Defect Characterization of 6H-SiC Studied by Slow Positron Beam

The defect formation and annealing behavior in as-grown and electron-irradiated 6H-SiC wafers were investi-gated by variable-energy slow positron beam. For the n-type as-grown samples, it was found that annealing decreased the defect concentration due to recombination with interstitial, and when it was annealed at 1400 ±C for 30 min in vacuum, a 20 nm thick Si layer was found on the top of SiC substrate, which is a direct proof of the Si atom diffusing to the surface when annealed at the high temperature stages. During the high temperature annealing stage, we found an obvious surface effect occurred that induced the higher S parameter close to the surface. This may be caused by the diffusion of the Si atoms to the surface during annealing. After 10 MeV electron irradiation of the n-type 6H-SiC, the positron effective diffusion length decreased from 86.2 nm to 39.1 nm. This shows that there are some defects created in n-type 6H-SiC. But in the p-type 6H-SiC irradiated by 10 MeV electrons, the change is very small. This may be because of the opposite charge of the vacancy defects. The same annealing behavior as that of as-grown 6H-SiC samples was also observed for the 1.8 MeV electron-irradiated 6H-SiC samples except that after being annealed at 300 ±C, its defect concentration increased. This may be explained as the generation of carbon vacancies, due to either the recombination between divacancies and silicon interstitial, or the charge of the charge states.     

Interdiffusion kinetics of miscible polymer/polymer laminates investigated by atomic force microscopy

The miscibility of poly(vinyl chloride)/poly(n-butyl methacrylate) (PVC/PnBMA) blend and the interdiffusion kinetics of PVC/PnBMA laminates have been investigated by differential scanning calorimetry (DSC) and atomic force microscopy (AFM), respectively. This blend exhibited a lower critical solution temperature behavior. Below 120℃, DSC results showed each blend with different PVC contents exhibited only a single glass transition temperature which increased with PVC content, indicating that PVC and PnBMA were miscible. After PVC/PnBMA laminates were annealed at different temperature for different time, a smooth cross-section across interface was prepared by ultramicrotoming. Combined with topography and phase images of tapping mode AFM, the relative concentration profile, interface width and the relationship between interface width and annealing time could be obtained. In a regime of rubbery/rubbery interdiffusion, the diffusion obeyed a typical Fickian Case-Ⅰ behavior where the interface width was proportional to the square root of annealing time. The mutual diffusion coefficient was in good agreement with that obtained from DSC and positron annihilation lifetime spectroscopy. However, in the regime of glassy/rubbery interdiffusion, the diffusion followed a typical Case-Ⅱ behavior where the interface width was proportional to annealing time. These results imply that AFM is a reliable and powerful tool for the investigation of polymer/polymer interdiffusion at a level of polymer chain size.     

用正电子湮没寿命谱法研究锡镀层缺陷

光亮镀锡工艺由于成本低、无毒、镀层稳定性好而广泛应用于电子元器件引线的电镀.但因锡镀层与基体之间会发生原子的相互扩散,致使产品在储存、焊接或使用期间因温度效应而使某些重要的物理和化学性能,如钎焊性、导电性和防腐性变差。金属界面原子的热扩散行为与金属晶体的结构缺陷密切相关,因此应用正电子湮没寿命谱法研究锡镀层在热处理过程中缺陷的运动规律,在理论和工艺方面都具有重要的意义。     

用正电子湮没寿命谱法研究电沉积镍结构缺陷

应用正电子湮没寿命谱研究了十二种典型镍镀层的结构缺陷。根据电沉积镍含有杂质的特点, 采用四态模型对寿命谱进行理论分析。利用寿命谱二组分拟合结果计算了未退火试样的类空位和类微洞的浓度。研究了第10号试样的退火行为, 根据有关的湮没参数与退火温度的关系曲线, 推断出镀层中的氢既以吸附态形式存在于微洞也以固溶态的形式存在于空位, 同时也观察到在退火过程中空位热迁移并入微洞和镀层杂质发生化学聚团作用的现象。     

Bio-inspired catechol chemistry for electrophoretic nanotechnology of oxide films

The stabilization of defects in ZnO at high temperatures has been investigated. The properties of unmodified and modified ZnO nanoparticles (NPs) with 2 at.% of Ag prepared by microwave assisted combustion method, have been systematically studied using X-ray diffraction (XRD), photoluminescence (PL), X-ray photoelectron spectroscopy (XPS) and photocatalytic activity measurements. Though the XRD data shows a marginal shift in the ZnO peak position upon Ag addition, the amount of shift does not change with annealing temperatures. The PL data reveals that the defect mediated visible emission intensity of unmodified ZnO NPs increases with increase in the annealing temperature, whereas it remains almost unchanged in Ag-ZnO. This study clearly establishes that silver is an efficient stabilizer of intrinsic defects in ZnO at high temperatures. This is further supported by the core and valence band XPS spectra.     

Photoluminescence quenching of quantum-confined cadmium sulfide clusters by norbornadiene derivatives

Influence of norbornadiene and its derivatives on the photoluminescence (PL) of quantum-confined cadmium sulfide clusters (Q-CdS) prepared in reverse micelles was investigated.It was found that norbornadiene-2,3-dicarboxylic acid (3) and its monopotassium salt (4) quenched PL intensity by 77% and 62%,respectively,whereas its dipotassium salt (5),norbornadiene (1) and norbornadiene-2,3-dimethylcarboxylate (2) had no effect on PL intensity.The formation constants for adducts formed between defect sites at the surface of Q-CdS clusters and 3 or 4 were also determined.PL quenching effect was attributed to the presence of ionizable proton which is considered to be able to trap photogenerated electrons and remove them from possible decay process.Measurements of the PL decay by single photon counting technique also supported these steady-state observations.     

Self-selective recovery of photoluminescence in amphiphilic polymer encapsulated PbS quantum dots

Self-selected recovery of the photoluminescence (PL) of amphiphilic polymer encapsulated PbS quantum dots (QDs) was observed in water for the first time and possible mechanisms were proposed based on investigations by means of transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction and fluorescence spectroscopy. Water-soluble PbS QDs were synthesized by transferring monodispersed QDs capped with hydrophobic ligands of oleylamine from an organic solvent into water via amphiphilic polymers poly(maleic anhydride-alt-1-octadecene-co-poly(ethylene glycol)). The water transfer process leads to a double size distribution (5.6 ± 0.9 nm and 2.7 ± 0.4 nm), attributed to ligand etching together with Ostwald ripening, as well as the fast decay of PL. The automatic recovery of the PL in PbS QDs stored in water in the dark for 3 months was only observed for the subset of smaller QDs and is largely due to the removal of surface defects with aging, as evidenced by the decreased percentage of unpassivated surface atoms from XPS studies. In contrast, the PL of the subset of larger QDs in the same sample does not self-recover in water and can only be slightly recovered by transferring them into environments with less external quenches. The results strongly suggest that it is the surface defect in the larger QDs themselves, introduced during Ostwald ripening, that is primarily responsible for their non-emitting status or rather low PL intensity under different conditions. The increase of unpassivated Pb atoms in larger PbS QDs after the 3 month aging has been confirmed by XPS, which explains their non-recovery behavior in water. The PL-recovered QD sample in water is very stable and shows comparable photostability to the initial QDs dispersed in an organic phase.     

Porogen approach for the fabrication of plasma-polymerized nanoporous polysiloxane films

Nanoporous polysiloxane films were fabricated by plasma polymerization of hexamethyldisiloxane mixed with cyclohexane under different conditions. The pores were generated through the elimination of carbonaceous aggregates (porogen) by annealing at 600 degrees C. Results of spectroscopic ellipsometry, Fourier transform infrared spectroscopy, and positron annihilation lifetime spectroscopy suggest that not only film porosity but also average pore size depends on the amount of the decomposable porogen. The pore size was controllable in a range between 0.6 and 1.0 nm in radius by proper selection of the substrate temperature and precursor composition.     

Direct evidence of molecular aggregation and degradation mechanism of organic light-emitting diodes under joule heating: an STM and photoluminescence study

The Joule heating effect on electroluminescent efficiency is important in the degradation origin of organic light-emitting diodes (OLED). Scanning tunneling microscopy (STM) and photoluminescence (PL) measurements were performed on the guest molecule BT (1,4-bis(benzothiazole-vinyl) benzene), host molecule TPBI (2, 2',2' '-(1,3,5-phenylene)tris-[1-phenyl-1H-benzimidazole]), and their mixture deposited on an HOPG surface to study the OLED degradation mechanism due to thermal heating. At room temperature, BT and TPBI in the mixed layer show good compatibility and high PL intensity, but at higher temperatures, they show phase separation and aggregation into their own domains and a concomitant decrease in PL intensity. The PL intensity loss suggests ineffective energy transfer from TPBI to BT due to phase separation, which may cause OLED degradation. Scanning tunneling spectroscopy (STS) results show that the band gaps of TPBI and BT remain unchanged with the annealing temperature, suggesting that the heat-induced decay of OLED is related to the interfacial structural change rather than the respective molecular band gap. The results provide direct evidence showing how the molecular structures of the mixed layer vary and affect the PL intensity due to temperature.     

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.     

两步互扩散法制备高性能CsPbCl3薄膜紫外光电探测器

紫外光电探测器无论在军用和民用上都有着巨大的应用前景,CsPbCl₃作为钙钛矿家族中形成能最大,化学性能稳定的成员,在可见光盲区的紫外光电探测器中有着很大潜在的应用价值。本文针对CsPbCl₃薄膜难以制备的问题,发展了一种两步互扩散溶液法,通过控制前驱体PbCl2的形貌,成功地制备了CsPbCl₃薄膜。利用扫描电镜、吸收光谱和X射线表征技术,证实了制备出的薄膜表面平整无孔洞、晶粒饱满和吸光度强。通过瞬态荧光和变激发光强的稳态荧光,揭示了薄膜具有载流子寿命长、缺陷态少等优异性能。最终构建出了响应度为0.75 A·W^?1的横向结构紫外光电探测器,为将来进一步发展高性能CsPbCl₃薄膜紫外光电探测器奠定了基础。     

Kinetics of PL quenching during single-walled carbon nanotube rebundling and diameter-dependent surfactant interactions

The kinetics of single-walled carbon nanotube rebundling have been investigated by photoluminescence (PL) spectroscopy. The rate of loss of PL intensity was measured for 12 different nanotubes in three common aqueous surfactants (sodium dodecyl sulfate, SDS; sodium dodecylbenzene sulfonate, SDBS; and sodium cholate, SC) as the surfactant suspensions were diluted to promote nanotube rebundling, quenching of semiconductor nanotube PL, and precipitation. The rate of PL decay was first-order in the concentration of isolated nanotubes, as expected if surfactant desorption is rate-limiting in the rebundling process. Temperature-dependent measurements permitted an Arrhenius analysis from which diameter-dependent activation energies were determined. SDS was found to have very strong diameter dependence for activation energy, with stronger binding to smaller-diameter nanotubes, whereas SDBS displayed a weaker diameter dependence. SC was found to bind strongly to certain nanotubes and weakly to the (10,2) nanotube. The PL emission red shifted with time after dilution as surfactant desorption proceeded. This effect is attributed to an increase in the micropolarity at the nanotube surface.     

Investigation of the growth parameters of hydrothermal ZnO nanowires for scale up applications

Zinc oxide nano-wires (ZnO NWs) are synthesized reproducibly with high yield via a low temperature hydrothermal technique. The influence of the growth duration time, growth temperature, zinc precursor and base concentration of Na₂CO₃ on the morphology of NWs is investigated. The growth products are characterised using scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL). SEM analysis shows that the optimum growth temperature is 140 °C and finds that length and diameter of ZnO NWs have a relationship with growth duration time and base concentrations of Na₂CO₃. In addition, it is reported that a high (～90%) yield of ZnO NWs can be synthesised via using any of three different precursors: zinc chloride, zinc acetate and zinc nitrate. TEM and XRD results indicate the high purity and the single crystalline nature of the ZnO NWs. XPS confirms the absence of sodium contaminants on the surface and indicates a near flat band surface condition. PL shows a large visible band in the yellow part of the spectrum, and a small exciton emission peak, indicating a large defect concentration, which is reduced after annealing in air.     

Effects of simultaneously doped and deposited Ag on the photocatalytic activity and surface states of TiO2

Ag-TiO2 catalysts with different Ag contents were prepared via a sol-gel method in the absence of light. Based on the characterizations of XRD, photoluminescence (PL), surface photovoltage spectroscopy (SPS), field-induced surface photovoltage spectroscopy (FISPS), and XPS as well as the evaluation of the photocatalytic activity for degrading rhodamine B(RhB) solutions, it was found that the Ag dopant promoted the phase transformation as well as had an inhibition effect on the growth of anatase crystallite. The PL and SPS intensities were decreased with increasing Ag content, indicating that the Ag dopant could effectively inhibit the recombination of the photoinduced electrons and holes. However, the active sites capturing the photoinduced electrons reduced, while the Ag content exceeded 5 mol %. At rather low Ag dopant concentrations, the migration and diffusion of Ag+ ions were predominant, while at rather high Ag dopant concentrations, the migration, diffusion, and reduction of Ag ions simultaneously occurred. The Ag-TiO2 photocatalysts with appropriate content of Ag (Ag species concentration is from about 3 to 5 mol %) possessed abundant electron traps so as to be favorable for the separation of the photoinduced electron-hole pairs, which could greatly enhance the activity of the photocatalysts. From the results of FISPS measurements, it could be found that the impurity bands and abundant surface states were introduced into the interfacial layer of TiO2 because of Ag simultaneously doping and depositing, which could improve the absorption capability for visible light of the photocatalysts.     

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．     

Experimental and theoretical study of temperature dependent exciton delocalization and relaxation in anthracene thin films

The spectroscopy of solid anthracene is examined both experimentally and theoretically. To avoid experimental complications such as self-absorption and polariton effects, ultrathin polycrystalline films deposited on transparent substrates are studied. To separate the contributions from different emitting species, the emission is resolved in both time and wavelength. The spectroscopic data are interpreted in terms of a three-state kinetic model, where two excited states, a high energy state 1 and a low energy state 2, both contribute to the luminescence and are kinetically coupled. Using this model, we analyze the spectral lineshape, relative quantum yield, and relaxation rates as a function of temperature. For state 1, we find that the ratio of the 0-0 vibronic peak to the 0-1 peak is enhanced by roughly a factor of 3.5 at low temperature, while the quantum yield and decay rates also increase by a similar factor. These observations are explained using a theoretical model previously developed for herringbone polyacene crystals. The early-time emission lineshape is consistent with that expected for a linear aggregate corresponding to an edge-dislocation defect. The results of experiment and theory are quantitatively compared at different temperatures in order to estimate that the singlet exciton in our polycrystalline films is delocalized over about ten molecules. Within these domains, the exciton's coherence length steadily increases as the temperature drops, until it reaches the limits of the domain, whereupon it saturates and remains constant as the temperature is lowered further. While the theoretical modeling correctly reproduces the temperature dependence of the fluorescence spectral lineshape, the decay of the singlet exciton appears to be determined by a trapping process that becomes more rapid as the temperature is lowered. This more rapid decay is consistent with accelerated trapping due to increased delocalization of the exciton at lower temperatures. These observations suggest that exciton coherence can play an important role in both radiative and nonradiative decay channels in these materials. Our results show that the spectroscopy of polyacene solids can be analyzed in a self-consistent fashion to obtain information about electronic delocalization and domain sizes.     

Photoluminescence Study on Charge Transfer Behavior of Poly(3‐hexylthiophene) and PCBM Blends

Charge transfer behavior of Poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl eser (PCBM) in solutions and in films were examined by photoluminescence (PL) spectroscopy. PL study in solutions indicated that separation distance between P3HT and PCBM affected charge transfer efficiency more seriously than the interface area issue between P3HT and PCBM. P3HT/PCBM film showed very effective photo‐induced charge transfer before post‐thermal annealing on the bi‐layer P3HT/PCBM film. Charge transfer efficiency was gradually diminished by the annealing‐induced phase separation between P3HT and PCBM as revealed by increasing PL emission intensity of P3HT.     

硫化镉量子点的合成及其光限幅效应

采用胶体化学法制备了四种表面修饰有不同有机功能团的CdS量子点(QDs),利用透射电子显微镜(TEM)、紫外-可见(UV-Vis)吸收光谱、光致发光(PL)光谱、开孔Z扫描技术分别研究了四种CdS样品的线性光学和非线性光学性能.结果表明:颗粒大小、表面形貌和缺陷浓度是影响CdS QDs非线性光学性能的主要因素.     

Effect of residual water and free volume on the glass‐transition temperature and heat capacity in polystyrene/poly(vinyl acetate‐co‐butyl acrylate) structured latex films

The dynamic heat capacity and glass‐transition temperature of polystyrene (PS)/poly(vinyl acetate‐co‐butyl acrylate) (VAc–BA) (50:50 w/w) structured latex films as a function of annealing time at 70, 77, and 85 °C were examined with modulated‐temperature differential scanning calorimetry. The PS and poly(vinyl acetate‐co‐n‐butyl acrylate) components were considered to be the cores and shells, respectively, in the structured latex. The dynamic heat capacity decreased with time. The glass‐transition temperatures of the PS and VAc–BA phases shifted to higher values after annealing. The results of thermogravimetry showed that there existed about 1.8% residual water in the films. The mean free volume and relative concentration of holes at room temperature (before and after annealing) and 85 °C, as a function of time, were obtained with positron annihilation lifetime spectroscopy (PALS). The PALS results indicated no significant change in free volume during annealing. It is believed that the loss, by diffusion, of residual water mainly caused a decrease in heat capacity and an increase in the glass‐transition temperatures. As little as 1.8% residual water in the structured latex films had a significant influence on the thermal properties. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1659–1664, 2001     

水溶性的高荧光CdTe/CdSeⅡ型核壳量子点的合成与表征

用L-半胱氨酸(L-cysteine)作为稳定剂,以制备的CdTe量子点为核模板,水相合成了具有近红外发光的Ⅱ型核壳CdTe/CdSe半导体量子点。实验考察了合成温度,核模板的尺寸和组分比等因素对合成高质量的CdTe/CdSe量子点的影响。用紫外-可见吸收和荧光光谱研究了合成的量子点的光学性质。在优化的合成条件下,荧光发射光谱在586～753nm范围连续可调,荧光量子产率高达68%;通过X-射线衍射(XRD),X射线光电子能谱(XPS)和透射电镜(TEM)对合成的Ⅱ型核壳CdTe/CdSe量子点进行了结构和形貌表征。