Time-resolved fluorescence of carbon nanotubes and its implication for radiative lifetimes

The temporal evolution of fluorescence from isolated single-wall carbon nanotubes (SWNTs) has been investigated using optical Kerr gating. The fluorescence emission is found to decay on a time scale of 10 ps. This fast relaxation arises from nonradiative processes, the existence of which explains the relatively low observed fluorescence efficiency in isolated SWNTs. From the measured decay rate and a determination of fluorescence quantum efficiency, we deduce a radiative lifetime of 110 ns.     

Measurement of the radiative and nonradiative decay rates of single CdSe nanocrystals through a controlled modification of their spontaneous emission

We present a simple method to measure the radiative and nonradiative recombination rates of individual fluorescent emitters at room temperature. By placing a single molecule successively close and far from a dielectric interface and simultaneously measuring its photoluminescence decay and its orientation, both the radiative and nonradiative recombination rates can be determined. For CdSe nanocrystals, our results demonstrate that the fluorescence quantum efficiency, determined at the single-molecule level, is 98% in average, far above the value expected from conventional ensemble experiments. The bidimensional nature of the transition dipole is also directly evidenced from a single-particle measurement.     

Radiative and nonradiative recombination times in semiconducting films

The radiation emitted spontaneously by a semiconductor which has been excited for a very short time decays exponentially with a time constant that depends on the recombination rate of electrons and holes. This recombination rate is the combination of radiative and nonradiative transition rates between conduction and valence bands of the semiconductor. The radiative recombination rate depends on the density of states of the electromagnetic field, which can be made to be dependent on the geometry. In this paper, we report on the dependence of the fluorescence lifetime upon the thickness of active thin films. For systems in which the radiative recombination rate is dominant over the nonradiative ones, the total recombination time can be changed by suitable modifications of the thickness of the film. In this situation, the nonradiative rate can be evaluated. We present experimental results for the case of cadmium sulphide (CdS) thin films.     

Bolometric observation of nonradiative decay of surface plasmons in silver

A bolometric technique was used to observe the nonradiative decay of surface plasmons in a silver film. This technique allowed us to separate the radiative and nonradiative relaxations of the plasmons and to determine the radiative quantum efficiency. It is suitable for both cw and pulsed laser beams and for both polarized and nonpolarized light.     

Y_2O_3∶Eu~(3+)纳米球的可控合成及尺寸效应所影响的发光性质

采用均匀沉淀法,通过改变稀土离子与尿素的量比成功合成了粒径分别为80,55,40 nm的Y_2O_3∶Eu~(3+)纳米球样品。通过X射线衍射(XRD)、场发射扫描电镜(FE-SEM)和发光光谱对不同尺寸纳米球的晶体结构、微观形貌和发光性质做了分析,对Y_2O_3∶Eu~(3+)纳米球的生长过程进行了研究。根据Judd-Ofelt理论,利用Eu~(3+)的发射光谱和荧光衰减等数据,计算了5D0→7FJ能级的辐射跃迁速率和荧光分支比,计算得到Y_2O_3基质材料的折射率为1.80以及不同粒径样品的光学跃迁强度参数。最后分析了5D0能级荧光发射与温度之间的依赖关系,结果证明了荧光温度猝灭行为符合Crossover过程,并通过阿伦尼乌斯公式非线性拟合获得了激活能,粒径为80,55,40 nm的Y_2O_3∶Eu~(3+)纳米球样品的活化能分别为0.201,0.193,0.200 eV。     

Recombination processes in structures with GaN/ALN quantum dots

Mechanisms of the generation and the radiative and nonradiative recombination of carriers in structures with GaN quantum dots in the AlN matrix are studied experimentally and theoretically. Absorption, stationary and nonstationary photoluminescence of quantum dots at different temperatures are investigated. It is found that the photoluminescence intensity considerably decreases with the temperature while the photoluminescence kinetics weakly depends on the temperature. The photoluminescence kinetics is shown to be determined by radiative recombination inside quantum dots. A mechanism of nonradiative recombination is proposed, according to which the main reason for the thermal quenching of photoluminescence is nonradiative recombination of charge carriers, generated by optical transitions between quantum dots and wetting layer states.     

Effect of hydroxyl groups on Er doped Bi2O3-B2O3-SiO2 glasses

A series of Er³⁺-doped Bi₂O₃-B₂O₃-SiO₂-Na₂O glasses with different hydroxyl groups were prepared and the interaction between the Er³⁺ ions and OH groups was investigated. Infrared spectra were measured in order to calculate the exact content of OH groups in samples. The observed increase of the fluorescence lifetime with the oxygen bubbling time has been related to the reduction in the OH content concentration evidenced by infrared (IR) absorption spectra, which confirmed that the OH groups were dominant quenching centers of excited Er³⁺ and a cause of concentration quenching of 1.5 μm band emission. Various nonradiative decay rates from ⁴I_13/2 of Er³⁺ with the change of OH content were determined from the fluorescence lifetimes and radiative decay rates, which were calculated on the basis of Judd-Ofelt theory.     

Specific features of the temperature quenching of luminescence of self-trapped excitons in alkali halide crystals under low-temperature deformation

The activation energy of temperature quenching of luminescence of self-trapped excitons in alkali halide crystals subjected to low-temperature uniaxial deformation is evaluated experimentally. It is found that an increase in the activation energy is observed in the following series of crystals: KBr → NaCl → KI → NaBr → CsBr → RbI. The effect of enhancement of intrinsic luminescence of alkali halide crystals due to the lowering of the symmetry of the crystal lattice under low-temperature uniaxial deformation is interpreted by analyzing the observed increase in the activation energy that characterizes the height of the potential barrier separating channels of radiative and nonradiative decay (with the formation of radiation defects) of self-trapped excitons.     

Phosphorescence of pi-conjugated oligomers and polymers

We observed phosphorescence from a ladder-type poly-(para-phenylene) and an analogous oligomer containing five phenylene rings. The spectra are similar to the intrinsic fluorescence spectra and bear out a singlet-triplet splitting of 5000 cm(-1) (polymer) and 6800 cm(-1) (oligomer). Phosphorescence decay of the polymer occurs on a 10-100-micros scale obeying a power law and suggestive of nonradiative quenching, while that of the oligomer is asymptotically exponential with an intrinsic decay time of approximately 250 ms. The polymer also exhibits delayed fluorescence. It originates from delayed recombination of geminate electron-hole pairs rather than from triplet-triplet annihilation.     

吲哚美辛与牛血清白蛋白结合作用的研究

应用紫外光谱和荧光光谱研究了生理条件下吲哚美辛与牛血清白蛋白的相互作用机理,确定静态猝灭和非辐射能量转移是导致吲哚美辛对BSA荧光猝灭的两大原因。利用荧光猝灭反应求得药物与牛血清白蛋白之间的结合常数和结合位点数,根据热力学参数确定它们之间的作用力类型,依据能量转移理论计算二者相互结合时给体-受体间的距离和能量转移效率,结合紫外吸收光谱和荧光光谱结果, 探讨了吲哚美辛与牛血清白蛋白的相互作用模式。     

Investigation of the Heavy-Atom Effect on the Spectral-Luminescent Properties of Dichloroanilines

The influence of the chlorine atom position on the spectral, geometric, and photophysical characteristics of free molecules of dichloroaniline is studied by electron spectroscopy, fluorescence, and quantum chemistry. A chlorine atom included in the aniline aromatic ring is shown to exhibit properties inherent in a heavy atom, that is, the radiation is dominated by phosphorescence. According to quantum-chemical calculations, the quenching of fluorescence is due to the fact that the efficiency of the intersystem crossing conversion proves to be much higher than the radiative decay rate of the S ₁ state.     

Enhancement and quenching of single-molecule fluorescence

We present an experimental and theoretical study of the fluorescence rate of a single molecule as a function of its distance to a laser-irradiated gold nanoparticle. The local field enhancement leads to an increased excitation rate whereas nonradiative energy transfer to the particle leads to a decrease of the quantum yield (quenching). Because of these competing effects, previous experiments showed either fluorescence enhancement or fluorescence quenching. By varying the distance between molecule and particle we show the first experimental measurement demonstrating the continuous transition from fluorescence enhancement to fluorescence quenching. This transition cannot be explained by treating the particle as a polarizable sphere in the dipole approximation.     

Visible fluorescence induced by the metal semiconductor transition in composites of carbon nanotubes with noble metal nanoparticles

We show that single-walled carbon nanotube (SWNT) bundles emit visible fluorescence in the presence of noble metal nanoparticles and nanorods in the solid state. Conductivity measurements with metallic nanotubes, isolated from pristine SWNTs, show that they become semiconducting in the presence of the metal nanoparticles. Nanoparticle binding increases the defects in the nanotube structures which is evident in the Raman spectra. The metal-semiconductor transition removes the nonradiative decay channels of the excited states enabling visible fluorescence. Nanotube structures are imaged using this emission with resolution below the classical limits.     

Modeling of dual fluorescence kinetics for 9-anthryl-substituted oligothiophenes

Expressions for time-dependent level populations in four- and five-level molecular models are obtained for the case of radiative and nonradiative decay from an initially populated state corresponding to the highest energy of the molecule. The two lowest energy levels in the models are assigned to vibrational levels of a molecular subsystem in the ground state; the others, to levels of the molecule in the excited electronic state. Examples of applying the obtained expressions to establish the formation mechanism for dual fluorescence pulses that accompany the phototransfer of a H-bond proton and other conformational transformations of molecules are presented.     

Silver nanoparticle size–dependent measurement of quantum efficiency of Rhodamine 6G

The plasmonic absorption band of silver nanoparticles in the visible range of electromagnetic spectrum has been successfully exploited to alter the emission characteristics of the Rhodamine 6G dye molecule. The influence of the nanoparticle size on the fluorescence quantum yield of Rhodamine 6G is interrogated via steady state fluorescence as well as dual beam thermal lens technique. The potential of the thermal lens technique that probe nonradiative path in contrast to radiative path exhibited in the fluorescence spectra as a complementary method to measure the quantum yield of a dye molecule is exploited. Analysis of the results clearly indicates that the particle size and the spectral overlap between the emission spectra of Rhodamine 6G, and absorption spectra of the silver nanoparticles determine the quantum yield value of dye–nanoparticle mixture.     

Surface plasmons in porous gold films

The surface plasmon resonance effects in porous gold (por-Au) films—nanocomposite porous films containing an ensemble of disordered gold nanoparticles—have been investigated by modulation-polarization spectroscopy. Por-Au films have been obtained by pulsed laser deposition (using a direct particle flow from an erosion torch formed by a YAG:Nd³⁺ laser in argon). The spectral and angular dependences of the polarization difference ρ(λ, θ) of internal-reflection coefficients of s- and p-polarized radiation in the Kretschmann geometry and the spectral dependences of isotropic reflection angles at ρ(θ) = 0 are measured. Two types of surface plasmon resonance are found: one occurs on isolated nanoparticles (dipole and multipole modes), and the other is due to the dipole–dipole interaction of neighboring nanoparticles. The frequency of electron plasma oscillations for the nanoparticle ensemble and the frequencies and decay parameters of resonances are determined. Dispersion relations for the radiative and nonradiative modes are presented. The negative sign of the dispersion branch of nonradiative modes of dipole–dipole interaction is explained by the spatial dispersion of permittivity. The relationships between the formation conditions of the films, their structure, and established resonance parameters (determining the resonant-optical properties of films) are discussed.     

热辐射对热团簇衰变率和丰度的影响

本文量化了辐射冷却对单分子衰变速率、热簇以及非特定激发能量的分子的影响.检测出两种不同的区域,可以通过发射光子的能量大小进行定义,并根据光子发射速率常数和颗粒的热性质确定它们之间的边界.此外,通过丰度光谱计算了相当于小光子能量的连续冷却情况.两种不同区域分别是连续性冷却和单分子衰变的单光子猝灭.辐射效应通过重新定义每个单独的团簇用于进行蒸发的时间进行参数化,可用有效辐射时间常数来表示.