Luminescence of molecules adsorbed on surfaces of wide gap materials

We report on the photoluminescence spectra of thin films of chain-like π-conjugated molecules on well-defined surfaces of wide gap inorganic materials. The aim is to study the energy transfer processes across the organic/substrate interface which limit the luminescence of molecules in close contact to substrate surfaces. We discuss quaterthiophene (4 T) adsorbed on the c(2×2)-ZnSe(0 0 1) surface and tetracene (Tc) on the surface of a thin epitaxial Al₂O₃ film on Ni₃Al(1 1 1). For thin films vapor-deposited at low substrate temperatures, we observe no luminescence signal for both systems, which indicates the presence of fast luminescence quenching processes at the organic/inorganic interface. After annealing, luminescence spectra corresponding to those of the bulk crystals are obtained. This can be explained by the formation of 3D-crystallites, which effectively separate most molecules from the organic/inorganic interface.     

X-ray luminescence of disperse SiO2 and porous silicon

We carry out a comparison between the luminescence spectra (photo-and x-ray luminescence) of porous silicon and disperse SiO₂, which by its physical characteristics is most similar to oxide films on porous silicon. The photoluminescence of porous silicon was also investigated using fluorescence (excitation by a nitrogen laser) and metallographic microscopes. We found that the natures of the luminescence centers of porous silicon and disperse SiO₂ are identical. A porous layer on single-crystal silicon ensures the creation of a highly branched surface of oxide film. Luminescence centers are located on its inner (as viewed from the porous silicon) surface. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 2, pp. 247–251, March–April, 1998.     

(t-bt)2Ir(acac)新型磷光染料的光谱特性及电致发光性能研究

对不同浓度的新型黄色铱配合物磷光染料bis[2-(4-tertbutylphenyl)benzothiazolato-N,C2']iridium (acetylacetonate)[(t-bt)2Ir(acac)]溶液和薄膜状态下的光致发光光谱(Photoluminescence,PL)和紫外-可见吸收(UV-Vis absorption)光谱进行了表征.结果表明,溶液浓度为3×10-4mol·L-1时的PL发光最强,浓度猝灭效应使得高浓度溶液的PL强度降低.薄膜的PL和吸收光谱相对溶液的光谱都发生了红移,这是由于固态时分子间距小、相互作用大,分子表现为聚集态的结果.基于光谱特性,制备了(t-bt)2Ir(acac)超薄层结构的电致发光器件,在13.2 V的偏置电压下,器件的发光亮度达到18 367 cd·m-2.     

Luminescence of Europium–Doped Anodic Oxide Films on Multilayer Titanium–Tantalum Composites

Luminescence of europium in anodic oxide films on thin–film Ti–Ta composites and the process of anodic oxidation of these by the method of chronovoltammetry are investigated for different orders of arrangement of metallic layers and temperatures of heat treatment. A correlation between the luminescence spectra and chronovoltammetric diagrams is noted. The luminescence is shown to be an efficient method for studying the complex phase composition of anodic oxide films. The luminescence spectra of samples are characterized by the presence of several types of luminescence centers inherent in the Eu³⁺ ion and the base. Conditions for the formation of Eu–doped anodic oxide films on a diffusion alloy, which are of interest for microelectronics as a new dielectric material, are determined.     

Absorption and photoluminescence properties of silver clusters in SiO<Subscript>2</Subscript> matrix

Absorption and luminescence properties of silver nanoclusters embedded in SiO₂ matrixes were studied experimentally. Thin SiO₂ films with different amount of silver were produced by co-deposition of Ag and SiO₂ onto the silica substrates in vacuum. The thus obtained films possess three peaks in absorption spectra at 297, 329 and 401 nm and two peaks in luminescence spectra at about 500 and 650 nm. We ascribed these spectral features to silver nanoclusters of different sizes that present in the film. Thermal annealing transforms both absorption and emission spectra of the films. Lager clusters that are formed after annealing possess one absorption band at 350–450 nm and one luminescence band at 510 nm. The luminescence was observed only in samples with the silver content of less than 2.2%. Quenching of the luminescence in samples with higher concentration of silver is due to the presence of larger particles with plasmonic properties.     

Luminescence of hafnium dioxide films produced from hafnium dipivaloylmethanate

A technique is developed for measuring luminescence spectra of hafnium dioxide using a hydrogen lamp as an excitation source. The luminescence spectra of the as-grown and annealed hafnium dioxide films prepared by chemical deposition from volatile hafnium dipivaloylmethanate on the Si(111) substrates are measured at room temperature. Intense luminescence at λ ≌ 280 nm is characteristic of nanocrystallites of monoclinic modification. The band gap width is found to be ≌ 5.76 eV. It is shown that the film composition significantly deviates from the stoichiometric one. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 63–67, April, 2007.     

Luminescence of europium-doped anode oxide films on titanium-aluminum composites

The luminescence of europium in anode oxide films (AOF) on titanium-aluminum film composites is investigated. It is shown that the intensity distribution in the continuous and line luminescence spectra of europium introduced into the AOF directly in the process of anodic oxidation essentially depends on the sequence of arrangement of the layers of metal films and on the temperature of their heat treatment preceding the process of anodic oxidation. It is established that the nature of the luminescence spectrum of the AOF correlates with the chronovoltammetry diagrams of anodic oxidation. Composites with a high degree of europium doping are found and methods of searching for composites for creating new materials of electronic technology are outlined. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 2, pp. 270–272, March–April, 2000.     

Gd2O3:Eu3+溶胶-凝胶薄膜发光特性研究

以无机稀土氧化物为原料制备了Gd2O3:Eu3 溶胶-凝胶薄膜,通过对不同Eu3 离子掺杂浓度、不同烧结温度薄膜发光强度的研究,得出Gd2O3薄膜中Eu3 离子的最佳掺杂浓度为10%、最佳热处理工艺为800℃下烧结2h;由薄膜和粉末激发谱的比较发现:薄膜中存在着比粉末更有效的能量传递,从而更有利于高能射线激发发光;首次观察到薄膜经过1000℃烧结2h后发光消失,并通过SEM和XRD的实验分析对这一现象进行了解释。     

不同射频输入功率下制备的氟化类金刚石碳膜疏水性研究

以高纯石墨作靶、氩气（Ar）和三氟甲烷（CHF₃）为源气体,用反应磁控溅射法在不同射频功率下制备了氟化类金刚石碳（F-DLC）膜,并对其疏水性进行研究.双蒸水液滴与膜表面接触角的测试结果表明,所制备薄膜表面的最大水接触角可达115°左右.通过原子力显微镜获得的薄膜表面AFM图谱、拉曼光谱以及傅里叶变换红外光谱探讨了影响薄膜的疏水性的因素.结果表明,薄膜的疏水性与薄膜的表面粗糙度和表面键结构直接相关,表面粗糙度越大,疏水性越好,但与薄膜中的F含量和sp³/sp²的比值并未呈单调增加或减小的对应关系.射频输入功率影响着薄膜的沉积速率,与薄膜表面粗糙度、薄膜中芳香环单核的比例以及薄膜表面的键结构（F的接入方式）直接相关. 关键词： 疏水性 反应磁控溅射 氟化类金刚石膜 射频功率     

Violet-to-red photoluminescence of spiro-TAD organic films doped with different organic dyes

Photoluminescence (PL) and photoluminescence excitation (PLE) spectra of undoped spiro-TAD films and spiro-TAD films doped either by the organic dyes coumarin 7 or DCM as well as by both of these dyes simultaneously were investigated at different dye concentrations. A widened PL spectrum caused by doping was encountered and violet-to-red emission was obtained. It was established that excitation of the dyes is realized most efficiently through spiro-TAD. The overall integral PL intensity of the coumarin 7 doped films increased with dye concentration due to the suppression of nonradiative recombination in the film caused by a transfer of spiro-TAD excitation energy to the dye molecules. Mainly radiative energy transfer from semiconductor to dye molecules occurs in the case of DCM doping. No mutual influence on the luminescence of both dyes in the spiro-TAD film was observed and as a consequence, the PL band intensity of each dye can be adjusted separately.     

非晶碳化硅材料与光学微腔的制备与发光

利用等离子体化学气相沉积技术在100℃的衬底温度下,制备了具有不同组分比的系列非晶碳化硅薄膜。结合傅里叶变换红外光谱与喇曼光谱对所制备的薄膜微结构进行了表征与分析,同时,对具有不同组分比的非晶碳化硅薄膜室温光致发光性质进行了系统的研究。结果表明在Ar⁺离子激光和Xe灯紫外光的激发下,不同组分的样品显示出不同的光致发光特性,并对样品的发光特性与其微结构的联系进行了讨论。在此基础上,用碳化硅薄膜设计和制备了全固体光学微腔,研究了微腔对碳化硅发光行为的调制作用。     

Effect of Temperature and Oxygen on Luminescence Spectra and Polarization of Divinylbenzoxazolylbiphenyl Thin Films

H-type molecular aggregation as assembly with chromophore dipoles arranged parallel to each other has been observed in absorption and luminescence spectra of divinylbenzoxazolylbiphenyl thin films deposited on quartz glass substrate by thermovacuum method. The reversible changes of fluorescence anisotropy have been observed under film heating below the glass transition temperature correlating with lifetime changes. The addition of oxygen was found to cause an essential luminescence quenching. The hexyloxy group in the side chain of dibenzoxazolylbiphenyl molecule decreases H-type molecular aggregation and energy migration, and increases luminescence quenching induced by adsorbed oxygen owing to the formation of more porous film morphology.     

光转换有机白光发光二极管发光性能研究

研究一种有机白光发光材料,采用热熔法制备出有机薄膜(核黄素、蒽酮衍生物和线性低密度聚乙烯)。研究结果表明：核黄素、蒽酮衍生物和线性低密度聚乙烯的配比和制膜的加热时间对有机薄膜的发光光谱具有一定影响;得到了从绿光到红光的宽带光谱;用此薄膜封装成白光发光二极管的性能良好。     

螺芴氧杂蒽LB膜的制备及光谱特性研究

为了研究聚芴材料DSFX-SFX分子在气液两相表面的行为,分子处于溶液、LB膜及粉末状态的光学特性,以及分子有序排列对其发光特性的影响,制备了聚芴材料DSFX-SFX的X型LB膜,研究了π-A等温曲线,测量了其紫外-可见吸收谱和稳态荧光光谱。结果表明,分子以face-on形式平躺在亚相表面,单分子面积为4.78 nm2。在氯仿溶液中吸收峰位在354 nm,归属于分子中三聚氧杂蒽部分与芴环间π-π*电子跃迁;荧光发射峰位在396,419,445 nm(肩峰),归属于发色团三聚氧杂蒽,是芴环与氧杂蒽环之间的电荷转移。在LB膜中,吸收谱和荧光光谱与其溶液光谱相比,整体红移6 nm。结果表明:在LB膜中,两个分子形成激基缔合物,与单分子状态相比,激基缔合物的HOMO升高而LUMO降低。与粉末状态相比,该材料在LB膜中有很强的荧光发射,表明该材料形成有序排列超薄膜有利于荧光发射。     

The influence of the preparation conditions on the energy disorder in poly(methylphenyl)silane films

The photoluminescence (T=5 K) and absorption (T=295 K) spectra and thermostimulated luminescence (T=5–300 K) curves of poly(methylphenyl)silane (PMPS) films are investigated as functions of the film thickness, annealing temperature, and oxygen content in air. It is revealed that the optical spectra and thermostimulated luminescence curves of PMPS films prepared in air at room temperature undergo changes after annealing at T=370–450 K. The assumption is made that the observed changes are associated with the formation of long polymer chain segments with a closer packing. This leads to an increase in the density of low-energy states of excitons and charge carriers. It is demonstrated that atmospheric oxygen substantially affects the formation processes and the energy disorder in the films prepared. The PMPS films are found to degrade after heating to T≥500 K.     

Structure and luminescence of CsI:Eu columnar films

Europium doped columnar films of CsI are produced by vacuum condensation. Eu²⁺ ions in the CsI:Eu films lead to the formation of a narrow (0.18 eV), intense luminescence band with a maximum at 456 nm, which is excited by x-rays, as well as by photons of various energies. The spectral and kinetic characteristics of the emission depend on the amount of activator and on the conditions under which the film is prepared and stored. The nature of the luminescence centers is determined by structural formations that contain divalent europium ions.     

Organic low-dimensional structure electroluminescent material characteristics and devices

Photoluminescence (PL) characteristics of organic doped films are studied as a function of dopant concentration, doped layer thickness. The luminescence properties of doped films are decided by Förster energy transfer rate between host and guest and fluorescence quenching effect of guest. For Alq:rubrene doped film at 5% doping level, we fabricated and characterized organic doped quantum-well structure device, and observed significant quantum size effect. For Alq:QAD doping system, at low doping level of 0.4%, the intermolecular spacing between QAD molecules is relatively large, the interaction between neighboring QAD molecules is very small due to the strong localization of the carriers in the single QAD molecules, the PL properties of Alq:QAD doped films only depends on the PL properties of single isolated QAD molecules, which is somewhat similar to the inorganic quantum dot structure. We also reported the electroluminescent performance of the Alq:QAD system.     

Directed energy transfer due to orientational broadening of energy levels in photosynthetic pigment solutions

The directed non-radiative energy transfer through monomeric molecules of chlorophyll “a” and pheophytin “a” at high concentrations (c~10^-2 M) in a rigid matrix of polyvinylbutyral has been found by using the nanosecond laser spectrofluorimeter. The phenomenon is caused by orientational broadening of pigment molecular spectra owing to its interaction with a solvent. The observed temporal shift of the luminescence spectrum to the red region in a nanosecond time scale as well as the red shift of the time integrated spectrum at a high concentration of pigment molecules and the monotonic growth of the luminescence lifetime with a shift to the red region of the spectrum served as indications of the directed energy transfer in the sample. The non-radiative energy transfer from monomeric molecules towards aggregates is also directly demonstrated by the deformation of instantaneous luminescence spectra in the long-wavelength range (λ>700 nm). The role and the possibility of the directed energy transfer between molecules with orientationally broadened spectra in the biological systens are discussed.     

Interaction of CdSe/ZnS core-shell semiconductor nanocrystals in solid thin films

The optical properties of CdSe/ZnS semiconductor nanocrystals with the core-shell structure are studied upon visible-laser excitation in a wide range of flux densities. It is demonstrated that the dimensional quantization effect is preserved in the films with a limiting high concentration of nanocrystals. A strong bathochromic shift of the absorption and luminescence peaks relative to the peak positions in the corresponding spectra of nanocrystals in films with a relatively low concentration of nanocrystals and solutions is caused by a high concentration of nanocrystals and the dipole moment related to the asymmetry of the nanoparticles. The shift is varied from 35 to 50 nm depending on the film thickness. The luminescence spectra of the films remain unchanged upon an increase in the laser intensity to 1 × 10⁶ W/cm². The laser action on the nanoparticle films is studied at intensities (5 × 10⁶?1 × 10⁹ W/cm²) higher than the damage threshold.     

分散橙3掺杂聚合物薄膜的全光极化特性及其驰豫过程研究

利用旋涂法制备了分散橙3(DO3)/PMMA主客体掺杂薄膜,对其吸收谱、厚度和折射率进行了测量,并采用全光极化的方法对薄膜的二阶非线性光学特性进行了研究.实验结果表明,随着厚度的增加其二阶非线性先增强后减弱,d33最大值约为0.827×10~(-2) pm/V.对极化饱和后的驰豫情况进行了分析,发现不同厚度薄膜的驰豫时间不同,这是由于薄膜中偶氮含量和厚度的不同,分子间的相互作用对顺反异构逆过程的快慢有较大的影响.