低压MOCVD法制备TiO_2薄膜的研究

以四异丙醇钛为原料 ,氧气作反应气体 ,高纯氮气作载气 ,采用低压MOCVD法在单晶Si基片上制备出了TiO2 薄膜。研究了基片温度和氧气流量对TiO2 薄膜沉积速率的影响 ,以及基片温度和退火温度对TiO2 薄膜的结构的影响。采用X射线衍射和喇曼光谱对TiO2 薄膜的结构进行分析。实验表明 :基片温度在1 1 0℃～ 2 5 0℃时制备的TiO2 薄膜是非晶态的 ,在 35 0℃～ 5 0 0℃时制备的TiO2 薄膜为锐钛矿和非晶态混杂结构 ,当基片温度超过 6 0 0℃时开始生成金红石。     

宽禁带氧化锌半导体薄膜的研究进展

氧化锌作为新一代化合物半导体,其禁带宽度对应紫外光的波长。氧化锌薄膜有望开发蓝光、蓝绿光、紫外光等多种发光器件,具有广阔的应用前景。重点介绍了氧化锌薄膜的研究进展以及存在的问题,并对氧化锌薄膜的未来进行了展望。     

斜角入射沉积TiO_2薄膜的光学特性和表面粗糙度

采用电子束热蒸发技术在K9玻璃基底上以不同的沉积入射角沉积了单层TiO2薄膜,研究了不同入射沉积角沉积的TiO2薄膜的光学特性、填充密度和表面粗糙度,并比较了不同膜层厚度下薄膜表面粗糙度与入射沉积角之间的关系。研究结果表明,随着入射沉积角的增加,TiO2薄膜的透射率增加,透射峰值向短波移动,薄膜的填充密度从入射沉积角0°时的0.801降低到入射沉积角为75°时的0.341;薄膜的表面粗糙度随着入射沉积角的增加而增加,当入射沉积角为75°时,薄膜的表面粗糙度略高于基底的表面粗糙度。在沉积入射角不变时,随着膜层厚度的增加,膜层的表面粗糙度降低。     

Solution Processing Route to Multifunctional Titania Thin Films: Highly Conductive and Photcatalytically Active Nb:TiO2

This paper reports the synthesis of highly conductive niobium doped titanium dioxide (Nb:TiO₂) films from the decomposition of Ti(OEt)₄ with dopant quantities of Nb(OEt)₅ by aerosol‐assisted chemical vapor deposition (AACVD). Doping Nb into the Ti sites results in n‐type conductivity, as determined by Hall effect measurements. The doped films display significantly improved electrical properties compared to pristine TiO₂ films. For 5 at.% Nb in the films, the charge carrier concentration was 2 × 10²¹ cm^?3 with a mobility of 2 cm² V^–1 s^–1 . The corresponding sheet resistance is as low as 6.5 Ω sq^–1 making the films suitable candidates for transparent conducting oxide (TCO) materials. This is, to the best of our knowledge, the lowest reported sheet resistance for Nb:TiO₂ films synthesized by vapour deposition. The doped films are also blue in colour, with the intensity dependent on the Nb concentration in the films. A combination of synchrotron, laboratory and theoretical techniques confirmed niobium doping into the anatase TiO₂ lattice. Computational methods also confirmed experimental results of both delocalized (Ti⁴⁺) and localized polaronic states (Ti³⁺) states. Additionally, the doped films also functioned as photocatalysts. Thus, Nb:TiO₂ combines four functional properties (photocatalysis, electrical conductivity, optical transparency and blue colouration) within the same layer, making it a promising alternative to conventional TCO materials.     

紫外光照下金属氧化物薄膜气敏特性研究进展

介绍了近期文献中对紫外光照下半导体金属氧化物薄膜气敏特性的研究结果:紫外光照引起SnO2,In2O3,ZnO薄膜电导显著增大;提高室温下薄膜对CO,NO2气体检测的灵敏度,减少响应和恢复时间;介绍了一种对紫外光增强气敏机制的物理模型分析方法。最后讨论了当前存在的难点问题(室温下气体检测的灵敏度不高及使用紫外光源不便)及未来研究方向(借改变薄膜的制备方法、工艺条件、优化金属氧化物薄膜的结构;通过掺杂复合改变薄膜的成分以及寻找禁带宽度窄的半导体材料等)。     

Electric Field‐Directed Convective Assembly of Ellipsoidal Colloidal Particles to Create Optically and Mechanically Anisotropic Thin Films

A method of simultaneous field‐ and flow‐directed assembly of anisotropic titania (TiO₂) nanoparticle films from a colloidal suspension is presented. Titania particles are oriented by an alternating (ac) electric field as they simultaneously advect towards a drying front due to evaporation of the solvent. At high field frequencies (ν > ～25 kHz) and field strengths (E > 300 V cm^?1), the particles orient with their major axis along the field direction. As the front recedes, a uniform film with thicknesses of 1–10 µm is deposited on the substrate. The films exhibit a large birefringence (Δn ≈ 0.15) and high packing fraction (? = 0.75 ± 0.08), due to the orientation of the particles. When the frequency is lowered, the particle orientation undergoes a parallel–random–perpendicular transition with respect to the field direction. The orientation dependence on field frequency and strength is explained by the polarizability of ellipsoidal particles using an interfacial polarization model. Particle orientation in the films also leads to anisotropic mechanical properties, which are manifested in their cracking patterns. In all, it is demonstrated that the field‐directed assembly of anisotropic particles provides a powerful means for tailoring nanoparticle film properties in situ during the deposition process.     

二氧化钒薄膜用于激光防护时膜层厚度的计算

VO2膜作为相变温度最接近室温的热致相变材料,相变前透过率高,探测器可正常工作,吸收来袭激光能量相变后透过率低,起到保护探测器作用,可用在激光防护领域。膜层厚度对透过率有很大影响,采用吸收膜的特征矩阵方法加以分析,通过VO2膜的折射率及消光系数等光学参数,计算出薄膜相变前后透过率。按照符合透过率相变前75%,相变后5%的薄膜,计算出厚度,结合对溅射产额和溅射速率的计算,可得到制备时间。在硒化锌基片上制备了VO2膜,用红外分光光度计测量出相变前后透过率为79.2%和12.3%。样品经轮廓仪测量得到的厚度与计算得到的厚度基本相符。     

Electrodeposition of Inorganic/Organic Hybrid Thin Films

Electrodeposition of inorganic compound thin films in the presence of certain organic molecules results in self‐assembly of various hybrid thin films with new properties. Examples of new discoveries by the authors are reviewed, taking cathodic formation of a ZnO/dye hybrid as the leading example. Hybridization of eosinY leads to the formation of highly oriented porous crystalline ZnO as the consequence of dye loading. The hybrid formation is a highly complicated process involving complex chemistry of many molecular and ionic constituents. However, electrochemical analyses of the relevant phenomena indicate the possibility of reaching a comprehensive understanding of the mechanism, giving us the chance to further develop them into industrial technologies. The porous crystals are ideal for photoelectrodes in dye‐sensitized solar cells. As the process also permits the use of non‐heat‐resistant substrates, the technology can be applied for the development of colorful and light‐weight plastic solar cells.     

ZnO纳米颗粒薄膜的制备及其光学特性

采用化学回流法制备了3种不同粒径的ZnO纳米颗粒,然后旋涂在ITO玻璃衬底上,形成样品a、b和c3种ZnO纳米颗粒薄膜.场发射扫描电子显微镜(FESEM)结果显示,3种样品晶粒都呈颗粒形状,形成的薄膜较平整,平均晶粒尺寸分别为(φ)5 nm、(φ)25 nm和(φ)40 nm.X线衍射(XRD)结果表明,ZnO纳米颗粒为多晶六方晶系纤锌矿结构.样品a、b在可见光区有很少的光吸收,在紫外光区有很强的吸收,而由于纳米颗粒的直径较大,样品c在紫外和可见光区都存在很强的吸收.室温下的光致发光谱表明,样品a有一个近带边(NBE)紫外发射峰和蓝光发射峰,样品b、c出现一很宽的深能级缺陷相关的可见光发光带,这说明3种薄膜都存在大量的本征缺陷.     

膜厚对氧化钒薄膜结构和光学性质的影响

利用真空热蒸发在石英基片上制备了不同厚度的氧化钒薄膜, 研究厚度对薄膜的结构、形貌和光学特性的影响。薄膜的结构由X射线衍射(XRD)仪和拉曼(Raman)光谱仪测得, 表面形貌用原子力显微镜(AFM)观测。利用分光光度计测量薄膜的光学透射率, 并且采用Forouhi-Bloomer模型与修正的德鲁德(Drude)自由电子模型相结合的方法拟合透射率来确定薄膜的折射率、消光系数和带隙。结果表明, 热蒸发的氧化钒薄膜呈非晶态, 薄膜的主要成分为五氧化二钒, 且含有少量的二氧化钒。薄膜表面的颗粒粘结在一起, 随着薄膜厚度的增加, 薄膜表面粗糙度以及颗粒尺寸变小, 膜层表面平整度越来越好, 颗粒之间的空隙变小, 导致折射率随膜厚的增加而增大, 消光系数减小。另外, 随着薄膜厚度从200 nm增加到450 nm, 光学带隙从2.67 eV减小到2.45 eV。     

Microdomain Transformations in Mosaic Mesocrystal Thin Films

An easy design route via simple evaporation is reported for macroscopic mosaic thin films comprising the quaternary system of dl ‐lysine·HCl, poly(acrylic acid), water, and EtOH. By depositing droplets of the quaternary dispersions onto hydrophilic cover slips, the formation of macroscopic crack‐free mosaic mesocrystal thin films are produced. The formation follows a multistage crystallization process, which includes the formation of a polymer‐induced liquid‐precursor (PILP) phase, the formation of spherulitic thin films, and the recrystallization of mosaic mesocrystal thin films. A slow cooling rate is noted to be beneficial for the mesocrystal thin films, enabling the films to be crack‐free and to display low surface roughness at the nanoscale.     

光电子薄膜的进展

由于光电子器件的迅速发展,对光电子器件应用的薄膜提出了很高的要求。本文简要地论述了光电子薄膜制备技术的重要进展,同时扼要地介绍了本实验室在这方面所开展的初步工作。     

HFCVD方法沉积金刚石薄膜的生长研究

本文讨论了金刚石薄膜应用于光学领域所遇到的问题，研究了热丝ＣＶＤ（ＨＦＣＶＤ）方法生长应用于光学膜的金刚石薄膜过程中，衬底表面的预处理和沉积条件如碳源浓度、衬底温度等对制备腹晶粒尺度和晶粒间界以及膜表面形貌的影响．     

氧化锌薄膜的电化学沉积法制备及受激发射研究

采用一种简单的电化学沉积法，在三电极化学池中，以单一的硝酸锌水溶液作为电沉积液，制备了高光学质量的半导体ZnO薄膜。透射光谱测量表明其光学带隙为3．35eV，400～2000nm波段的光学透过率大于80％。X射线衍射(XRD)和原子力显微镜(AFM)研究表明，ZnO薄膜为纤锌矿结构的无序多晶颗粒膜，微晶尺寸小于250nm。当用355nm的皮秒脉冲激光作为抽运源垂直入射薄膜表面时，可以检测到400nm附近的近紫外受激发射光，其强度随入射强度呈超线性增长关系，阈值在196．8kW／cm^2处，并且激光发射是多模的和各个方向的，还与被激发的面积有关，表现为随机激光发射机制。     

Thermally Conductive Reduced Graphene Oxide Thin Films for Extreme Temperature Sensors

Reduced graphene oxide (RGO) films are promising in applications ranging from electronics to flexible sensors. Though high electrical and thermal conductivities have been reported for RGO films, existing thermal conductivity data for RGO films show large variations from 30 to 2600 W m^?1 K^?1. Further, there is a lack of data at low temperatures (<300 K), which is critical for the understanding of thermal transport mechanisms. In this work, a temperature‐dependent study of thermal (10–300 K) and electrical (10–3000 K) transport in annealed RGO films indicates the potential application of RGO films for sensing temperatures across an extremely wide range. The room‐temperature thermal conductivity increases significantly from 46.1 to 118.7 W m^?1 K^?1 with increasing annealing temperature from 1000 to 3000 K with a corresponding increase in the electrical conductivity from 5.2 to 1481.0 S cm^?1. In addition, films reduced at 3000 K are promising for sensing extreme temperatures as demonstrated through the measured electrical resistivity from 10 to 3000 K. Sensors based on RGO films are advantageous over conventional temperature sensors due to the wide temperature range and flexibility. Thus, this material is useful in many applications including flexible electronics and thermal management systems.     

PLD法制备PbSe薄膜的性能分析

通过脉冲激光沉积(PLD)法在Si(111)和SiO2玻璃基片上制备了PbSe薄膜。X射线衍射、X射线能谱、原子力显微镜、傅里叶变换红外光谱仪测试结果表明：所有制备的薄膜都为多晶薄膜,发现薄膜生长温度对薄膜衍射峰有一定影响;PLD法制备的薄膜的成分与靶材的基本一致,实现了同组分沉积;所有薄膜表面比较平滑,表面不平整度小于200nm,结构比较致密;PbSe薄膜对红外光具有敏感的响应特性;在波长为5μm处存在有明显的吸收边,此吸收边对应于直接带隙PbSe材料的禁带宽度;对应于波长小于5μm的红外光,PbSe薄膜存在有明显的强吸收。     

脉冲激光沉积法制备氧化锌薄膜

ZnO是一种新型的Ⅱ-Ⅵ族半导体材料,具有优良的晶格、光学和电学性能,其显著的特点是在紫外波段存在受激发射。利用脉冲激光沉积法(PLD)在氧气氛中烧蚀锌靶制备了纳米晶氧化锌薄膜,衬底为石英玻璃,晶粒尺寸约为28-35 nm。X射线衍射(XRD)结果和光致发光(PL)光谱的测量表明,当衬底温度在100-250℃范围内时,所获得的ZnO薄膜具有c轴的择优取向,所有样品的强紫外发射中心均在378-385 nm范围内,深能级发射中心约518-558 nm,衬底温度为200℃时,得到了单一的紫外光发射(没有深能级发光)。这归因于其较高的结晶质量。     

Novel Method of Preparation of Gold‐Nanoparticle‐Doped TiO2 and SiO2 Plasmonic Thin Films: Optical Characterization and Comparison with Maxwell–Garnett Modeling

SiO₂ and TiO₂ thin films with gold nanoparticles (NPs) are of particular interest as photovoltaic materials. A novel method for the preparation of spin‐coated SiO₂–Au and TiO₂–Au nanocomposites is presented. This fast and inexpensive method, which includes three separate stages, is based on the in situ synthesis of both the metal‐oxide matrix and the Au NPs during a baking process at relatively low temperature. It allows the formation of nanocomposite thin films with a higher concentration of Au NPs than other methods. High‐resolution transmission electron microscopy studies revealed a homogeneous distribution of NPs over the film volume along with their narrow size distribution. The optical manifestation of localized surface plasmon resonance was studied in more detail for TiO₂‐based Au‐doped nanocomposite films deposited on glass (in absorption and transmittance) and silicon (in specular reflectance). Maxwell–Garnett effective‐medium theory applied to such metal‐doped nanocomposite films describes the peculiarities of the experimental spectra, including modification of the antireflective properties of bare TiO₂ films deposited on silicon by varying the concentration of metal NPs. The antireflective capabilities of the film are increased after a wet etching process.     

激光化学气相沉积法制备TiO2薄膜

利用激光化学气相沉积(LCVD)方法,以钛金属有机化合物为前驱体,以O2为反应气体,在激光功率PL为0～200 w、基板预热温度为400～700℃的条件下,制备出了金红石型TiO2薄膜和金红石型与锐钛矿型混合TiO2薄膜.研究表明,激光功率和基板预热温度对所沉积的TiO2薄膜的物相组成、截面组织,表面形貌和薄膜生长速度均有着显著的影响.