阴阳离子菁染料超快荧光动力学特性研究

采用飞秒荧光上转换技术,研究了阴阳离子菁染料及对应的阴离子和阳离子菁染料吸附在立方型和T型溴碘化银表面上形成J-聚集体的荧光衰减时间分辨特性,分析了几种菁染料增感体系的超快电子转移动力学过程及其对增感效率的影响.通过比较几种菁染料增感体系的荧光衰减特性,两种阴阳离子染料要明显快于阴离子染料、阳离子染料及二者的加合,说明阴阳离子染料聚集体到溴碘化银的电子注入速率较快,增感效果更好.对两种阴阳离子染料聚集体荧光衰减特性的比较,可以看出染料在T型颗粒溴碘化银上形成聚集体的荧光寿命更短,因而对T型颗粒的增感效果更好.染料Dye2的荧光衰减要快于染料Dye1,说明染料Dye2到溴碘化银的电子注入速率更快,增感效率更高.     

吸附在溴化银颗粒表面上的增感染料的ESR波谱研究

本文用电子顺磁共振技术研究了光照条件下三十八种增感染料与溴化银之间发生的电子转移过程。增感染料和溴化银无论在黑暗处还是在光照下,均不产生ESR信号。当增感染料吸附在溴化银颗粒表面上时,如不加光照,仍看不到ESR信号。只有在光照条件下,才有可能观察到ESR信号,这主要取决于增感染料分子的最高占有能级与溴化银价带的相对位置。若染料分子的最高占有能级比溴化银价带顶部高0.7 eV,就可以观察到ESR信号,反之则观察不到。顺磁性中心是由染料正空穴Dye^©形成的。根据ESR信号的强度可以判断增感染料是否有较强的减感作用。     

染料聚集态中空穴传递的顺磁共振研究

本文应用了顺磁共振波谱技术,研究了染料J-聚集体对染料正空穴俘获电子的影响。实验所用乳剂是未经化学增感的溴化银(AgBr),染料用量2.5×10^-4摩尔染料/摩尔银。涂片厚度为3微米左右。     

纳米硫化铅增感的溴化银微晶中光电子衰减特性研究

采用纳米硫化铅作为增感剂对边长为0.8μm的溴化银立方体颗粒进行了化学增感.利用微弱信号的微波吸收相敏检测技术,在超短脉冲激光作用下,获得了立方体溴化银乳剂中自由光电子和浅束缚光电子随增感时间变化的衰减曲线.通过测量溴化银光作用过程的时间分辨谱,讨论了卤化银晶体中电子陷阱对光电子运动行为的影响,分析了电子陷阱效应同增感时间之间的关系以及两个一级衰减区间寿命值同增感时间的关系.通过未增感样品与增感样品的衰减曲线对比,得到了在此实验条件下的最佳增感时间为60 min.     

卤化银乳剂颗粒上不对称菁染料J-聚体荧光的研究

光谱增感机理的研究是感光科学中的一个重要课题Gilman^[1]和Kuhn等^[2]曾经提出光谱增感的电子转移和能量传递理论。随着现代谱学手段的出现,为人们了解光谱增感的初始过程提供了条件。近年来,电子转移的机理已被广泛接受,并用来解释与光谱增感有关的各种现象。但在ns~ps范围内的光谱增感动力学方面的研究还不多见。Dahne认为光谱增感不仅决定于染料与卤化银的能级关系,而且是由动力学控制的^[3],激发态染料向卤化银导带注人电子的电子转移过程与辐射及其他无辐射去活过程是竞争的^[4]我们通过对两种不对称的苯并咪哇唾碳著染料在AgBrI乳剂颗粒上吸附形成的J一聚体的荧光性质的研究,以求深人了解光谱增感的电子转移机理及其动力学过程,无疑是有重要意义的。     

溴化银中氯离子含量对增感染料吸附及增感作用的影响

本文研究了在氯溴化银上不同类型染料的吸附和不同氯离子含量的溴化银乳剂中染料的增感作用。证明在溴化银乳剂中加入氯离子以后,光谱增感的倍率增加了。不同类型的染料呈现出不同的增感规律。份菁染料在氯溴化银乳剂上具有最好的吸附能力和光谱增感作用。实验结果还表明,染料的吸附与乳剂光谱增感效果,有着良好的对应关系。证实了染料和卤化银所形成的吸附络合物是具有照相活性的。对不同类型染料的增感现象进行了讨论。     

不同取代基的噻碳菁和吲哚碳菁染料对其在溴化银微晶上吸附能力及形成J-聚集体尺寸分布的影响

本文研究了5-位不同取代基的噻碳菁和吲哚碳菁染料对其在立方型颗粒和T-颗粒溴化银微晶上吸附能力的影响,并采用ACFEM(Analytical Color Fluore scence Electron Microscopy)研究了上述结构染料对其吸附在溴化银微晶所形成的J-聚集体尺寸分布的影响。实验结果表明,对吲哚碳菁染料来说,立方体溴化银微晶表面的吸附能力较T-颗粒溴化银微晶表面的吸附能力强;但对噻碳菁染料来说则相反,它们在T-颗粒溴化银微晶表面的吸附能力较立方体溴化银微晶表面的吸附能力强。另外,对5-位不同取代基的噻碳菁染料而言,无论是在立方型颗粒或T-颗粒溴化银微晶上的吸附能力来说,含取代基(无论4-取代基是吸电子型还是推电子型)的噻碳菁染料较未取代的噻碳菁染料强;而5-位取代基是吸电子型的噻碳菁染料更有利于其吸附在T-颗粒溴化银微晶表面。此外,本文还进一步证明了溴化银微晶表面上染料J-聚集体的生长过程是符合奥斯瓦尔特成熟过程的。吲哚碳菁染料在T-颗粒溴化银微晶上形成的J-聚集体的平均尺寸明显大于在立方体溴化银微晶上形成的J-聚集体的平均尺寸。吸附在立方体溴化银微晶上的5-不同取代基的噻碳菁染料对其形成J-聚集体尺寸分布的影响的研究结果表明,含取代基(-CH₃,-Ph,-Cl)的噻碳菁染料形成的J-聚集体的尺寸分布几乎相同,但与未取代的噻碳菁染料形成的J-聚集体的尺寸分布明显不同;5-位含取代基的噻碳菁染料形成的J-聚集体平均尺寸大于未取代的噻碳菁染料的。     

增感染料与卤化银微晶之间的作用及其聚集态的研究

本文研究了光谱增感染料的结构对立方体卤化银乳剂的感光性能的影响,并利用反射光谱和彩色分析荧光电镜研究了染料在卤化银微晶上的聚集态和Ｊ 聚集体的相对尺寸,通过测定乳剂离子电导率研究了染料的结构对乳剂离子电导率的影响．实验结果表明：本文中所用的九个染料不管是增感还是减感染料都能在立方体卤化银乳剂上形成Ｊ 聚集态;对噻碳菁染料而言,其５位上无论是吸电子基团还是推电子基团的染料形成的Ｊ 聚集体的平均尺寸皆较未取代染料的大,其增感效果也较好;苯环５位上吸电子基取代或平面性好的噻碳菁染料可提高立方体ＡｇＢｒＩ乳剂的离子电导率,证明它们的增感效果也好;６位硝基取代的吲哚碳菁染料是典型的减感染料,其在立方体乳剂上所形成的Ｊ 聚集体较小,但是对乳剂的离子电导无影响．此外,本文还试图对不对称插烯菁染料Ｄｙｅ９使立方体ＡｇＢｒＩ乳剂减感的作用进行了解释     

菁染料在TiO2胶体表面光诱导的电子转移

本文用紫外-可见光谱及荧光光谱研究了吸附在TiO₂胶体表面上的染料1,1'-二乙基-3,3'-二磺丁基-5,5'-二氰基咪碳菁与胶体间发生的光诱导电子转移过程。荧光实验表明,菁染料荧光发射强度随着体系中TiO₂胶体浓度的增加而降低,这是由于电子从染料的激发单重态注入到TiO₂的导带所致。通过染料荧光寿命的测定得到光诱导电子转移速率常数K_et约为4×10₈s^-1。     

阻光染料对氯化银乳剂光谱增感的影响

增感染料在卤化银微晶上吸附并形成J-聚集体是染料光谱增感和超增感的关键步骤.本文利用紫外-可见吸收光谱研究了增感染料和阻光染料在氯化银微晶上的吸附,并考察了阻光染料对增感染料J-聚集体的形成及乳剂感光性能的影响.结果表明:不同阻光染料在氯化银微晶表面的吸附程度不同,对增感染料J-聚集体形成的影响也有差异.其中,吸附较小的不影响增感染料J-聚集体的形成,而吸附较大的阻碍增感染料J-聚集形成,特别是阻光染料在增感染料之前加入乳剂中时.在氯化银微晶上吸附很小的阻光染料基本不影响增感染料对乳剂的光谱增感,而吸附较强的阻光染料不仅吸收入射光,还抑制或破坏增感染料的光谱增感.因此,在氯化银微晶表面没有吸附的阻光染料才是优良的阻光染料.     

染料增感AgBr乳剂的光电子衰减动力学研究

本工作利用微波吸收薄膜介电谱测量技术,测量了菁染料光谱增感后的AgBr晶体乳剂在脉冲激光曝光后产生的光电子衰减时间特性,分析了不同类型的染料及其增感条件对材料光电子时间特性的影响关系.通过比较增感后的T 颗粒乳剂和立方体乳剂的光电子衰减特性,实验验证了吸附在T 颗粒(111)晶面上的染料比吸附在立方体(100)晶面上的染料更有效、更有助于形成潜影的论据.     

Effect of Hydrophobic Chain of Dye Molecule and Surface of Active Crystal on the Organized Assemblies Formation of Dyes

Four derivatives of 5,5',6,6'-tetrachlorobenzimidazolocarbocyanine iodide with different long alkyl chain substituents in N-position of polymethine chromophore have been used for investigating the influence of hydrophobicity of dyes on the aggregation.It has been found that all dyes formed monomeric species in methyl alcohol. However, after addition of water to CH_3OH to change the polarity of the solvent, difference between dyes appeared.Addition of inorganic salt facilitated the J-aggregation of easy soluble dye, but it seems useless for the sparely soluble dye.Platelets cut from AgBr polycrystal or pressed AgBr powder have been used as substrate for adsorbing dyes. After addition of hexanoic acid, eventually the J-aggregate on AgBr surface could be destroyed.Voltammetry is a useful tool to investigate the interaction between dyes and AgBr. Experimental results showed that the longer the carbon chain substituents is, the stronger the interaction between AgBr and dyes would be.     

某些硫碳菁染料在溴碘化银乳剂中聚集态的研究

本文应用三种不同晶形的溴碘化银乳剂(立方体、八面体和T-颗粒)和八种硫碳菁染料(大部分为内铵盐结构染料)进行了染料的聚集态的研究。试验结果表明,染料的J-聚集态的形成主要取决于染料的结构,其次依赖于卤化银的晶形。三种不同结构的表面活性剂对染料聚集态的形成均有影响,其中两性的表面活性剂最强,阴离子的表面活性剂次之,中性的表面活性剂最弱。二种中位甲基取代的硫碳菁染料的聚集态受表面活性剂影响最为明显,形成较强的J-态,而对其它六种染料的聚集态影响较小,J-聚集态稍有增强。     

STRUCTURE OF DYE AGGREGATES AND THE MECHANISM(S) OF PHOTOSENSITIZATION OF AgBr*,†

Abstract— This paper reports the present conclusions of an extended investigation on photo-sensitization of silver bromide. A general molecular packing structure for dye aggregates on the AgBr (111) surface is proposed. This structure, along with the observed spectral absorption displacements of small aggregates, is used to elucidate the phenomena of antisensitization and supersensitization. Supersensitization is seen as a partitioning of large dye aggregates into small aggregates by a deliberately added second component or by gaps between the aggregates. This partitioning isolates antisensitizing dye in a small fraction of the aggregates and minimizes its effect. The smallest aggregates are least likely to contain an antisensitizer, and show the highest quantum efficiency for photoconductivity and photographic action. Photoconductivity measurements establish that supersensitization occurs before the electron appears in the AgBr phase.
The question of direct electron injection vs. energy transfer as mechanisms for AgBr photosensitization is examined in terms of radiationless transfer to surface Ag₂S on AgBr. The absorption of surface Ag₂S is shown to be adequate for acceptance of Förster transfer from the dye, and surface Ag₂S is known to be photographically active. However, this mechanism is inefficient, and inadequate to account for observed high efficiency infrared sensitization. Direct electron injection is seen as the more probable mechanism for efficient dye sensitization of AgBr.     

Photoinduced charge carrier dynamics of Zn-porphyrin-TiO2 electrodes: the key role of charge recombination for solar cell performance

Time resolved absorption spectroscopy has been used to study photoinduced electron injection and charge recombination in Zn-porphyrin sensitized nanostructured TiO(2) electrodes. The electron transfer dynamics is correlated to the performance of dye sensitized solar cells based on the same electrodes. We find that the dye/semiconductor binding can be described with a heterogeneous geometry where the Zn-porphyrin molecules are attached to the TiO(2) surface with a distribution of tilt angles. The binding angle determines the porphyrin-semiconductor electron transfer distance and charge transfer occurs through space, rather than through the bridge connecting the porphyrin to the surface. For short sensitization times (1 h), there is a direct correlation between solar cell efficiency and amplitude of the kinetic component due to long-lived conduction band electrons, once variations in light harvesting (surface coverage) have been taken into account. Long sensitization time (12 h) results in decreased solar cell efficiency because of decreased efficiency of electron injection.     

Femtosecond to millisecond studies of electron transfer processes in a donor-(π-spacer)-acceptor series of organic dyes for solar cells interacting with titania nanoparticles and ordered nanotube array films

Time-resolved emission and absorption spectroscopy are used to study the photoinduced dynamics of forward and back electron transfer processes taking place between a recently synthesized series of donor-(π-spacer)-acceptor organic dyes and semiconductor films. Results are obtained for vertically oriented titania nanotube arrays (inner diameters 36 nm and 70 nm), standard titania nanoparticles (25 nm diameter) and, as a reference, alumina nanoparticle (13 nm diameter) films. The studied dyes contain a triphenylamine group as an electron donor, cyanoacrylic acid part as an electron acceptor, and differ by the substituents in a spacer group that causes a shift of its absorption spectra. Despite a red-shift of the dye absorption band resulting in an improved response to the solar spectrum, smaller electron injection rates and smaller extinction coefficients result in reduced dye sensitized solar cell (DSSC) conversion efficiencies. For the most efficient dye, TPC1, electron injection from the hot locally excited state to titania on a time scale of about 100 fs is suggested, while from the relaxed charge transfer state it proceeds in a non-exponential way with time constants from 1 ps to 50 ps. Our results imply that the latter process involves the trap states below the conduction band edge (or the sub-bandgap tail of the acceptor states), localized close to the dye radical cation, and is accompanied by fast electron recombination to the parent dye's ground state. This process should limit the efficiency of DSSCs made using these types of organic dyes. The residual, slower recombination can be described by a stretched exponential decay with a characteristic time of 0.5 μs and a dispersion parameter of 0.33. Both the electron injection and back electron transfer dynamics are similar in titania nanoparticles and nanotubes. Variations between the two film types are only found in the time resolved emission transients, which are explained in terms of the difference in local electric fields affecting the position of the emission bands.