Single photon emission from a single molecule

Photon emission from a single molecule at room temperature exhibits nonclassical features. Continuous wave fluorescence excitation provides antibunching in the emitted photons sequence as a signature of the property to only emit one photon at a time. A short pulsed excitation can then produce single photons on demand, with an overall quantum efficiency up to 4.5% in our experimental setup. Direct measurement of the Mandel parameter Q(T) for an observation period of duration T follows a subpoissonian statistics on short time scale and superpoissonian statistics on longer time scale. The latter is attributed to blinking in the fluorescence due to the occurence of a metastable molecular triplet state. To cite this article: F. Treussart et al., C. R. Physique 3 (2002) 501–508.     

Observation of triplet doubly excited states in single photon excitation from ground state helium

We have observed, for the first time, LS-forbidden triplet doubly excited states, in single photon excitation of ground state helium, below the second ionization threshold. These states are identified as (3)D(o) and (3)P(o) and their excitation is due to spin-orbit interaction that mixes them with the optically allowed (1)P(o) states. This observation is possible due to the very high efficiency in detecting metastable atoms created after the fluorescence decay of the doubly excited states, and the new capabilities of third generation synchrotron vacuum ultraviolet sources with high resolution beam lines.     

Kinetics of Triplet-Triplet Annihilation in Organic Glasses

In the present paper, the results of the investigation of the decay kinetics of delayed luminescence of organic glasses are presented. A strong deviation of the decay of both phosphorescence and annihilation delayed fluorescence from the exponential law is observed. This effect is shown to be due to the relaxation process of electronic excitation energy in the system with large energetic disorder. At the same time, the presence of two time intervals in which the rate coefficient for triplet-triplet annihilation (TTA) reaction shows different dependence on time is observed. On a short time scale the classical behavior is observed, i.e., the reaction is well described by the second-order equation with a time-independent rate coefficient. At the limit of long times, we have strong dependence of rate coefficient on time, i.e., the electronic excitation energy transport is dispersive. It is shown that behavior observed for the rate coefficient for TTA reaction is due to the relaxation process (on short time scale) and the equilibrium energy migration (in long time limit).     

A single molecule as a probe of optical intensity distribution

Single terrylene molecules embedded in microscopic p-terphenyl crystals are identified with the technique of fluorescence excitation spectroscopy. By use of the architecture of a scanning-probe microscope at T = 1.4 K , a single molecule is scanned through an excitation laser beam while the fluorescence signal is recorded. In this manner we have mapped the intensity distribution in a one-dimensional optical standing wave, demonstrating the potential of a single molecule as a nanometric probe. We discuss future experiments aimed at combining the high spatial and spectral sensitivity of a single molecule.     

Detection and characterization of single molecules in aqueous solution

Using a confocal microscope with a single-photon avalanche photodiode as detector, we studied photon bursts of single Rhodamine 6G (R6G) and Rhodamin B-zwitterion (RB) molecules in aqueous solution by excitation of the lowest excited singlet stateS ₁ with a frequency-doubled titanium: sapphire laser. Multichannel scaler traces, the fluorescence autocorrelation function and fluorescence decay times determined by time-correlated single-photon counting have been measured simultaneously. The time-resolved fluorescence signals were analyzed with a maximum likelihood estimator. Fluorescence lifetime patterns in steps of 100 ps were generated by convolution with the excitation pulse. The lifetime of theS ₁ state was derived from the Kullback-Leibler minimum discrimination information. We are able to demonstrate for the first time identification of two different single dye molecules via their characteristic fluorescence lifetimes of 1.79 ± 0.33 ns (RB) and 3.79 ± 0.38 ns (R6G) in aqueous solution.Dedicated to Prof. F. P. Schäfer on the occasion of his 65th birthday.On leave from Department of Physics, Mokwon University, Taejon, 301-729, Korea     

Nonclassical photon statistics in single-molecule fluorescence at room temperature

The fluorescence of single terrylene molecules in a crystalline host is investigated at room temperature by scanning confocal optical microscopy. Photon arrival times are analyzed in terms of interphoton time distributions, second order correlation functions, and the variance of the photon number probability distribution. Antibunching at short times and bunching behavior for longer times is observed, associated with sub- and super-Poissonian statistics, respectively. A rate-equation analysis of the molecular level populations indicates an accelerated reverse intersystem crossing.     

Optical tailoring of electron spin coherence in quantum dots

We address the precession of an ensemble of electron spins, each confined in a (In, Ga)As/GaAs self-assembled quantum dot. The quantum dot inhomogeneity is directly reflected in the precession of the optically oriented electron spins about an external magnetic field, which is subject to fast dephasing on a nanoseconds time scale. Proper periodic laser excitation allows synchronization of the electron spin precessions with the excitation cycle. The experimental conditions can be tailored such that eventually all (about a million) electron spins that are excited by the laser precess with a single frequency. In this regime the ensemble can be exploited during the single electron spin coherence times being in the microseconds range.     

Fluorescence enhancement of radix angelica dahurica by binding to single silver sphere

We present a theoretical study of the influence of a single silver sphere on the fluorescence of radix angelica dahurica,which is a kind of traditional Chinese medicine. The enhancement factors of the excitation and the relaxation processes are deduced. The excitation can be enhanced more than 100 times at 315 nm. The enhancement factor of the emission can reach up to 9 at a center wavelength of 400 nm.     

Bunching and antibunching in the fluorescence of semiconductor nanocrystals

The fluorescence of single-colloidal CdSe quantum dots is investigated at room temperature by means of the autocorrelation function over a time scale of almost 12 orders of magnitude. Over a short time scale, the autocorrelation function shows complete antibunching, indicating single-photon emission and atomiclike behavior. Over longer time scales (up to tens of seconds), we measure a bunching effect that is due to fluorescence intermittency and that cannot be described by fluctuations between two states with constant rates. The autocorrelation function also exhibits nonstationary behavior related to power-law distributions of On and Off times.     

电介质球复合纳米天线对荧光定向发射的增强

在纳米光子学中,提高荧光物质的定向发光强度是许多应用要解决的关键问题。为了优化电介质纳米天线的荧光增强能力,本文提出了一种由硅纳米球二聚体与TiO 2微球组成的电介质球复合纳米天线。通过时域有限差分法,本文分别从量子产率增强、荧光收集效率增强以及荧光激发率增强3个方面研究了该复合纳米天线对荧光的增强效果。结果表明,这种复合纳米天线不仅可以解决单个TiO 2微球增强荧光时量子产率较低的问题,还可以弥补单个硅纳米球二聚体增强荧光时荧光收集效率较差的不足。该复合纳米天线可使CdSe量子点的量子产率增强约4倍、荧光收集效率增强约2倍。此外,由于硅纳米球二聚体与TiO 2微球对荧光激发过程具有增强效果,该复合天线最终可以产生较高的荧光定向增强倍数。在量子点发光的中心波长523 nm处,荧光定向增强约为3064倍。     

Exciton-spin memory with a semiconductor quantum dot molecule

We report on a single photon and spin storage device based on a semiconductor quantum dot molecule. Optically excited single electron-hole pairs are trapped within the molecule, and their recombination rate is electrically controlled over 3 orders of magnitude. Single photons are stored up to 1 μs and read out on a subnanosecond time scale. By using resonant excitation, the circular polarization of individual photons is transferred into the spin state of electron-hole pairs with a fidelity above 80%, which does not degrade for storage times up to the 12.5 ns repetition period of the experiment.     

基于时间相关单光子计数的荧光寿命成像技术

采用时域法中的时间相关单光子计数方法记录荧光寿命,时间相关单光子计数采用多波长通道同时记录荧光光子数,可以提高计数效率和信息量,还可以在稳态图像中分离不同荧光团,形成4维图像。并采用多光子激发技术,利用长波长光源发出的两个或多个光子可以激发出一个短波长的光子。多个光子必须几乎同时到达激发点,才能提供被激发分子足够的能量以产生荧光。多光子激发波长较长,生物组织对其散射减小,因而可以穿透到更深层的组织,从而提高荧光成像深度和空间分辨力,并减少对活体样品的损伤。     

基于SiPM单光子探测器的荧光光谱仪研究

为了解决激光诱导荧光检测系统存在的光学结构复杂、体积大、成本高以及灵敏度不足等主要问题,研制了一种高灵敏、小型化的荧光光谱仪。该光谱仪以349 nm半导体激光器作为激发光源,采用正交型光路,将4×4窄带滤光片阵列与具有单光子灵敏度的硅光电倍增器（SiPM）阵列耦合,可实现光谱信息的多通道探测,具备结构紧凑、成本较低以及稳定性好等优点。以荧光素钠为测试样品,对光谱仪性能进行了评估。实验结果表明,光谱仪的检测限优于5×10?11 mol·L?1,在5×10?11 mol·L?1到1×10?9 mol·L?1的溶液浓度范围内,被测溶液浓度与检测所得荧光强度满足良好的线性关系,线性相关系数为0.998 39。此外,光谱仪还具备良好的重复性,荧光峰值强度的相对标准偏差小于10%。因此,该光谱仪兼具灵敏度高、线性度好、重复性与可靠性强等优点,可以满足现场实时检测的需求。     

Enhancement of single-molecule fluorescence using a gold nanoparticle as an optical nanoantenna

We investigate the coupling of a single molecule to a single spherical gold nanoparticle acting as a nanoantenna. Using scanning probe technology, we position the particle in front of the molecule with nanometer accuracy and measure a strong enhancement of more than 20 times in the fluorescence intensity simultaneous to a 20-fold shortening of the excited state lifetime. Comparisons with three-dimensional calculations guide us to decipher the contributions of the excitation enhancement, spontaneous emission modification, and quenching. Furthermore, we provide direct evidence for the role of the particle plasmon resonance in the molecular excitation and emission processes.     

An anomalous emission excited near the absorption edge of pyrene crystals

Emission spectra and decay times of the fluorescence excited at the absorption edge region in pyrene crystals were measured. At liquid nitrogen temperature, the fluorescence under the excitation at 390 nm is considered as the excimer emission and its band peak shifts a little to the short wavelength in comparison with that of the excimer emission under the excitation at 360 nm. The emission decay times under the excitation at the 390 nm and 360 nm are about 155 ns and 180 ns, respectively, at liquid nitrogen temperature. The former decay time changes its value abruptly near 127 K. This abrupt change of the decay time may be due to the phase transition in pyrene crystals.     

Pseudo Real-Time Method for Monitoring of the Limiting Anisotropy in Membranes

Data acquisition and analysis of the time-resolved fluorescence anisotropy is typically a time consuming process preventing usage of this experimental method for monitoring of time-dependent phenomena. We describe a method for pseudo real-time monitoring of the limiting fluorescence anisotropy r(infinity) allowing to track changes of the membrane order occurring on the time scale of minutes. Principle and performance of the method is demonstrated in the time domain with the time-correlated single photon counting detection. DMPC liposomes stained with 1,6-diphenyl-1,3,5-hexatriene (DPH) have been used to test influence of the diffusion membrane potential on the membrane order during the temperature-induced phase transition in DMPC membranes. It has been found that the transmembrane field of the order of -70 mV increases the phase transition temperature by about 1.5 degrees C-2 degrees C. It is proposed that the full advantage of the method can be utilized with a gated detection, which besides a faster data acquisition brings additional advantage of excitation light suppression. The method can be also used for imaging.     

脉冲激发三能级体系半导体量子点的单光子发射效率

研究了脉冲激发下单个半导体量子点中单光子发射的统计特性.在旋转波近似条件下，由系统粒子数演化主方程并结合量子回归理论推导了二阶相关函数的运动方程，利用此方程讨论了二阶相关函数随输入脉冲面积的关系.在窄脉冲宽度的脉冲激发下，单光子的发射概率p和效率η都随着强度的增强而产生振荡.研究表明，采用窄脉冲宽度，当输入脉冲面积在π附近时可以得到较高的单光子发射效率. 关键词： 半导体量子点 单光子发射 三能级系统     

Single molecule fluorescence detection of BODIPY-FL molecules for monitoring protein synthesis

We have observed single DNA strands labeled with a small fluorescent molecule, BODIPY-FL, using objective based total internal fluorescence microscopy. In spite of its photobleaching, this small fluorophore is potentially useful for monitoring biochemical processes like protein synthesis because it can be efficiently incorporated into proteins by the ribosome through a charged epsilon-labeled fluorescent lysine tRNA. Using evanescent wave laser excitation at 488 nm, we have been able to observe single Bodipy molecules using integration times as low as 20 ms with a good signal to noise ratio, and for several images before photobleaching. We have measured the fluorescence decay due to photobleaching and have been able to lengthen it by a factor of 5 using oxygen scavenger systems.     

Resonance enhanced two photon spectroscopy of magnetically trapped atomic hydrogen

We show that resonant enhanced two photon spectroscopy is a very powerful and promising diagnostic method for trapped atomic hydrogen and antihydrogen. This method, in which photons of different wavelengths are used to excite H atoms from the 1S to the 3D or 3S level, uses the resonant enhancement of the intermediate 2P level to obtain high sensitivity while at the same time offering potentially much higher spectral resolution than single photon (Lyman α) excitation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Fluorescence anisotropy of indole molecules under two-photon excitation in the spectral range of 485–510 nm

Decay of polarized fluorescence in indole dissolved in propylene glycol under two-photon excitation by femtosecond laser pulses in the wavelength range of 485–510 nm has been studied. It is shown that under the experimental conditions used the fluorescence decay signal can be well described by a single excited state lifetime τ_f and a single rotation diffusion time τ_rot. By processing the data obtained, the times τ_f and τ_rot as well as anisotropy parameter r ₀ characterizing the symmetry of two-photon excitation of indole molecules have been determined. Decreasing of the anisotropy parameter r₀ down to zero under two-photon excitation energy higher than 5.1 eV has been observed. Interpretation of the obtained results have been done on the basis of ab initio quantum-mechanical computations. A model of energy relaxation under the condition of twophoton excitation of indole in a polar solvent has been discussed.