,推导了在一维条件下光声信号与压电系数、介电系数、热导、比热、调制频率之间的关系。实验表明光声信号的幅度和调制频率、入射光功率之间的理论分析吻合较好。同时还计算了ZnO薄膜的压电系数e_(33)=0.817e/m~2,e_(31)=-0.43e/m~2。     

B掺杂ZnO纳米薄膜的结构和光学特性研究

采用脉冲磁控溅射法制备了B掺杂ZnO(ZnO:B)纳米薄膜,并用X射线衍射(XRD)、扫描电子显微镜(SEM)和紫外-可见-近红外分光光度计分别研究了薄膜的结构和光学特性。结果表明:ZnO:B为多晶纳米薄膜,具有六方钎锌矿结构,且薄膜沿着c轴取向择优生长;在可见光和近红外光谱区的透光性能良好,其中在可见光区的平均透光率大于84%,而在近红外区的透光率随着波长增加而逐渐降低至45%。运用逐点无约束最优化法分析计算了薄膜的光学常数,在可见光区,ZnO:B纳米薄膜的光学常数随波长的变化很小且数值基本恒定,折射率约为2.0,而在紫外区,光学常数随波长的变化显著。     

ZnO薄膜紫外光敏特性及晶界势垒的研究

以二水合醋酸锌为原料,采用sol-gel法在石英衬底上制备了ZnO薄膜。用AFM观察表面形貌,通过测量真空条件下不同温度热处理后薄膜的I-V特性,拟合计算晶界势垒高度。研究了热处理温度对ZnO薄膜性能的影响。结果表明:经650℃热处理制备的ZnO薄膜样品具有较佳性能,结构均匀致密,粒径分布为20～32nm。在10V偏压和1.24×10–3W/cm2光强下,紫外光灵敏度为43.95;无光照条件下晶界势垒高度为0.079eV。紫外光照使晶界势垒高度下降为0.011eV,薄膜的紫外光灵敏度与势垒高度的相对变化密切相关。     

氧气浓度对ZnO薄膜表面形貌和微结构的影响

采用反应磁控溅射技术,在SiO2基底上制备了ZnO薄膜。通过原子力显微镜(AFM)和X射线电子能谱仪(XPS)对薄膜表面形貌及微结构进行了表征,分析了氧气之体积分数φ(O2)为40%~60%时,对薄膜表面形貌和微结构的影响。结果表明:随着氧气体积分数的增大,薄膜c轴晶向生长减弱,表面形貌趋向平整,氧化反应程度增强;?(O2)为60%时,薄膜表面粗糙度约为3nm,其内部的r(Zn:O)接近1:1。     

Nanoporous characteristics of sol-gel-derived ZnO thin film

Sol-gel-derived nanoporous ZnO film has been successfully deposited on glass substrate at 200℃ and subsequently annealed at different temperatures of 300, 400 and 600℃. Atomic force micrographs demonstrated that the film was crack-free, and that granular nanoparticles were homogenously distributed on the film surface. The average grain size of the nanoparticles and RMS roughness of the scanned surface area was 10 nm and 13.6 nm, respectively, which is due to the high porosity of the film. Photoluminescence (PL) spectra of the nanoporous ZnO film at room temperature show a diffused band, which might be due to an increased amount of oxygen vacancies on the lattice surface. The observed results of the nanoporous ZnO film indicates a promising application in the development of electrochemical biosensors due to the porosity of film enhancing the higher loading of bio-macromolecules (enzyme and proteins).     

Effect of pH on the properties of electrochemically prepared ZnO thin films

Zinc Oxide (ZnO) thin films have been electrochemically deposited on fluorine doped tin oxide (FTO) coated glass substrates from an aqueous electrolyte. Deposition potential −0.96 V was optimized by cyclic voltammetry experiment for slow scan rate 5 mV/s with moderate agitation of electrolyte. The effect of pH on the electrodeposition of ZnO is studied by cyclic voltammetry, X-ray diffraction (XRD), scanning electron microscopy (SEM), optical spectroscopy and photoelectrochemical I-t transient characteristics. It is revealed that the pH of the electrolyte has significant influence on the surface morphology and structural properties. Highly crystalline ZnO layers with hexagonal crystal structure deposited for all pH of the solutions. A systematic shift observed in the reflections (002) and (101) is correlated with an effective tensile strain developed in the crystal lattice. A remarkable improvement in the crystallinity was noticed in the as-deposited ZnO samples with increasing pH and upon heat treatment. Optical direct band gap ~ 3.26–3.33 eV and transmittance ~70 −80% was measured by optical spectroscopy. PL measurement showed the band edge emission at 375–382 nm and a visible light emission at 410–550 nm. The intensities of emission peaks are found to be affected by the pH of bath. The compact, densely packed and well adherent thin films of ZnO electrodeposited in zinc nitrate bath for pH 2.0, 3.5 and 6.0. The surface morphology has been changed from granular to disc shaped and finally a large hexagonal sheets were obtained with an increase in the pH of bath. Nearly stoichiometric ZnO thin films are electrodeposited at −0.96 V versus Ag/AgCl reference electrode for pH 6.0. The photoelectrochemical (PEC) measurement (I-t transient curve) shows the enhancement in photocurrent with increasing the pH of zinc nitrate solution. After heat treatment the photocurrent is increased by 54%, 98% and 130% in the samples deposited from 2.0, 3.5 and 6.0 pH of the bath. I-V measurements were further confirmed the current enhancement in all samples after heat treatment.     

ZnO薄膜的丙酮气敏特性研究

用直流磁控反应溅射法,分别在Si(111)基片及Al2O3陶瓷基片上制备了ZnO薄膜,并进行TiO2、SnO2、Al2O3或CuO的掺杂和退火处理。用XRD分析了退火前后晶型的变化,利用气敏测试系统对各样品进行了气敏特性测试。结果表明:经过700℃退火后的样品,在最佳工作温度为220℃时,对丙酮有很好的选择性和很高的灵敏度(34.794)。掺杂TiO2或SnO2,可提高ZnO薄膜传感器对丙酮的灵敏度(57.963)。     

沉积时间对Sn-Mg共掺ZnO薄膜光电性能的影响

采用超声喷雾热解法在石英玻璃衬底上,在衬底 温度为440 ℃,喷嘴到衬底距离为4cm,掺杂原子(Zn∶Mg∶Sn)比例为97.6∶2∶0.4,载气流量为0.8 L/min的固定条件下,制备了不同薄膜沉积时间(5min、 7min、9min、11 min)的Sn-Mg共掺的ZnO薄膜。并用X射线衍射仪 (XRD)、扫描电子显微镜(SEM)、 光致发光谱(PL)、紫外可见分光光度计(UV-VIS)、薄膜测厚仪(SCG-10)和伏安特性曲线(I-V)对 薄膜的结构、表面形貌、发光性能、透过率、膜厚和电学性能进行了一系列表征。当沉积时 间为7min时, XRD表明,薄膜的(101)峰强度最大,择优取向明显。SEM图显示薄 膜表面致密光滑,颗粒均匀,尺寸 最大且形貌最佳。PL谱在372 nm处的发射峰强度最大,峰形最尖锐, 所有薄膜的透过率在可见光区域都 超过了80%,表现出了很好的光透过性能。从薄膜的I- V特性曲线可计算出此时的电阻最小,导电性能最佳。     

Optical properties of ZnO thin films prepared by sol-gel process

The present study focused on ZnO thin films fabricated by sol-gel process and spin coated onto Si (1 0 0) and quartz substrates. ZnO thin films have a hexagonal würtzite structure with a grain diameter about 50 nm. Optical properties were determined by photoluminescence (PL) and absorption spectroscopy. The absorption spectrum is dominated by a sharp excitonic peak at room and low temperatures. At room temperature, two transitions were observed by PL. One near to the prohibited energy band in ultraviolet (UV) region and the other centered at 640 nm, characteristic of the electronic defects in the band-gap. The spectrum at 6 K is dominated by donor-bound exciton lines and donor-acceptor pair transition. LO-phonon replica and two-electron satellite transitions are also observed. These optical characteristics are a signature of high-quality thin films.     

脉冲激光扫描淀积类金刚石薄膜

采用能量密度为1.178×109W/cm2的XeCl准分子激光直接辐照高纯度的石墨靶,并同时采用辅助放电,在1×10-5Torr的真空环境中,于温度为80℃的Si(100)的基片上淀积出类金刚石薄膜,Raman光谱显示在1330cm-1处出现较强的散射峰值;对薄膜红外光谱进行测试,其光谱在2900cm-1处有吸收峰,表明所淀积的类金刚石薄膜含有C-H键,其H元素与C元素的比为45%.薄膜的电阻率为1.89×106Ω/cm,通过光吸收测得的该薄膜的能隙为1.55eV.     

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.