显影机理的正电子化学研究

采用正电子湮没技术(PAT)研究了照相明胶中的自由体积空穴在显影过程中的作用机理,为显影过程中银丝的生成机理探讨了一个新的模式,并为感光科学的研究拓展了一种新的研究技术和手段.结果表明:明胶的自由体积空穴的平均尺寸在显影过程中基本保持不变.照相明胶的自由体积空穴在电子密度空间限制了银离子还原为银原子的过程,并使得银原子的沉积生长以丝状的形式进行.照相明胶大分子结构和组份的复杂性导致了其自由体积空穴在空间分布无序混乱性,可能正是这种无序混乱性导致了银丝缠绕成团的松散空间结构.     

用铜物理显影的多级放大成像过程Ⅲ.影像中铜和银的分布及明胶对Au3+的还原

本文研究了铜物理显影后影像中铜和银的分布以及在非影像区明胶对Au³⁺的还原作用。铜含量随着影像深度的增加而增加,银含量却随着深度的增加而减少。Ag3d结合能向低值位移说明影像内部的银处于单原子和多原子的混合状态,但是影像表面的银却为单原子状态,如果铜物理显影进行得足够长,铜最终会将银全部遮盖。在这以后的铜物理显影是铜的自催化过程,样片浸入氯金酸溶液中后,非影像区中吸收的氯金酸量大大高于影像区,因而铜的沉积速度在非影像区也比影像区大得多。明胶能还原Au³⁺.还原过程可分为两步:第一步由Au³⁺还原成Au⁺,这一步在室温下是快反应;第二步由Au⁺还原成金,这个反应比较慢,Au⁺和Au在物理显影中可作为催化核,使铜在非影像区沉积。     

在照相明胶层中金催化的铜无电沉积

利用X射线光电子能谱的原位氩离子束溅射和ESCA技术，研究了无电沉积前后照相明胶中硫元素化学形态的变化，对无电沉积所形成的导电膜进行了深度剖析，探讨了照相明胶层中金催化的铜无电沉积机理．结果表明：在酸性条件下（pH＝3．20），明胶大分子的蛋氨酸亚砜对AU3 仍具有较大的还原能力，明胶大分子的蛋氨酸、蛋氨酸亚砜将Au3 最终还原为胶态金，而蛋氨酸和蛋氨酸亚砜均被氧化为蛋氨酸砜．在无电沉积初期，胶态金作为催化中心引发铜的无电沉积，之后的反应为Cu2 在新生态铜的自催化下的还原沉积．在无电沉积过程的碱性条件下（pH＝12．50），明胶中的部分蛋氨酸砜又被甲醛还原为蛋氨酸．     

明胶与Ag+相互作用的XPS研究

X射线光电子能谱(XPS)技术是一种高灵敏、高分辨的元素定性定量和结构分析技术.本文用该技术研究了照相明胶中S原子与Ag⁺相互作用的本质.研究结果表明,照相明胶中的蛋氨酸、蛋氨酸亚砜残基均能通过S原子与Ag⁺作用,而且在所研究的明胶中蛋氨酸亚砜残基的含量远高于蛋氨酸残基的含量,这意味着在与Ag⁺键合过程中前者占有更重要的地位.此外,本文还比较了不同原料制成的明胶与Ag⁺的作用情况.     

n型半导体硅电极表面Au的电化学成核机理

在成功实现半导体硅表面电沉积致密金膜的柠檬酸盐镀金实际应用体系中,运用循环伏安和电位阶跃法研究了Au在n型Si(111)电极表面的电沉积过程和成核机理.结果表明,在该体系中, Au在Si表面呈现不可逆电极过程,成核过电位达到250 mV;根据Cottrell方程求得扩散系数D = (1.81 ± 0.14) × 10^-4 cm₂·s^-1;运用Scharifker-Hills (SH)理论模型对比分析拟合实验结果,表明Au在n型Si表面遵循扩散控制下的三维连续成核机理;通过扫描电子显微镜观察Au初期成核、生长形貌,进一步证实了Au的三维连续成核机制,并讨论了阶跃电位和阶跃时间对Au核形貌和密度的影响.     

明胶/卤化银乳剂体系正电子湮没研究

长期以来,显影过程特别是银丝的生成机理一直是感光工作者关注和研究的焦点.但迄今为止,众说纷坛的各种假说尚未达到共识,本文用正电子湮没技术 (PAT)测定了乳剂的正电子湮没寿命谱,探讨了银丝在自由体积空穴中的生长机理,并采用透射电子显微镜观察除去明胶后的银丝形貌,验证了PAT实验中银丝生长的结论.同时本文根据明胶中蛋氨酸及其氧化产物的大致含量,首次采用正电子湮没技术 (PAT)研究将蛋氨酸及其氧化产物加到照相乳剂中,观察蛋氨酸及其氧化产物的还原性以及在水洗前加入蛋氨酸和在水洗后加入蛋氨酸的差别.     

离子液体中Au(111)和Pt(111)表面Ge欠电位沉积的现场STM研究

本文研究BMIPF₆离子液体中Au(111)和Pt(111)表面Ge的电沉积行为. 循环伏安法测试结果表明,在含0.1 mol·L^-1 GeCl₄的BMIPF₆溶液Au(111)和Pt(111)表面均有两个与Ge沉积过程相关的还原峰. 第一个还原峰包含了Ge⁴⁺还原成Ge²⁺及Ge的欠电位沉积,第二个还原峰对应Ge的本体沉积. 现场扫描隧道显微镜研究结果表明,Ge在Au(111)和Pt(111)表面均有两层欠电位沉积. 第一层欠电位沉积厚度约为0.25 nm、形貌平整、带有缝隙的亚单层结构. 第二层欠电位沉积形貌相对粗糙的点状团簇结构. 该欠电位沉积过程伴随表面合金化.     

照相明胶与化学增感剂相互作用的XPS研究

本文采用X射线光电子能谱技术研究了两种照相明胶与化学增感剂相互作用的机理.当两种照相明胶样品在HAuCl₄溶液中反应5min后,明胶中的蛋氨酸、蛋氨酸亚砜均被氧化为蛋氨酸砜.与此同时,明胶吸附的大部分Au³⁺被还原为Au⁺,并且Au⁺以络合形态存在于明胶之中.根据与AuCl₃反应之后明胶中Au³⁺与Au⁺的比例,法国明胶的还原性略高于包头明胶.添加到明胶中的Na₂S₂O₃能将明胶大分子所含的蛋氨酸亚砜全部还原为蛋氨酸.S₂O₃^2-、蛋氨酸和蛋氨酸砜可以稳定共存于明胶体系之中,外加的S₂O₃^2-的还原性高于明胶中蛋氨酸、蛋氨酸亚砜的还原性.添加Na₂S₂O₃后的两种照相明胶均可以将其溶胀吸附的Au³⁺全部还原为胶态金.此时,参与氧化还原反应的主要基团是S₂O₃^2-而非明胶中的蛋氨酸残基.由于Na₂S₂O₃的添加,照相明胶对AuCl₃的还原能力增强.     

用铜物理显影的多级放大成像过程——Ⅱ.获得能导电的影像

前文^[1]中我们报道了利用铜物理显影的多级放大成像过程能够明显地提高影像密度,从而大大提高了感光材料的感光度或者大幅度地降低感光材料的用银量,并且可以达到特高反差和特短趾部等特殊效果。本文介绍铜物理显影多级放大成像过程的另一种应用:在乳剂层表面或绝缘材料表面上定域沉积能导电的铜影像,为将感光胶片直接用于轻印刷以及制作印刷电路板开辟了新途径.     

激光刻蚀模板中电沉积特殊结构CIGS薄膜

本文利用激光刻蚀模板,在水溶液中电沉积制备金属铜薄膜,讨论了温度、电流、硫酸铜浓度对薄膜形貌的影响. 采用SEM对制备的铜薄膜进行表征,结果表明在沉积温度为30 ℃,沉积电流为4 A·dm^-2(表观工作电流密度),硫酸铜浓度在20 ~ 50 g·L^-1的水溶液中电沉积可以得到中空馒头状和开口碗状结构的铜薄膜. 利用激光刻蚀模板,在离子液体1-丁基-3-甲基咪唑三氟甲磺酸盐([BMI][TfO]) - 30 Vol%丙醇混合电解质中电沉积CIGS薄膜,研究了沉积电势、沉积时间对薄膜形貌的影响. SEM观察发现,在沉积电势为-1.8 V,沉积时间为1.5 h条件下电沉积可以得到近似柱状的簇状花束样的CIGS薄膜, 电沉积铜后再进一步电沉积CIGS,得到了均匀有序的鼓包柱状结构的Cu/CIGS复合薄膜. 用恒电势方波法对制备的薄膜真实表面积进行测试,计算结果表明,与无模板电沉积制备的CIGS薄膜相比,激光刻蚀模板法制备的Cu/CIGS复合薄膜的表面积提高了约8倍.     

Interfacial bonding of gold nanoparticles on a H-terminated Si(100) substrate obtained by electro- and electroless deposition

Dome-shaped gold nanoparticles (with an average diameter of 10.5 nm) are grown on H-terminated Si(100) substrates by simple techniques involving electro- and electroless deposition from a 0.05 mM AuCl3 and 0.1 M NaClO4 solution. XPS depth profiling data (involving Au 4f core-level and valence band spectra) reveal for the first time the formation of gold silicide at the interface between the Au nanoparticles and Si substrate. UV-visible diffuse reflectance spectra indicate that both samples have surface plasmon resonance maxima at 558 nm, characteristic of an uniform distribution of Au nanoscale particles of sufficiently small size. Glancing-incidence XRD patterns clearly show that the deposited Au nanoparticles belong to the fcc phase, with the relative intensity of the (220) plane for Au nanoparticles obtained by electroless deposition found to be notably larger than that by electrodeposition.     

Bottom-up filling in electroless plating with an addition of JGB-RPE

Bottom-up filling of copper for different sub-micrometer trenches was investigated by electroless deposition technique using Janus Green B (JGB) and Triblock copolymers RPE-2520. The bottom-up copper filling usually achieves a relative high deposition rate of copper in the bottom of trenches through inhibiting the surface deposition or accelerating the bottom deposition of copper. The bottom-up filling behavior of electroless copper deposition for different trenches was investigated in a plating bath containing 0.3 mg/L JGB and 1.0 mg/L RPE-2520. The cross-section image with SEM indicated that the trenches with different widths ranging from 110 to 520 nm were completely filled with electroless copper and that no void was found.     

Cluster-size dependence of alloying behavior in gold clusters

Cluster-size dependence of alloying behavior in nm-sized atom clusters has been studied by transmission electron microscopy, using clusters in the Au-Cu system. It was revealed that occurrence of rapid spontaneous alloying becomes more difficult with increasing cluster size. In gold clusters of approximately 4 nm in the mean size, a rapid dissolution of copper atoms took place and homogeneously mixed Au-Cu alloy clusters were formed. In gold clusters of approximately 10 nm in the mean size, rapid alloying of copper took place only at a shell-shaped region beneath the free surface of individual clusters and pure gold was retained at the central region of clusters. In gold clusters of approximately 30 nm in the mean size, no rapid alloying of copper was induced. The ease with which spontaneous alloying takes place is discussed in terms of the lattice softening in atom clusters.     

Effect of additive triblock copolymer PEP-3100 on bottom-up filling in electroless copper plating

Bottom-up copper filling for different sub-micrometer trenches was investigated by electroless deposition technique using a PO-EO-PO triblock copolymer termed PEP-3100 as an additive. It was found that PEP-3100 (molecular weight 3100) had a strong inhibition for the electroless copper deposition. The bottom-up filling behavior of electroless copper bath for different trenches was investigated in a plating bath containing 1.0 mg l⁻¹ PEP-3100. The cross-section SEM observation indicated the trenches with different widths ranging from 100 to 380 nm were all filled completely by electroless copper.     

The voltammetric response of bipolar cells: Mechanistic investigations of electroless deposition

The voltammetric response of a bipolar cell is described where the cell is applied to electroless deposition processes. The method is illustrated with copper deposition on gold surfaces, driven by the oxidation of dimethylamine borane.     

Comparison of Bottom-up Filling in Electroless Plating with an Addition of PEG,PPG and EPE

The bottom‐up filling capabilities of electroless copper plating bath with an addition of additives, such as polyethylene glycol (PEG), polypropylene glycol (PPG) and triblock copolymers of PEG and PPG with ethylene oxide terminal blocks termed EPE, were investigated by the cross‐sectional scanning electron microscopy (SEM) observation of sub‐micrometer trenches. Though three additives had inhibition for electroless copper deposition, the suppression degrees of three additives were different. EPE‐2000 had the strongest suppression for electroless copper deposition, and the suppression of PEG‐2000 was the weakest. The bottom‐up filling capability of electroless copper was investigated in a plating bath containing different additives with the concentration of 2.0 mg/L. The cross‐sectional SEM observation indicated the trenches with the width of 280 nm and the depth of 475 nm were all completely filled by the plating bath with an addition of EPE‐2000, but the trenches were not completely filled by the plating bath with an addition of PEG‐2000 or PPG‐2000, and some voids appeared. Linear sweep voltammetry measurement indicated that three additives all inhibited the cathodic reduction reaction and the anodic oxidation reaction, and the inhibition of EPE‐2000 was the strongest among three additives, which agreed with that of the deposition rate of electroless copper. Significant differences in surface roughness of deposited copper film were observed by UV‐visible near‐infrared for different suppressors, and the bright and smooth of deposited copper film were in accordance with the inhibition of three additives.     

Room temperature synthesis of silver nanowires from tabular silver bromide crystals in the presence of gelatin

Long silver nanowires were synthesized at room temperature by a simple and fast process derived from the development of photographic films. A film consisting of an emulsion of tabular silver bromide grains in gelatin was treated with a photographic developer (4-(methylamino)phenol sulfate (metol), citric acid) in the presence of additional aqueous silver nitrate. The silver nanowires have lengths of more than 50 μm, some even more than 100 μm, and average diameters of about 80 nm. Approximately, 70% of the metallic silver formed in the reduction consists of silver nanowires. Selected area electron diffraction (SAED) results indicate that the silver nanowires grow along the [111] direction. It was found that the presence of gelatin, tabular silver bromide crystals and silver ions in solution are essential for the formation of the silver nanowires. The nanowires appear to originate from the edges of the silver bromide crystals. They were characterized by transmission electron microscopy (TEM), SAED, scanning electron microscopy (SEM), and powder X-ray diffraction (XRD).