热处理对溶胶-凝胶TiO2薄膜的晶相转变和性能影响

以钛酸丁酯（TPOT）为有机醇盐前驱体，采用溶胶－凝胶技术制备了TiO2溶胶。为测量方便起见，分别制备了凝胶粉体和薄膜，并对样品进行了不同温度的热处理。X射线衍射（XRD）、椭偏仪和紫外－可见光谱（UV－vis)的测量表明：随热处理温度的升高，TiO2的结构由非晶到锐钛矿再到金红石相转变，400℃为锐钛矿相，600℃开始出现金红石相，800℃完全转变为金红石相；晶粒尺寸随热处理温度的升高而逐渐增大，锐钛矿结构的晶粒尺寸范围是2.5-5.5nm，金红石结构的晶粒尺寸范围是5.9-6.8nm；TiO2薄膜的折射率随热处理温度的升高而增大，同时薄膜厚度降低；禁带宽度随热处理温度的升高而增大，同时薄膜厚度降低；禁带宽度随热处理温度升高而变窄，锐钛矿结构的禁带宽度为3.45eV，而金红石结构的禁带宽度为3.30eV。     

退火温度对TiO2薄膜结构与光学性能的影响

研究退火温度对薄膜相结构、表面化学组成、形貌及光学性能的影响.采用射频磁控溅射法在单晶硅片和石英玻璃片上负载TiO2薄膜,通过X射线衍射(XRD)、原子力显微镜(AFM)、X光电子能谱(XPS)和紫外可见光谱(UV-vis)对其进行表征.结果表明,常温制备400℃以下退火的TiO2薄膜为无定形结构,400℃以上退火的TiO2薄膜出现锐钛矿相,600℃以上退火的TiO2薄膜开始出现金红石相,退火温度在1000℃以上时样品已经完全转变为金红石相;高温退火薄膜的组成为TiOx;随着退火温度的升高,薄膜透射率下降,折射率和消光系数有所增加.     

纳米TiO2薄膜的脉冲激光沉积及其光学特性

采用脉冲激光沉积技术(PLD)在硅基片上生长了二氧化钛纳米晶氧化物薄膜, 系统讨论了基片温度、氧分压等因素对薄膜结构特性的影响.X射线衍射结果表明在氧气氛下, 生长的薄膜为锐钛矿结构, 其结晶性随着基片温度的升高而增强, 在750℃、5Pa氧压的情况下为完全c轴取向的锐钛矿相TiO₂薄膜, 在750℃、5Pa氩气氛下则为(110)取向的金红石相薄膜. 场发射扫描电子显微镜结果表明薄膜表面致密, 呈纳米晶结构, 其晶粒尺寸在35nm左右.用傅立叶红外光谱和拉曼光谱对不同条件下制备的TiO₂薄膜进行了表征.紫外-可见透射光谱的测试结果表明, 薄膜在可见光区具有良好的透过率, 计算得到制备的锐钛矿和金红石相TiO₂薄膜在550nm处的折射率分别为2.3和2.5, 其光学带隙分别为3.2和3.0eV.因此通过沉积条件的改变可得到结晶性能和光学性能都不同的TiO₂薄膜.     

电子束蒸镀纳米TiO_2薄膜结构、相组成及亲水性研究

利用电子束蒸镀技术在石英玻璃和单晶Si〈100〉上制备了纳米TiO2薄膜,研究了衬底温度和退火温度对其结构、相组成和亲水性能的影响。结果表明,衬底温度为40~240℃时,石英玻璃上制备的薄膜为无定型TiO2,单晶Si〈100〉上制备的薄膜为弱结晶性的金红石TiO2,两类薄膜的亲水性均很差。退火温度显著影响薄膜的相组成及亲水性能。石英玻璃上不同衬底温度制备的TiO2薄膜经550,650℃退火后均转变为锐钛矿TiO2,具有很好的亲水性能。单晶Si〈100〉上不同衬底温度制备的TiO2薄膜经550~950℃退火后,均由金红石和锐钛矿TiO2混晶组成,且随退火温度升高,薄膜中锐钛矿TiO2含量逐渐增加;随退火温度升高,衬底温度为40℃时制备的TiO2薄膜的亲水性能逐渐降低,而衬底温度为240℃时制备的TiO2薄膜的亲水性能逐渐增强。     

硅基板上Fe掺杂TiO2氧敏薄膜的制备、结构与性能研究

采用溶胶-凝胶法,以Ti(OC4H9)4为前驱体,用提拉法在硅基板上制备了掺Fe的TiO2氧敏薄膜,对薄膜物相结构进行了X射线衍射(XRD)测定,利用扫描电镜(SEM)对薄膜微结构进行了观察.结果表明在硅基板上生长的TiO2薄膜中锐钛矿相为均匀小晶粒分布结构,金红石相以大尺度团聚结构形貌出现.Fe离子的掺杂对硅基板上制备的TiO2薄膜中金红石相的形成有很大的影响.Fe的掺入降低了金红石相的形成温度约100℃,Fe掺量在6mol%时,形成金红石相的量达到最大,即析晶能力最强.薄膜中形成晶相的晶格常数在＜6mol%的低Fe范围内,随较小的Fe离子取代较大的Ti离子,锐钛矿相和金红石相的晶格常数都随之减小;在＞6mol%的高Fe掺量范围内,随Fe掺量的增加,体系缺陷过量增加,晶格结构畸变严重,伴随着畸变能的释放,金红石相的晶格常数c轴逐渐增长,a轴略有下降(或基本不变).TiO2氧敏薄膜的氧敏性能受金红石相含量和氧空位浓度控制.当Fe离子掺杂浓度为6mol%时,金红石相及相应氧空位达到最大值,TiO2氧敏薄膜的氧敏性能也达到最大值,比刚形成金红石相的薄膜的氧敏性能增加近19倍.     

煅烧温度对溶胶-微波法制备Pr掺杂纳米TiO_2及其光学性能的影响

以钛酸丁酯和硝酸镨为原料,采用溶胶-微波法合成纳米Pr-TiO_2。采用X射线衍射、扫描电镜、X射线能谱和紫外-可见光等手段研究了煅烧温度对其晶体结构、表观形貌及光学性能的影响。结果表明:镨的掺杂对纳米TiO_2的形貌及光催化性能有显著影响。镨的掺杂抑制了晶粒的生长,抑制了晶型由锐钛矿相向金红石相的转变。随着煅烧温度的增加,纳米TiO_2团聚加剧,比表面积降低,锐钛矿相逐渐向金红石相转变,并且光催化过程中产生的活性羟基量逐渐减少,光催化活性逐渐降低,其中当煅烧温度为500℃时所合成的纳米Pr-TiO_2的光催化效果最优。Pr掺杂TiO_2提高了可见光的利用率并且红移了50nm。     

纳米TiO2薄膜的脉冲激光沉积及其光学特性

采用脉冲激光沉积技术(PLD)在硅基片上生长了二氧化钛纳米晶氧化物薄膜, 系统讨论了基片温度、氧分压等因素对薄膜结构特性的影响.X射线衍射结果表明在氧气氛下, 生长的薄膜为锐钛矿结构, 其结晶性随着基片温度的升高而增强, 在750℃、5Pa氧压的情况下为完全c轴取向的锐钛矿相TiO₂薄膜, 在750℃、5Pa氩气氛下则为(110)取向的金红石相薄膜. 场发射扫描电子显微镜结果表明薄膜表面致密, 呈纳米晶结构, 其晶粒尺寸在35nm左右.用傅立叶红外光谱和拉曼光谱对不同条件下制备的TiO₂薄膜进行了表征.紫外-可见透射光谱的测试结果表明, 薄膜在可见光区具有良好的透过率, 计算得到制备的锐钛矿和金红石相TiO₂薄膜在550nm处的折射率分别为2.3和2.5, 其光学带隙分别为3.2和3.0eV.因此通过沉积条件的改变可得到结晶性能和光学性能都不同的TiO₂薄膜.     

热处理对铁掺杂TiO2锐钛矿-金红石相变的影响

采用溶胶-凝胶法制备了纯TiO_2和不同浓度Fe掺杂TiO_2纳米粉末,并对各样品进行了350℃、500℃、650℃的热处理。通过SEM、XRD、EDS、XPS等测试方法对其表面形貌、晶体结构及成分组成进行了表征,研究了热处理温度对Fe掺杂TiO_2相变的影响。实验结果表明:纯TiO_2与Fe-TiO_2在350℃、500℃时均为单一的锐钛矿,650℃时大部分转变为金红石;热处理温度升高有利于锐钛矿向金红石的转变;Fe掺杂后以+3价的形式存在,Fe离子掺杂能够明显减小TiO_2的晶粒尺寸,高浓度的Fe掺杂对锐钛矿-金红石相变有微弱的促进作用。     

稀土Ce2O3掺杂TiO2薄膜的结构和光学特性

采用真空热蒸发法在玻璃、单晶硅衬底上制备Ce2O3掺杂TiO2薄膜，研究热处理和Ce2O3掺杂对薄膜性能的影响。结果显示，热处理可明显改善薄膜的结构和光学性能，Ce2O3掺杂可降低薄膜晶型转化温度。TiO2薄膜（玻璃衬底）经600℃热处理由锐钛矿转为金红石结构；当掺Ce2O3含量为5at％时热处理温度为500℃薄膜就已开始发生晶型转变。薄膜表面颗粒较均匀，存在程度不同的孔洞和颗粒聚集现象；掺Ce2O3后薄膜表面致密度明显增强。薄膜（玻璃衬底）的光学带隙从3．74eV降至3．60eV。     

氮气流量和退火处理对射频磁控溅射氮掺杂二氧化钛薄膜性能的影响

常温下利用TiO2陶瓷靶采用射频磁控溅射法在玻璃衬底上制备了N掺杂TiO2薄膜。利用光学轮廓仪、X射线衍射仪(XRD)、X射线光电子能谱仪分析(XPS)和分光光度计等对薄膜的沉积速率、化学组成、晶体结构和禁带宽度进行了系统研究。结果表明:磁控溅射N2流量和退火处理对薄膜的微观结构和性能有重要的影响。退火前,薄膜由非晶态TiO2构成;退火后,薄膜呈现锐钛矿相和金红石相的混合相。随着磁控溅射系统中N2流量的增加,退火前禁带宽度从3.19eV减少到2.15eV;退火后,薄膜由非晶相TiO2组织转化为锐钛矿TiO2和金红石TiO2构成的浑河相组织,禁带宽度相比退火前的非晶相TiO2薄膜略有增加。     

Ti靶及TiO2靶溅射TiO2薄膜微观形貌、结构及光学性质研究

利用射频磁控溅射技术通过Ti靶及TiO2靶在氩氧气氛中同时溅射制备TiO2薄膜,并对所得的样品进行不同温度的退火处理。采用X射线衍射、扫描电子显微镜、拉曼光谱和吸收谱研究了不同的靶材及退火温度对TiO2薄膜晶体结构、微观形貌及光学性质的影响。结果表明:由于靶材的不同,Ti靶溅射时氧分压较低,造成薄膜中存在大量的氧缺陷,晶相发育不完善,颗粒相比TiO2靶溅射时较小,从XRD和拉曼光谱来看,Ti靶溅射得到的TiO2薄膜更有利于金红石相的形成。薄膜的透过率随退火温度的升高而降低,TiO2靶材溅射的薄膜的光学带隙随温度升高而明显降低,而Ti靶得到的薄膜的光学带隙对退火温度的依赖关系不明显。     

热原子层沉积技术制备的TiAlC薄膜的性能

为了解以热原子层沉积技术制备的TiAlC薄膜的特性,在不同基底温度下,以硅和二氧化硅为基底材料制备了TiAlC薄膜;采用椭偏仪、分光光度计、X射线光电子能谱、原子力显微镜、X射线衍射仪对薄膜的性能进行了测试。结果表明:随着基底温度的升高,TiAlC薄膜平均透射率逐渐降低,吸收边产生红移,光学带隙由2.56eV降低到0.61 eV;薄膜的沉积速率由0.09 nm/cycle升高到0.20 nm/cycle,表面粗糙度由1.82 nm降低到0.49 nm;不同基底温度下生长的薄膜均为无定型结构;膜层中的氧源于空气的自然氧化,且膜层的氧化程度与膜层中TiC的含量及膜层的致密性有关;TiAlC薄膜的形成主要源于高温条件下TiC的形成及三甲基铝的分解。     

Preparation of rutile and anatase phases titanium oxide film by RF sputtering

Titanium oxide films were prepared by RF magnetron sputtering onto glass substrates. The effects of RF power and deposition temperature on crystalline structure, morphology and energy gap were investigated, which were analyzed by X-ray diffraction, SEM and UV-Vis spectrometer, respectively. Results show that rutile phase is the favored structure during deposition. Applying RF power in the range of 50-250 W, the amorphous, rutile, and both rutile and anatase phases TiO2 films were obtained in sequence, while the content of anatase is similar in the range of 34-37% although the RF power increases. Increasing the deposition temperature, the anatase phase coexists in the rutile phase in the range of 100-200 degrees C, and the content of anatase increases from 20 to 41% with the deposition temperature. In addition, according to the morphology observation, the granulous surface is found in rutile phase while facetted surface in anatase phase when titanium oxide films deposited at various RF powers and substrate temperatures. The band gap energy of titanium oxide evaluated from (alphahv)1/2 versus energy plots show that the energy gap decreases with RF power increasing.     

Thickness dependent properties of nickel oxide thin films deposited by dc reactive magnetron sputtering

Nickel oxide thin films of various thicknesses were grown on glass substrates by dc reactive magnetron sputtering technique in a pure oxygen atmosphere with sputtering power of 150 W and substrate temperature of 523 K. Crystalline properties of NiO films as a function of film thickness were investigated using X-ray diffraction. XRD analysis revealed that (200) is the preferred orientation and the orientation of the films changed from (200) to (220) at film thickness of 350 nm. The maximum optical transmittance of 60% and band gap of 3.82 eV was observed at the film thickness of 350 nm. The lowest electrical resistivity of 5.1 Ω cm was observed at a film thickness of 350 nm, thereafter resistivity increases with film thickness.     

Effect of Al Doping on Structural, Electrical, Optical and Photoluminescence Properties of Nano-Structural ZnO Thin Films

The nano-structural Al-doped ZnO thin films of different morphologies deposited on glass substrate were successfully fabricated at substrate temperature of 350 C by an inexpensive spray pyrolysis method. The structural, electrical, optical and photoluminescence properties were investigated. X-ray diffraction study revealed the crystalline wurtzite (hexagonal) structure of the films with nano-grains. Scanning electron mi- croscopy (SEM) micrographs indicated the formation of a large variety of nano-structures during film growth. The spectral absorption of the films occurred at the absorption edge of ～410 nm. In the present study, the optical band gap energy 3.28 eV of ZnO decreased gradually to 3.05 eV for 4 mol% of Al doping. The deep level activation energy decreased and carrier concentrations increased substantially with increasing doping. Exciting with the energy 3.543 eV (λ=350 nm), a narrow and a broad characteristic photoluminescence peaks that correspond to the near band edge (NBE) and deep level emissions (DLE), respectively emerged.     

Synthesis and characterization of nanostructured SnO<Subscript>2</Subscript> film

Nanostructured tin dioxide (SnO₂) film was deposited on glass substrate by thermal evaporation of tin metal followed by thermal oxidation at 600 °C for 2 h. XRD investigation confirms that grown film is crystalline tetragonal rutile. The average optical transmittance of the film was as high as 90%. The optical band gap of the nanostructured SnO₂ was estimated from transmittance data and found to be 3.4 eV. The variation of electrical conductivity with temperature was investigated. The root mean square (RMS) roughness and topography of the film were investigated by atomic force microscopy and found to be 2 nm with grain size of 17 nm.     

The effect of substrate temperature on the spray-deposited TiO2 nanostructured films for dye-sensitized solar cells

The nanostructured TiO2 films have deposited on SnO2:F (FTO) coated glass substrate by spray pyrolysis technique at different substrate temperatures of 200-500 degrees C. The structural, surface morphological and optical properties of TiO2 films significantly vary with the substrate temperature. The surface of the TiO2 films deposited at 400 degrees C shows the nanoflakes and short nanorods (approximately 130 nm) like structures while the TiO2 films prepared at 500 degrees C shows only the nanoflakes like structures. The band gap of the TiO2 films prepared at higher temperatures (300-500 degrees C) becomes narrow due to presence the rutile phases in their crystal structure. Ruthenium (II) complex as a dye, KI/I2 as an electrolyte and carbon on FTO glass as a counter electrode has used to fabricate the dye-sensitized solar cell (DSC). The TiO2 film deposited at 400 degrees C has showed the best photovoltaic performance in DSC with the efficiency of 3.81%, the photovoltage of 773 mV, the photocurrent of 8.34 mA/cm2, and the fill factor of 56.17%. The photovoltage of the DSC increases with the increase of substrate temperature during the deposition of TiO2 films. Moreover, all the DSCs exhibit reasonably high fill factor value.     

Photocatalytic Property of TiO2 Films Deposited by Pulsed DC Magnetron Sputtering

TiO2 thin films were prepared by DC magnetron sputtering with the oxygen flow rate higher than the threshold. The film deposited for 5 h was of anatase phase with a preferred orientation along the <220> direction, but the films deposited for 2 and 3 h were amorphous. The transmittance and photocatalytic activity of the TiO2 films increased constantly with increasing film thickness. When the annealing temperature was lower than 700℃, only anatase grew in the TiO2 film. TiO2 phase changed from anatase to rutile when the annealing temperature was above 800℃. The photocatalytic activity decreased with increasing annealing temperature.     

Annealing effects on the structural and optical properties of growth ZnO thin films fabricated by pulsed laser deposition (PLD)

Annealed ZnO thin film at 300, 350, 400, 450 and 500 °C in air were deposited on glass substrate by using pulsed laser deposition. The effects of annealing temperature on the structural and optical properties of annealed ZnO thin films by grazing incident X-ray diffraction (GIXRD), transmittance spectra, and photoluminescence (PL) were investigated. The GIXRD reveal the presence of hexagonal wurtzite structure of ZnO with preferred orientation (002). The particle size is calculated using Debye–Scherrer equation and the average grain size were found to be in the range 5.22–10.61 ± 0.01 nm. The transmittance spectra demonstrate highly transparent nature of the films in visible region (>70 %). The calculation of optical band gap energy is found to be in the range 2.95–3.32 ± 0.01 eV. The PL spectra shows that the amorphous film gives a UV emission only and the annealed films produce UV, violet, blue and green emissions this indicates that the point defects increased as the amorphous film was annealed.