等离子体增强MOCVD法生长ZnO薄膜

利用等离子体增强MOCVD法生长出 ZnO薄膜，用X射线衍射谱观察到位于 2θ34．56°处（0002）的衍射峰，表明ZnO沿c方向呈柱状生长．通过荧光光谱，观察到来自于激子的高强度的近带边紫外光发射（375um）．紫外发射光强度与深能级复合发射光强度比高达 193，显示出材料的高质量，并通过原子力显微镜加以验证．为了实现高阻ZnO薄膜，利用高温富氧分段退火和用N2 气进行掺氮两种方法生长高阻ZnO薄膜．结果表明，电阻率由0．65 Ω·cm分别升高到1100 Ω·cm（分段退火）和5×104Ω·cm（掺氮）．进一步比较发现，掺氮的样品不仅电阻率高，而且光荧光特性好，显示出更高的薄膜质量．     

溶胶-凝胶法制备的MgxZnl—xO纳米薄膜结构和光学性质

用溶胶-凝胶法制备了不同组分的MgxZn1-xO薄膜．X射线衍射结果表明，薄膜为具有六角纤锌矿结构的纳米薄膜，晶粒尺寸3～5nm，随着Mg进入ZnO晶格，其晶格常数变小．紫外-可见吸收光谱表明，随着Mg含量的增加带隙变宽，自由激子吸收峰明显蓝移．室温光致发光光谱由很强的且与氧空位相关的深能级缺陷发光和较弱的紫外激子发光组成，激子发光强度和缺陷发光强度比随x的增大而减小，表明Mg原子进入ZnO晶格会引起深能级缺陷的增加．Mg0.03Zn0.97O薄膜经700℃热氧化后，紫外与可见发光强度比达到30．     

纳米铝/金对纳米2,5-二苯基噁唑薄膜荧光特性的调制

以直流溅射方法和真空蒸镀方法结合制备了单组份纳米铝薄膜、纳米金薄膜、纳米2,5-二苯基噁唑(DPO)薄膜和双组份纳米Al/DPO、Au/DPO复合叠层薄膜。利用双势垒伏安特性曲线模拟计算、荧光分光光度计和扫描电镜表征了薄膜样品的电学性质、荧光性质和表面形貌。固态荧光光谱中观察到Au/DPO和Al/DPO叠层结构复合纳米薄膜样品的荧光主峰发生了明显红移。Au/DPO叠层结构复合薄膜样品与单组份DPO纳米薄膜样品的荧光发射光谱相比较,叠层薄膜内相互作用较弱,而Al/DPO叠层结构复合纳米薄膜样品相互作用较强、谱线峰型变化较大,Al的谱线的半高全宽明显增大,推测颗粒内部存在离散的能级结构。     

纳米铝/金对纳米二,五-二苯基噁唑薄膜荧光特性的调制

以直流溅射方法和真空蒸镀方法结合制备了单组份纳米铝薄膜、纳米金薄膜、纳米二,五-二苯基噁唑(DPO)薄膜和双组份纳米Al/DPO、Au/DPO复合叠层薄膜。利用双势垒伏安特性曲线模拟计算、荧光分光光度计和扫描电子显微镜(SEM)表征了薄膜样品的电学性质、荧光性质和表面形貌。固态荧光光谱观察到500nm膜厚的Au/DPO、Al/DPO叠层结构复合纳米薄膜样品的荧光主峰发生了明显红移。Au/DPO叠层结构复合薄膜样品与单组份DPO纳米薄膜样品的荧光发射光谱相比较,叠层薄膜内相互作用较弱,而Al/DPO叠层结构复合纳米薄膜样品相互作用较强、谱线峰型变化较大,Al的谱线的半高全宽明显增大,推测颗粒内部存在离散的能级结构。     

退火时间对6H-SiC(0001)表面外延石墨烯形貌和结构的影响

在分子束外延(MBE)设备中,采用高温退火的方法在6H-SiC(0001)表面外延石墨烯,并研究了退火时间对外延石墨烯形貌和结构的影响.利用反射式高能电子衍射(RHEED)、原子力显微镜(AFM)、激光拉曼光谱(Raman)和近边X射线吸收精细结构(NEXAFS)等实验技术对制备的样品进行了表征.RHEED结果发现,不同退火时间的样品在SiC衍射条纹的外侧都出现了石墨烯的衍射条纹.AFM测试表明,外延石墨烯的厚度随退火时间增加而增大,且样品孔洞减少、表面更加平整.Raman测试表明,外延石墨烯拉曼谱中2D峰和G峰的位置相对高定向热解石墨(HOPG)中2D峰和G峰的位置蓝移,且退火时间增加,峰的蓝移量减小.对样品中碳原子K边NEXAFS谱测量显示,样品中存在sp2杂化的碳原子,退火时间增加使碳原子的1s→π以及1s→σ吸收的强度增大,且1s电子到π态的吸收峰相对HOPG的向高能偏移.     

退火温度对PLD法制备ZnO:Eu3+,Li+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)衬底上制备了Eu3+,Li+共掺杂的ZnO薄膜,分别在450,500,550和600℃条件下进行退火,退火气氛为真空。利用X射线衍射(XRD)仪和荧光分光光度计研究了退火温度对薄膜结构和光致发光(PL)的影响。研究结果表明,Eu3+,Li+共掺杂的ZnO薄膜具有c轴择优取向,Eu3+,Li+没有单独形成结晶的氧化物,均以离子形式掺入ZnO晶格中。PL谱中有较宽的ZnO基质缺陷发光,ZnO基质与稀土Eu3+之间存在能量传递,但没有有效的能量传递。随着退火温度的增加,薄膜发光先增强后减弱,退火温度为550℃时发光最强。当用395 nm的激发光激发样品时,仅观察到稀土Eu3+在594 nm附近的特征发光峰,但发光强度随退火温度变化不明显。     

溶液法制备的碳纳米管薄膜的结构分析与场致电子发射机理研究

结合紫外光电子能谱和拉曼光谱对溶液法制备的碳纳米管薄膜的场致电子发射性能进行研究。采用溶液滴涂法制备的碳纳米管薄膜的场致电子发射开启电场约为3.33 MV/m,阈值电场约为5.44 MV/m,以福勒-诺得海姆(Fowler-Nordheim,FN)理论对电子发射进行解释,其发射的增强因子接近103。通过对紫外光电子能谱的分析,发现碳纳米管薄膜的低能量截止端在外加电场作用下逐步降低,表明纳米管薄膜的表面有效势垒在外加电场作用下逐步下降,从而使得碳纳米管薄膜的电子更加容易发射进入真空。结合拉曼光谱和电学特性的研究,发现界面过渡层的接触电阻与碳纳米管薄膜中的非晶碳成分均可以增强场致电子发射。     

甲基三乙氧基硅烷修饰的Ti3+/SiO2复合薄膜的发光性能

采用溶胶-凝胶(Sol-Gel)法, 以正硅酸乙酯(TEOS)和甲基三乙氧基硅烷(MTES)为先驱物, 盐酸为催化剂, 用二步水解法制备了Ti3+/SiO2薄膜和甲基三乙氧基硅烷修饰的Ti3+/SiO2复合薄膜. 采用红外光谱仪、X射线衍射仪、椭偏仪、荧光光谱仪等对膜层性质进行了分析. 结果表明, 掺杂Ti3+的SiO2薄膜分别在250 nm附近有一弱的激发峰, 294 nm附近有一强的激发峰, 在393 nm附近出现一强的发射峰. IR光谱发现, MTES修饰的Ti3+/SiO2复合薄膜的Si—OH的吸收峰强度比Ti3+/SiO2薄膜的略减小, Si—O—Si的吸收峰明显增强, 表明复合薄膜硅氧网络结构更规则, 有利于Ti3+的均匀分散. Ti3+/SiO2薄膜与复合薄膜的孔隙率分别为13.64%和6.66%, 表明MTES的加入使薄膜更致密. 在空气中陈放30 d后, Ti3+/SiO2薄膜已经检测不到荧光发射峰, 而MTES修饰的Ti3+/SiO2复合薄膜荧光强度只下降了18%. 在氮气中陈放30 d后, 普通薄膜与复合薄膜的荧光强度均仅下降了10%. 表明Ti3+的荧光猝灭的主要原因是由于Ti3+被氧化造成的. 溶胶中加入MTES后, 薄膜表面结构得到改善, 有效地防止了Ti3+的氧化, 荧光强度更稳定.     

Ce-Sn-O复合氧化物的制备和表征

采用柠檬酸法制备了CexSn1-xO2复合氧化物，并对复合氧化物的结构和还原性能进行了表征。结果表明，少量Sn能取代CeO2晶格中Ce原子形成立方相的固溶体，并使晶胞参数变小；Sn超过20％时形成混合相。650℃焙烧的CexSn1-xO2复合氧化物有3个还原峰（α、β和γ）。α峰归属为表面Sn^4 的还原（－330℃）；β峰归属为体相SnO2和表面Ce^4 （－630℃）的还原；γ峰归属为体相CeO2的还原。焙烧温度的提高使得β峰增强，α峰变弱，γ峰几乎不变；而低温焙烧有利于CexSn1-xO2固溶体的形成，再氧化处理对样品的还原性能有很大的影响。     

C60掺杂聚苯乙烯薄膜的荧光发射

采用铸模的方法制得Ｃ６０掺杂的聚苯乙烯薄膜。Ｘ－射线衍射实验表明Ｃ６０已均匀分布在聚苯乙烯薄膜中，在氢离子激光器的激发下，发现该薄膜在５８３ｎｍ处有荧光发射，与空白样品的实验结果进行比较，发现该荧光发射为一新的荧光峰。详细的分析表明其是由于Ｃ６０与聚合物基质间的相互作用，使得跃迁禁阻能极化为跃迁允许能级而造成的。     

Effects of ZnO Buffer Layer Thickness on Properties of MgxZn1-xO Thin Films Deposited by MOCVD

High-quality MgxZn1-xO thin films were grown on sapphire（0001 ） substrates with a ZnO buffer layer of different thicknesses by means of metal-organic chemical vapor deposition. Diethyl zinc, bis-cyclopentadienyl-Mg and oxygen were used as the precursor materials. The crystalline quality, surface morphologies and optical properties of the Mg, Zn1-xO films were investigated by X-ray diffraction, atomic force microscopy and photoluminescence spectrometry. It was shown that the quality of the MgxZn1-xO thin films depends on the thickness of the ZnO buffer layer and an Mg, Zn1-xO thin film with a ZnO buffer layer whose thickness was 20 nm exhibited the best crystal-quality, optical properties and a flat and dense surface.     

Binding studies of molecular linkers to ZnO and MgZnO nanotip films

Two bifunctional linkers, a rigid-rod p-ethynyl-isophthalic acid capped with a Ru(II)-polypyridyl complex and 3-mercaptopropionic acid, were covalently bound to ZnO nanotip films grown by metal-organic chemical vapor deposition (MOCVD) technology. This highly vertically aligned, crystalline form of ZnO had not been functionalized before. The binding was studied by Fourier transform (FT) IR and UV spectroscopies and probed, in the case of the Ru complex, by static and dynamic fluorescence quenching. The molecules did bind through the carboxylic acid groups, and the FT-IR attenuated total reflectance spectra are indicative of a bidentate carboxylate binding mode. Other molecules (heptanoic acid, isophthalic acid, and trimethoxy(2-phenylethyl)silane) were also bound to the ZnO nanotips. A comparison was made with epitaxial ZnO films grown by MOCVD and ZnO mesoporous films prepared from colloidal solutions to investigate the effect of the ZnO morphology. The ZnO nanotips were excellent binding substrates, particularly for the rigid-rod linker. Since ZnO films are etched at low pH (< 4), novel nanotip films made of ternary MgxZn1-xO, which is formed by alloying ZnO with MgO and is more resistant to acids, were developed. The MgxZn1-xO nanotip films were employed to use linkers with acidic groups and to study the effect of pH pretreatment of the surface on the binding.     

ZnO纳米棒薄膜的湿化学法制备及光致发光特性

在80 ℃水浴下, 采用简易的湿化学法在不导电玻璃基底上制备了ZnO纳米棒阵列, 利用X射线衍射仪(XRD)和场发射扫描电镜(FE-SEM)对样品的结构形貌进行了表征. 结果表明, 晶化30 min所得产物为六方纤锌矿相的ZnO纳米棒, 直径大约为80~90 nm. 为了分析不同的低温退火温度和退火气氛对其光致发光性能的影响, 研究了ZnO纳米棒薄膜在不同的后处理条件下的光致发光谱(PL). 实验结果表明, 在O₂气氛下于450 ℃退火1 h后, ZnO纳米棒薄膜的红光发射(约650 nm)强度相对在空气和5%H₂/95%N₂气氛下退火的样品变得更强, 而且该样品的激发波长范围(200~370 nm)与近紫外发光二极管(LEDs)的发射波长范围(350~420 nm)匹配得很好.     

Effect of annealing on photoluminescence of blue-emitting ZnO nanoparticles by sol–gel method

In this work, we investigated the influence of annealing on the crystallinity, microstructures, and photoluminescence (PL) properties of ZnO nanoparticles prepared by sol–gel method. The annealing was carried out both in air and vacuum. X-ray powder diffraction, scanning electron microscopy, and ultraviolet–visible spectroscopy were used to characterize the crystal structures, diameter, surface morphology, and PL properties of ZnO nanoparticles. It has been found that both the as-grown and annealed ZnO nanoparticles had a hexagonal wurtzite crystal structure, and their average diameter and crystallinity increased with the anneal time and temperature. Pure blue-emitting behavior was observed in all samples. The emission intensity of ZnO nanoparticles was found to be enhanced after annealing, but it was highly dependent on the annealing conditions. Optimal annealing conditions both in air and vacuum were obtained for achieving maximum emission intensity in the ZnO nanoparticles. The dependence of PL properties of the ZnO nanoparticles on the annealing conditions was discussed.     

射频磁控溅射制备纳米TiO2薄膜的光电化学行为

在室温下采用射频磁控溅射法制备了纳米晶粒的TiO2薄膜,用循环伏安法研究了ITO/TiO2薄膜电极的光电化学行为,并测量了相应TiO2薄膜的亲水性与光催化能力.结果表明,在室温下制备的TiO2薄膜为无定形结构,当退火温度超过400 ℃时转化为锐钛矿结构.在400 ℃下退火的TiO2薄膜具有良好的亲水性和光催化能力. TiO2薄膜电极用254 nm的紫外光照射一定时间后会产生新的氧化峰,且随着光照时间的增加,峰电流也增加.初步认为用紫外光照射一定时间后, TiO2薄膜的循环伏安图的氧化峰属于光生的Ti3＋,而光致亲水性可能与Ti3＋的生成有关.     

Surface hydrophobicity of fluorinated block copolymers enhanced by supercritical carbon dioxide annealing

Supercritical carbon dioxide (scCO2) annealing enhances the hydrophobicity of the surfaces of asymmetric perfluorinated block copolymers. X-ray photoelectron spectroscopy (XPS) and contact angle measurement reveal that the surface domains of the fluorinated block (PF) of poly[styrene-block-4-(perfluorooctylpropyloxy)styrene] (PS-PF) become thicker than those annealed in a vacuum. Consequently, the contact angles of water on the surfaces of PS-PF block copolymers significantly increase after the scCO2 annealing compared to those annealed in a vacuum. The surface hydrophobicity enhanced by the scCO2 annealing is related to the thickness of the surface PF domain and the conformation of the PF block.     

Passivation of GaAs nanocrystals by chemical functionalization

The effective use of nanocrystalline semiconductors requires control of the chemical and electrical properties of their surfaces. We describe herein a chemical functionalization procedure to passivate surface states on GaAs nanocrystals. Cl-terminated GaAs nanocrystals have been produced by anisotropic etching of oxide-covered GaAs nanocrystals with 6 M HCl(aq). The Cl-terminated GaAs nanocrystals were then functionalized by reaction with hydrazine or sodium hydrosulfide. X-ray photoelectron spectroscopic measurements revealed that the surfaces of the Cl-, hydrazine-, and sulfide-treated nanocrystals were As-rich, due to significant amounts of As0. However, no As0 was observed in the photoelectron spectra after the hydrazine-terminated nanocrystals were annealed at 350 degrees C under vacuum. After the anneal, the N 1s peak of hydrazine-exposed GaAs nanocrystals shifted to 3.2 eV lower binding energy. This shift was accompanied by the appearance of a Ga 3d peak shifted 1.4 eV from the bulk value, consistent with the hypothesis that a gallium oxynitride capping layer had been formed on the nanocrystals during the annealing process. The band gap photoluminescence (PL) was weak from the Cl- and hydrazine- or sulfide-terminated nanocrystals, but the annealed nanocrystals displayed strongly enhanced band-edge PL, indicating that the surface states of GaAs nanocrystals were effectively passivated by this two-step, wet chemical treatment.     

ZnO荧光粉中的紫外发射和绿色发射之间的关系

通过在低氧分压和真空中热处理ZnO粉末, 获得了ZnO荧光粉. ZnO荧光粉有两个发射谱带, 分别位于380 nm(紫外)和510 nm(绿色). 紫外谱带对应于ZnO中的激子发射, 是一个单中心发光过程；绿色谱带是一个复合发光过程, 与ZnO中的本征缺陷相关, 如氧空位、锌空位等. 实验表明, 高密度的激发条件有利于紫外发射, 而低氧分压下的热处理有利于提高绿色发射谱带的强度. 研究结果还表明, 与紫外发射相联系的激子可向与本征缺陷相联系的绿色发光中心传递能量, 这种传递可能是通过激子扩散实现的.     

Zr掺杂对La（Ba）ZrxCo1-xO3-δ钙钛矿催化N2O分解性能的影响（英文）

采用溶胶凝胶法制备了Zr掺杂的钴基钙钛矿La(Ba)ZrxCo1-xO3-δ,并将其用于航天推进剂领域的高浓度N2O催化分解反应.发现Zr的引入明显提高了钙钛矿La(Ba)ZrxCo1-xO3-δ的催化活性,尤其是当Zr掺杂量分别为0.05和0.2时,LaZrxCo1-xO3-δ和BaZrxCo1-xO3-δ催化剂性能较为优异.应用N2物理吸附、X射线衍射、H2程序升温还原、O2程序升温脱附和氧脉冲吸附技术表征了Zr掺杂对La(Ba)ZrxCo1-xO3-δ催化剂的物化性质的影响.结果表明,Zr掺杂增大了钴基钙钛矿的比表面积,改善了晶格结构,从而提高了钴物种的还原及氧吸附脱附能力,因而催化剂上N2O分解活性增加.