基于电荷转移过程的PAN-C60共聚物薄膜的时间分辨荧光研究

利用吸收光谱和皮秒时间分辨荧光研究PAN－C60星状共聚物的电荷转移过程。PAN－C60共聚物的吸收和荧光光谱结果显示共聚物中存在着电荷转移过程。时间分辨荧光结果表明PAN的荧光衰减遵循双指数衰减规律（一快过程160ps和一慢过程1500ps)，快衰减过程主要来源于聚合物中主链间相互作用产生的空间间接极化子对的影响，慢变过程主要来源于单重态激子的辐射跃迁弛豫。在共聚物中，C60分子的存在除导致PAN激发态寿命缩短外，还影响聚合物链间的相互作用，C60分子对PAN荧光猝 灭作用主要通过慢变过程影响的，而对PAN的空间极化子对的影响主要与其快衰减过程有关。     

水溶性TGA-CdTe量子点的超快弛豫动力学过程探究

本文以三个不同粒径(1^#:2.3 nm, 2^#:2.8 nm和3^#:3.5 nm)的巯基乙酸包覆的CdTe量子点(thioglycolic acid capped CdTe quantum dots, TGA-CdTe QDs)样品为研究对象, 其时间相关单光子计数(time-correlated single photon counting, TCSPC)实验得到的时间分辨光谱显示, 三个量子点的荧光平均寿命依次是～6 ns, ～10 ns和～12 ns, 其动力学过程包括慢过程和快过程两部分. 随其粒径尺寸的增加, 其慢过程延长, 快过程在变短. 然后, 通过瞬态吸收和荧光上转换两种基于飞秒的时间分辨光谱技术, 对TGA-CdTe量子点的带间弛豫过程做了探究. 实验结果显示, 三个TGA-CdTe量子点样品, 随其粒径增大, 最高激发态和最低激发态填充速率减慢, 其中, 最高激发态从0.33 ps增加至0.79 ps; 最低激发态从0.53 ps增至～1 ps. 另外, 由瞬态吸收和荧光上转换两种时间分辨手段相结合, 可得到CdTe量子点带间弛豫的完整图像, 结果显示了TGA-CdTe 量子点的一个本征特征:即在基态漂白恢复过程中的初始上升阶段, 荧光上转换信号要慢于瞬态吸收信号. 这可以为量子点在光电转换应用上提供帮助.     

高等植物外周捕光天线LHCⅡ中的超快光动力学过程

利用飞秒抽运探测技术及时间分辨荧光(TRPL)等光谱技术对高等植物LHCⅡ中的超快光动力学过程进行了研究。在其时间分辨荧光光谱中表现出了明显的各向异性特性。实验上观察了LHCⅡ中色素间的能量传递过程,由飞秒动力学发现,单体内Chlb到邻近的Chla之间的能量传递在200～300fs的时间尺度,Chla激子带间的能量弛豫发生在几百飞秒,不同单体Chla分子间能量分布过程在几个皮秒。而时间分辨荧光和飞秒动力学过程中上百皮秒的慢过程归属于不同聚集体间的能量平衡过程或分子构象变化。     

Ultrafast dynamics process of platinum nanoparticles under femtosecond laser

The energy relaxation dynamics process of Pt nanoparticles with a diameter of 25 nm after a 400-nm femtosecond laser excitation was investigated using pump-probe technology with 130 fs laser pulse. Experimental results show that the process includes a fast decay with time constant of 850 fs and a slow decay with time constant of 9 ps. Theoretical discussion indicates that the former results from electron-phonon coupling process, while the latter is from phonon-phonon coupling process.     

利用BaF2晶体快速闪烁发光性质改进正电子湮没寿命谱仪

测量BaF2晶体闪烁发光长短两种寿命成分的光电子产额,利用它的短成分发光极快的特点研制核辐射探测中的定时探测器,采用于正电子湮没寿命谱仪中使谱仪的时间分辨率由FWHM=270ps(ps:微微秒)改进到190ps(计数效率不改变)或者使计数效率提高10倍(时间分辨率相同)。     

The kinetics of exciton photoluminescence in mercuric iodide

Time-resolved photoluminescence (TRPL) of red mercuric iodide single crystal is measured at low temperatures and its two-photon luminescence is measured at room temperature. Sharp near band-gap luminescence is observed around 530 nm and was ascribed to radiative annihilation of free and bound excitons; the phonon replica of exciton luminescence are found between 533 and 540 nm at low temperatures. TRPL experiment reveals that near band-gap luminescence comprises fast and slow decay components and shows the different relaxation processes between free and bound exciton annihilation. Luminescence of bound excitons steeply lowers with increasing temperature and disappears about 40 K. A luminescence tail band is observed around 540 nm that is ascribed to defects in the anion sublattice. The temporal behavior of the tail band is described by rate equations very well. A broad luminescent band appears at 630 nm. The decay curves suggest that the luminescence is ascribed to the radiative recombination of donor-acceptor pairs and there are two kinds of mechanisms to control the decay. At room temperature, a luminescent band appears at the band-gap region, which shows the band-gap at room temperature is about 2.125 eV.     

Yb:YAG晶体性能实验测量

为了测量脉冲时间宽度小于20 ns时的射线时间分辨图像,发展了新型无机闪烁体Yb:YAG,并实验测量了晶体的发光衰减时间、X射线激发发光光谱、相对发光效率和空间分辨等性能,研究了Yb:YAG晶体的发光性能。实验表明,Yb:YAG发光有三种衰减成分,快成分衰减常数为1.2 ns,慢成分衰减常数与射线种类有关;X射线激发发光光谱在250~800 nm范围,有三个发光峰,分别为320,380和500 nm,且320 nm处强度最大;相对发光效率为1900 ph/MeV;使用钨分辨卡测得Yb: YAG空间分辨能力为2 lp/m,使用刀口法测得空间调制传递函数为0.5时的频率为0.7 lp/mm。结果说明Yb:YAG晶体性能能够满足所需测量要求。     

Ultra-Fast Decay Process of Electrons in LiNbO3 Crystal Induced by Femtosecond Pulse

Temporal evolution of absorption induced by single femtosecond pulse （13Ors, 800nm） with high intensity in LiNbO3 is obtained using the probe shadow imaging technique in order to investigate light-induced electron relaxation processes. By saturating the polaron density with a high intensity laser pulse, ultra-fast decay process on picosecond time scale is observed. The decay time constant is about 141 ps and it is attributed to the direct interband electron-hole recombination process.     

Picosecond time resolved fluorescence spectroscopy study of aggregation of porphyrin derivative Mn(3,4,5-OMeTPP)Cl

The picosecond time-resolved fluorescence spectrum I(, t) of the porphyrin derivative Mn(3,4,5-OMeTPP)Cl is measured. Experiments show that the fluorescence relaxation of the concentrated sample solution is composed of a fast (ps), a moderately fast (100 ps) and a slow (ns) decay process. Furthermore, the fluorescence spectra for various times after excitation have different shapes. Detailed analysis shows that the fluorescence is composed of three components with different relaxation times and spectrum shapes. The three components are attributed to monomers, dimers, and aggregates respectively.     

PSⅡ颗粒复合物飞秒分辨低温荧光动力学研究

采用飞秒时间分辨荧光光谱学对PSⅡ颗粒复合物在83 K,160 K,273 K下进行研究,实验表明随温度升高,光谱加宽.并且发现在PSⅡ颗粒复合物中至少存在以下几种特征Chl分子：Chl b640639,Chl b645640,Chl a663660,Chl a668667,Chl a676673,Chl a681680,Chl a682680/681,Chl a688/689684,685,Chl a698688.在不同的温度下,参与能量传递的色素分子传能途径各不相同,但都有一个共同点：在到达反应中心之前能量传递高效进行,绝大多数能量传递到了反应中心,而在680 nm之后的波段,能量损耗明显增大,这是由于电子传能受阻,能量绝大多数以荧光形式耗散.对荧光衰减曲线进行时间拟合,得到四组时间常数：30～40 ps,260 ps,550～670 ps,1～8 ns.几个ns的长寿命组分,反映了两个能量传递过程,即与基对态P680＋pheo－,以及能量传递过程中Chl a分子由激发态辐射荧光衰退到基态以辐射荧光形式丢失能量的过程有关.550～670 ps的时间组分,反映的是部分电荷重组的过程.260 ps的组分只在83 K出现,应归于LHCⅡ中的Car分子经中间传递体传能到Chl b 639分子后继续将能量传递到反应中心P680的时间.30～40 ps的时间组分为LHCⅡ中的Chl分子吸收光能后通过一系列中间体将能量传递到反应中心,Chl a680/681分子的能量传递过程.     

苯乙炔分子电子激发态超快动力学研究

采用飞秒时间分辨质谱技术结合飞秒时间分辨光电子影像技术研究了苯乙炔分子电子激发态超快非绝热弛豫动力学.用235 nm光作为泵浦光,将苯乙炔分子激发到第二激发态S2,用400 nm光探测激发态的演化过程.时间分辨的母体离子的变化曲线用指数和高斯函数卷积得到不同的两个组分,一个是超快衰减组分,时间常数为116 fs,一个是慢速组分,时间常数为106 ps.通过分析时间分辨的光电子影像得到光电子动能分布,结合时间分辨光电子能谱数据发现,时间常数为116 fs的快速组分反映了S2态向S1态的内转换过程.实验还表明S1态通过内转换被布局后向T1态的系间窜跃过程为重要的衰减通道.本工作为苯乙炔分子S2态非绝热弛豫动力学提供了较清晰的物理图像.     

Transient optical properties of excimer-laser-irradiated polyimide

Reflectivity, transmission and scattering measurments in ArF (193 nm) excimer-laser irradiated polyimide are reported. The time dependence of transient changes in all three quantities were measured together for the first time, confirming a transient refractive-index change in the first 150 ns after irradiation. The relaxation time of the effect was measured and found to consist of both a fast and slow component similar to that previously reported in acoustic wave measurements. The fast decay in about 60 ns and the slow decay is 115 ns. Several potential mechanisms are examined which may explain the result.     

超短脉冲激光场中间二氯苯的激发态动力学

利用飞秒时间分辨的飞行时间质谱技术研究了间二氯苯的激发态动力学.间二氯苯分子吸收一个200 nm或者267 nm的光子被抽运到激发态,随后再吸收多个800 nm的光子被电离.实验获得了电离产生的离子质谱信号及其随抽运探测激光延迟时间的变化曲线.在200 nm时,分子被抽运到激发态(π,π*),可观察到三个相互竞争的解离通道的寿命:内转换到排斥态(n,σ*)或者(π,σ*)并发生快速解离,其寿命约(0.15±0.01)ps;内转换到基态的高振动态,能量在基态"热"振动态间弛豫的寿命约为(4.94±0.08)ps;系间窜越到相邻的三重态从而发生预解离过程,其寿命约为(110.09±4.33)ps.在267 nm时,分子被抽运到第一激发态的低振动态,可观察到一个长寿命(约(1.06±0.05)ns)的系间窜越过程.除此之外,在碎片离子信号中还观察到了激发态与基态的高振动态之间的内转换过程.     

多晶碲化锌薄膜载能子超快动力学实验研究

利用双波长飞秒激光抽运-探测实验方法测量了掺氮多晶ZnTe薄膜在飞秒激光加热情况下载能子超快动力学过程. 采用包含电子弛豫过程和晶格加热过程的理论模型拟合实验数据, 二者符合得很好. 拟合得到10 ps以内影响掺氮多晶ZnTe薄膜表面超快反射率变化的三个弛豫过程的时间常数均为亚皮秒量级. 其中, 正振幅电子弛豫过程是由电子-光子相互作用引起的载流子扩散和带间载流子冷却过程, 负振幅电子弛豫过程是由缺陷造成的光激载能子的俘获效应引起的, 晶格加热过程主要通过电子-声子耦合过程进行的.     

Vibrational dynamics of the CN stretching mode of [Ru(CN)_6]~(4-) in D_2O studied by nonlinear infrared spectroscopy

We have studied vibrational dynamics of the T1u mode of the CN stretching mode of [Ru(CN)6 ]4- in D2O by infrared(IR) nonlinear spectroscopy such as an IR three-pulse photon echo experiment and polarization-sensitive IR pump-probe spectroscopy. The isotropic component of the pump-probe signal shows a bi-exponential decay with time constants of 0.8 ps and 20.8 ps. The fast and slow components correspond to the rapid equilibration between the T1u mode and the Raman active modes of the CN stretching mode and the vibrational population relaxation from the v=1 state of the T1u mode,respectively. Anisotropy of the pump-probe signal decays with a time constant of 3.1 ps,which is due to the time evolution of the superposition states of the triply degenerate T1u modes. Three pulse photon echo measurements showed that the time correlation function of the frequency fluctuation decays bi-exponentially with time constants of 80 fs and 1.4 ps. These time constants depend only on the solute and are independent of the solvent,whereas the amplitudes depend on both the solute and solvent.     

Temperature-dependent luminescence dynamics for ZnO thin films

The paper presents the photoluminescence investigation of zinc oxide thin films. A high quality ZnO films fabricated by dip-coating (sol–gel) method were grown on quartz wafers. The films with different thickness (number of layers) were annealed at different temperatures after the preparation process. It was found that high quality, transparent ZnO thin films could be produced on quartz substrates at relatively low annealing temperature (450–550  $^{\circ }\mathrm{C}$ ). The dependence of the ZnO thin film quality was studied by X-ray diffraction and atomic force microscopy techniques. Optical properties were investigated by classic and time-resolved photoluminescence (TRPL) measurements. Photoluminescence spectra allowed us to estimate energy of the free excitons, bond excitons and their longitudinal optical (LO) phonon replicas as a function of the annealing temperature. An innovative TRPL technique let us precisely measure the decay time of the free- and bond excitons’ in the real time. TRPL measurements as a function of temperature reveal a biexponential decay behavior with typical free/bound exciton decay constants of 970/5310 ps for the as-grown sample and 1380/5980 ps after annealing process. Presented spectra confirm high structural and optical quality of investigated films. We proved that the thermal treatment improve both optical and structural quality and extend the photoluminescence’s lifetimes. The obtained experimental results are important for identification of exciton’s peaks and their LO phonon replicas for the investigated ZnO films.     

Visible and near-infrared excited-state dynamics of single-walled carbon nanotubes

Excited-state lifetimes of isolated single-walled semiconducting carbon nanotubes (SWNTs) have been measured for the first time; these excited states, observed over the 400- to 1800-nm spectral domain, possess lifetimes that range from several ps to more than 100 ps. Sub-ps to ps decay components are assigned to relaxation in SWNT bundles. Interrogation of the samples with different SWNT mean diameters further confirms the dependence of the excited-state lifetime on roll-up vector. The ratio of fast and slow decaying component contributions in the first van Hove band can be viewed as a measure of the bundle content. PACS 78.67.Ch; 78.47.+p; 61.46.+w; 73.22.-f     

偏置电场对聚对苯乙烯激发态弛豫特性的影响

为探讨洞悉电场对有机发光二极管电致荧光量子效率的影响,通过激发-探测超快光谱技术研究了激子在电场下的瞬态行为.与单重态激子相应的激发态在230 μJ/cm2激发强度下,显示了快慢两个弛豫过程. 快慢组分的权重因子及快组分弛豫时间常数是电场相关的, 在6.4×10⁵ V/cm的电场下,与无偏置电场相比,激子的快组分弛豫时间加速,快组分的权重因子由22%增加为72%,约50%的初始激子又通过电场而离解. 慢组分是电场无关的,其弛豫时间常数为890 ps. 实验结果还揭示了由激发光所产生的长程声学声子,其声速为17 /ps. 关键词： 聚对苯乙烯 超快光谱 激子 有机发光二极管     

上海光源XAFS线站时间分辨X射线激发发光谱实验系统

介绍了上海光源XAFS线站（BL14W1）的时间分辨X射线激发发光光谱（TRXEOL）实验系统。该系统基于时间相关单光子计数法的原理设计,以同步辐射光源的脉冲特性及其良好的时间结构为基础,通过集成定时系统、光谱仪系统和核电子学系统,在国内同步辐射装置上首次实现了TRXEOL实验方法。定时系统提供同步触发电脉冲,用来标志X射线脉冲打到样品上的时刻,同步精度约6 ps,延时分辨率5 ps;光谱仪经光电探测器把样品发光信号转换成电脉冲,核电子学系统对定时电脉冲和发光电脉冲之间的时间差进行统计分析,可得到样品的发光衰减曲线,再结合光谱仪的扫描控制和数据获取系统,可得到样品的TRXEOL光谱。利用该实验系统可以测量发光样品的普通XEOL光谱、发光衰减曲线和TRXEOL光谱。用ZnO纳米线样品,进行了实验验证。实验得到的普通XEOL光谱能够明显区分该样品在390和500 nm处的两个发光中心;得到的发光衰减曲线能够区分小于2 ns的快发光过程和200 ns的慢发光过程;分别在0～1, 2～200和0～200 ns时间窗口内测量得到了ZnO纳米线样品的TRXEOL光谱,在这3个发光时间带内得到了对应的发光信息;ZnO纳米线样品发光衰减曲线快发光峰的半高宽约为0.5 ns,证明了TRXEOL系统的最小时间分辨率小于1 ns。该系统在国内同步辐射装置上提供了用于研究发光材料的TRXEOL实验方法,该方法与发光模式的XAFS方法相结合,可更深入的研究发光材料的发光行为。整个实验平台操作简便、工作稳定可靠,不仅为发光材料的研究提供了研究手段,还为进一步开展发光模式XAFS和TRXEOL成像等实验方法提供技术前提。     

PPV衍生物的激发态动力学特性研究

利用共振飞秒光学克尔效应研究了C10－PPV溶液的非线性光学响应。实验结果表明，在共振激发条件下，C10－PPV挑学克尔效应信号表现为快速上升和随后的驰豫过程，其驰豫过程由两部分组成，一个200fs的快过程和一个400ps的慢过程。通过比较C10－PPV和掺杂C60后的C10－PPV荧光光谱，400ps的慢过程可归属为聚合物链内单重态激子在不同共轭段间的迁移过程。