Two-photon fluorescence properties of a styrylpyridinium derivative organic chromophore in different solvents

The fluorescence properties of a new two-photon absorption chromophore in dimethyl formamide, methanol, acetone, benzyl alcohol, methylene chloride and chloroform are reported. The lifetime, intensity and central wavelength of the fluorescence signal vary significantly in different solvents. The fluorescence properties are explained by using the twisted intra-molecular charge-transfer model, the viscosity of the solvents and the formation of the hydrogen bond. For the dye in all solvents, the longer the fluorescence lifetime, the higher the fluorescence intensity. Generally, the higher the dipole moments, the longer the central wavelengths of the dye. PACS 42.65.-k; 42.65.Ky; 87.64.Ni     

Spectroscopic and lasing characterisation of a dicarbazovinylene-MEH-benzene dye

The dye 1,4-bis(9-ethyl-3-carbazovinylene)-2-methoxy-5-(2′-ethyl-hexyloxy)-benzene (abbreviated 2CzV-MEH-B) dissolved in tetrahydrofuran (THF) and as neat film is characterised by optical absorption and emission spectroscopy. The absorption and stimulated emission cross-section spectra, the fluorescence quantum distributions, fluorescence quantum yields, degrees of fluorescence polarisation, and fluorescence lifetimes are determined. A lasing characterisation is carried out by pumping with single second harmonic pulses of a mode-locked ruby laser (wavelength 347.15 nm, pulse duration 35 ps). The excited-state absorption at the pump laser wavelength is determined by saturable absorption measurements. Laser oscillation of the dye in THF in a rectangular cell is achieved by transverse pumping using the uncoated cell windows for light feedback. From the emission behaviour around threshold the excited-state absorption cross-section spectrum in the laser active spectral region is extracted. The wave-guided travelling-wave lasing behaviour of the dye as neat film is studied by analysis of the amplification of the transverse pumped spontaneous emission. Surface emitting distributed-feedback lasing was achieved with a neat film on corrugated second-order periodic gratings.     

Temporal and spectral properties of picosecond two-photon pumped cavity lasing of an organic dye HEASPS

The operation of cavity lasing of a two-photon absorption (TPA) organic dye, trans-4-[p-(N-hydroxyethyl-N-ethylamino)styryl]-N-methylpyridinium p-toluene sulfonate (abbreviated as HEASPS), by using a picosecond infrared laser as the pump source, is reported. The lifetimes of TPA fluorescence of this dye in different solvents were measured. Temporal profiles of cavity lasing show obvious oscillations and magnification of the feedback light. By using the difference of re-absorption coefficients at different conditions, we explained the blue shift for cavity lasing and superradiance compared with TPA-induced fluorescence. The long lifetime of fluorescence is helpful to the generation of cavity lasing. Received: 18 June 2001 / Revised version: 5 November 2001 / Published online: 17 January 2002     

Two-photon excitation properties of a class of novel organic dye chloride

We present the two-photon excited (TPE) upconverted fluorescence and lasing efficiencies of a class of new pyridinium chloride having donor-π-acceptor (D-π-A) structure. Based on the excitation upon 40 ps laser pulses at 1064 nm, the experimental results showed that: the red-shift of TPE fluorescence emission peaks and the TPE fluorescence lifetime were gradually increased with the enhancement of electron-donating capability of the donor. To a certain extent, the enhanced donor would increase the two-photon pumped (TPP) upconversion lasing efficiencies, but the overlong alkyl chains would result in decreased lasing efficiencies. We could obtain TPE fluorescence lifetime of 754 ps, TPP upconversion lasing efficiency of ∼8.4%, and TPA cross-section of 6.14 × 10⁻⁴⁹cm⁴s/photon in these compounds.     

Absorption and Emission Properties of a New Two-photon Absorption Dye

1　Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ｔｗｏ ｐｈｏｔｏｎａｂｓｏｒｐｔｉｏｎ (ＴＰＡ )ｉｓａｎｉｍｐｏｒｔａｎｔｎｏｎｌｉｎｅａｒａｂｓｏｒｐｔｉｏｎｐｒｏｃｅｓｓｉｎｂｏｔｈｂａｓｉｃａｎｄａｐｐｌｉｅｄｒｅｓｅａｒｃｈｅｓ.Ｆｏｒｍａｎｙｙｅａｒｓ,ｄｕｅｔｏｔｈｅｒｅｌａｔｉｖｅｌｙｓｍａｌｌＴＰＡｃｒｏｓｓ ｓｅｃｔｉｏｎｓｏｆｍｏｓｔｍａｔｅｒｉａｌｓ,ｔｗｏ ｐｈｏｔｏｎｐｒｏｃｅｓｓｅｓｗｅｒｅｆｏｕｎｄｌｉｍｉｔｅｄａｐｐｌｉｃａｔｉｏｎｓ.Ｌａｔｅｌｙ ,ｇｒｅａｔｐｒｏｇｒｅｓｓｅｓｈａｖ…     

Optical Properties of a New Two-photon Absorption Dye DEASPI

1　Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ｔｗｏ ｐｈｏｔｏｎａｂｓｏｒｐｔｉｏｎ (ＴＰＡ)ｉｓａｐｒｏｃｅｓｓｉｎｗｈｉｃｈｔｗｏｐｈｏｔｏｎｓａｒｅｓｉｍｕｌｔａｎｅｏｕｓｌｙａｂｓｏｒｂｅｄｔｏａｎｅｘｃｉｔｅｄｓｔａｔｅｉｎａｍｅｄｉｕｍｖｉａａｖｉｒｔｕａｌｓｔａｔｅ .ＴＰＡｉｎｔｅｎｓｉｔｙｉｓｃｈａｒａｃｔｅｒｉｚｅｄｂｙＴＰＡｃｒｏｓｓｓｅｃｔｉｏｎ .ＳｕｃｈｍａｔｅｒｉａｌｓｗｉｔｈｌａｒｇｅＴＰＡｃｒｏｓｓｓｅｃｔｉｏｎｈａｖｅｒｅｃｅｉｖｅｄｃｏｎｓｉｄｅｒａｂｌｅａｔｔｅｎｔｉｏｎｉ…     

Optical Properties of a New Two-photon Absorption Dye DEASPI

The two-photon absorption (TPA), TPA-induced frequency up-conversion emission, and two-photon pumped (TPP) frequency up-conversion lasing properties of a new synthesized dye Trans-4-［p-(N,N-diethylamino)styryl］-N-methylpyridinium iodide (DEASPI) were experimentally studied. This new dye has a moderate TPA cross-section of σ2=6.9×10-48 cm4*s/photon at 1064 nm, but exhibits a high lasing efficiency. The overall superradiant lasing conversion efficiency is as high as 10.7% at the pump energy of 2.14 mJ.     

Photophysical and lasing properties of pyrromethene 567 dye in solid poly(trifluoromethyl methacrylate) matrices with different degrees of crosslinking

The effect of increasing the rigidity of the host matrix by controlled crosslinking of the polymeric chains on the lasing and photophysical properties of pyrromethene 567 (PM567) was evaluated. To this end, the dye was dissolved in 2,2,2-trifluoromethyl methacrylate (TFMA) together with different amounts of the crosslinking monomer ethylene glycol dimethacrylate (EGDMA). Increasing the concentration of this crosslinker monomer resulted in significant increases in both lasing efficiency and photostability. Good correlation between fluorescence and lasing properties has been observed, indicating the existence of an optimum degree of crosslinking for which lasing efficiency and photostabilty reach their highest values. These new solid materials show lasing efficiencies up to 18% when transversely pumped at 534 nm and good photostabilities, with a decrease in the initial laser output of 45% after 10000 pump pulses. Received: 16 February 2001 / Revised version: 9 April 2001 / Published online: 8 June 2001     

Absorption and Emission Properties of a New Two-photon Absorption Dye

The emission properties of a newly synthesized organic two-photon absorption dye, trans-4-[p-(N-ethyl-N-ethylamino)-styryl]-N-methyl-pyridinium tetraphenylborate, have been investigated. When pumped by infrared pulses from a picosecond Nd∶YAG laser, the dye exhibits intense upconverted fluorescence and strong superradiance properties. For comparison, the one-photon induced fluorescence and superradiance are also measured. The one- and two-photon excited fluorescent lifetimes are 86 and 64 ps, respectively. The maximum efficiency of the dye is measured to be 1.97% and the upconversion efficiencies at different pump wavelengths have also been investigated by the optical parametric amplifier.     

Influence of solvent on the physical and lasing properties of dye-doped sol-gel host

Pyrromethene 597 dye is synthesised in two routes by sol-gel process and ethanol and tetrahydrofuran are used as solvents for hydrolysis. To understand the role and the influence of solvent in sol-gel host, absorption and emission spectra of the dye diluted in ethanol and tetrahydrofuran are recorded. Similarly, the absorption, emission spectra and their lasing performance of the molecule obtained by both sol-gel host matrices are also measured and compared. It is shown that the gelation of sol-gel with tetrahydrofuran is faster than that with ethanol. Effect on absorption and emission spectra due to influence of solvent are observed. The lasing performance of pyrromethene 597 dye doped in sol-gel was measured and the output properties are shown and found to be different.     

Photobleaching and stabilization of. fluorophores used for single-molecule analysis. with one- and two-photon excitation

Fluorescence spectroscopic measurements at the single-molecule level usually require large absorption cross sections and fluorescence quantum yields for the dyes under study. In addition to these parameters, the collectable number of fluorescence photons and, thus, the signal-to-noise ratio of the measurement, is influenced by processes like triplet-state population and photobleaching, shifting the saturation threshold of the dye to lower excitation intensities. Confocal fluorescence correlation spectroscopy (FCS) is a versatile method to precisely determine photon emission rates of single molecules but also gives access to rate constants of dynamic bleaching and intersystem crossing. In recent FCS studies in solution and living cells, two-photon excitation with its inherent spatial sectioning has proven to be a very valuable alternative to minimize background and cumulative signal loss. However, there is evidence that in many dye systems, the photobleaching rates with two-photon excitation are significantly enhanced with respect to one-photon excitation at comparable photon-emission yields. The reasons have so far remained mainly speculative. In the present study, potential photobleaching pathways are investigated by adding chemical stabilizers and by working at different oxygen concentrations. The results suggest that the population of triplet states does not appear to be responsible for the limited emission rate with two-photon excitation. Rather, photobleaching pathways via the formation of radicals seem to be plausible causes for the signal limitation. Favorable conditions are discussed to maximize the overall photon-collection yield in two-photon experiments. Received: 4 July 2001 / Published online: 23 November 2001     

Linear and nonlinear optical properties of two-photon absorption dye doped linear copolymer

2-hydroxyethyl methacrylate (abbreviated as HEMA) and acrylonitrile have been used as the monomers to form a trans-4-[p-(N-hydroxyethyl-N-methylamino)styryl]-N-methylpyridinium p-toluene sulfonate (abbreviated as HMASPS) doped linear copolymer. The spectra of one and two-photon excited fluorescence and two-photon pumped superradiance and two-photon pumped lasing of the polymer all shifted to short wavelengths compared with the solution sample of the dye. The copolymer shows much longer one- and two-photon excited fluorescence lifetimes of nanoseconds. When pumped by the picosecond Nd:YAG laser, the superradiance and lasing can be simultaneously obtained. The maximum two-photon pumped lasing conversion efficiency is 3.3%. The place of the maximum upconversion efficiency of the copolymer does not coincide with that of the maximum nonlinear absorption.     

Properties of two-photon absorption-induced cavity lasing of an organic dye HEASPI pumped by picosecond infrared laser beam

The first operation of cavity lasing of a two-photon absorption (TPA) organic dye, trans-4-[p-(N-ethyl-N-hydroxyethylamino) styryl]-N-methylpyridinium iodide (HEASPI), by using picosecond infrared laser as pump source is reported in this paper. Temporal profile of cavity lasing shows obvious oscillations, and magnification of the feedback light can be obtained. By using the difference of re-absorption coefficient at different conditions, we explained the blue shift for cavity lasing and superradiance compared with TPA-induced fluorescence. The lifetime of TPA-induced fluorescence is measured to be 134 ps.     

A microchip-laser-pumped DFB-polymer-dye laser

A miniaturized, high repetition rate, picosecond all solid state photo-induced distributed feedback (DFB) polymer-dye laser is described by applying a passively Q-switched and frequency-doubled Cr⁴⁺:Nd³⁺:YAG-microchip laser (pulse width Δτ=540 ps, repetition rate ν=3 kHz, pump energy E_pump=0.15 μJ) as a pump source. A poly-methylmethacrylate film doped with rhodamine B dye serves as active medium. The DFB-laser pulses are temporally and spectrally characterized, and the stability of the thin polymer/dye film at high repetition rates is analyzed. The shortest DFB-laser pulses obtained have a duration of 11 ps. After the emission of 350000 pulses the intensity of the DFB-laser output has decreased by a factor of two and the pulse duration has increased by a factor of 1.2. For single DFB-laser pulses of 20-ps duration the spectral bandwidth is measured to be Δλ=0.03 nm, which is only 0.005 nm above the calculated Fourier limit assuming a Gaussian profile for the temporal shape of the pulses. Coarse wavelength tuning of the DFB laser between 590 and 619 nm is done by turning the prism. Additionally, a fine tuning of the DFB-polymer-laser wavelength is achieved by changing the temperature of the polymer/dye layer (=-0.05 nm/°C) in the range from 20 to 40 °C. Received: 1 March 2001 / Revised version: 23 May 2001 / Published online: 18 July 2001     

Photo-stability of laser dye solutions under Copper-vapour-laser excitation

The photo-stability of laser dyes, Rhodamine-6G, Rhodamine-B, and Kiton-Red, under high repetition rate (6.3 kHz) Copper-vapour-laser (CVL) irradiation has been investigated. Exhaustive photo-bleaching of these dyes in different solvents has been carried out to study the extent to which the dye photo-degraded products would interfere with the lasing process in high-power CVL-pumped dye lasers. Our results indicate that the photo-degradation of dyes occurs predominantly through excited-state intermolecular reactions, involving the singlet state, rather than the process of nonlinear optical absorption in individual molecules. Received: 13 March 2000 / Revised version: 2 August 2000 / Published online: 21 March 2001     

High efficiency lasing of a dye-doped polymer laser with 1.06 μm pumping

For the first time, tunable lasing from a dye laser with an active polymer medium has been obtained using 1.06 μm pumping. The conversion efficiency of 43% and the tunable range of Δλ=63 nm have been reached with the use of polymethine dye in a polyurethane matrix. Received: 20 April 2001 / Revised version: 16 July 2001 / Published online: 19 September 2001     

Spectroscopic and travelling-wave lasing characterisation of tetraphenylbenzidine and di-naphtalenyl-diphenylbenzidine

The organic light emitting diode (OLED) hole transport molecules N,N,N’,N’-tetraphenylbenzidine (TPB, triphenylamine dimer TAD or TPD) and N,N’-bis(2-naphtalenyl)-N,N’-bis(phenylbenzidine) (β-NPB, naphtyl-diphenylamine dimer β-NPD), dissolved in tetrahydrofuran (THF) and as neat film, are characterized by optical absorption and emission spectroscopy. The absorption and stimulated emission cross-section spectra, the fluorescence quantum distributions, fluorescence quantum yields, degrees of fluorescence polarization, and fluorescence lifetimes are determined. The lasing behaviour is studied by picosecond laser pulse excitation (excitation wavelength 347.15 nm, pulse duration 35 ps). The excited-state absorption at the pump laser wavelength is determined by saturable absorption measurement. Low-Q laser oscillation of TPB in THF is achieved by transverse pumping of the dye in a cell. The excited-state absorption of TPB in THF at the laser wavelength is extracted from the laser threshold. In TPB neat films, wave-guided travelling-wave lasing was obtained. No laser action was achieved for β-NPB because of small S₁-S₀ stimulated emission cross-section, and the presence of excited-state absorption in the fluorescence wavelength region. The TPB and β-NPB results are compared with the corresponding spectroscopic and lasing behaviour of the related methyl-substituted triphenylamine dimers, 3-methyl-TPD and 4-methyl-TPD, which are well established OLED hole transport materials.     

Electrically switchable reflection holograms formed using two-photon photopolymerization

Two-photon holographic photopolymerization was used to form switchable Bragg gratings composed of layers of phase-separated liquid-crystal (LC) domains interspersed with cured, crosslinked polymer. These holographic polymer-dispersed liquid crystals form a periodic structure which diffracts red light due to nanostructured planes ∼250 nm in spacing. These structures were formed by interfering two 90-fs pulses coherently upon a reactive syrup consisting of acrylate monomer, liquid crystal, and a two-photon dye. The large two-photon cross-section allows excitation of the two-photon dye that results in electron transfer between this dye and the monomer. Diffraction efficiencies of approximately 10% were obtained, which can be modulated using an electric field applied across the film. Switching speeds below 1 ms were observed due in part to the small size of the LC domains. Received: 10 April 2001 / Accepted: 1 July 2001 / Published online: 2 October 2001     

双氰基荧光染料的合成、光学性质及其生物成像

设计合成了一种A-π-D-π-A型的双光子荧光染料3,6-双(4-乙烯基苯腈)-9-乙基咔唑,测试了其在二氯甲烷(DCM)、乙酸乙酯(EA)、乙醇(Et OH)、乙腈(ACN)、二甲亚砜(DMSO)和磷酸缓冲盐溶液(PBS)等不同溶剂中的紫外吸收光谱、单光子及双光子荧光光谱。化合物3,6-双(4-乙烯基苯腈)-9-乙基咔唑在紫外吸收光谱中存在两个相似的特征吸收带并呈现出复杂的溶剂化效应,在DMSO中具有最大荧光量子产率(86.02%),其相应的活性吸收截面为12.56 GM。在双光子荧光成像方面,染料分子具有优良的细胞膜通透性并且在双光子荧光显微镜下呈现出明亮的绿色荧光,表现出较好的双光子荧光成像性能。这些数据表明,化合物3,6-双(4-乙烯基苯腈)-9-乙基咔唑可用作一种较为理想的双光子荧光标记染料。     

Opto-acoustic study of tinuvin-P and rhodamine 6G in solid polymeric matrices

Laser-induced opto-acoustic calorimetry has been used to examine the thermo-elastic properties of two polymer matrices doped with tinuvin-P and the radiation-less decay processes of rhodamine 6G (Rh6G) in them. The matrices assayed were methyl methacrylate (MMA) homopolymers P(MMA), and methyl methacrylate and 2-hydroxyethyl methacrylate (HEMA) copolymers P(MMA:HEMA). A slight difference in the thermo-elastic properties of the polymers, namely their adiabatic expansion coefficients, has been detected and found to correlate with the long-term stability of the laser material. This suggests a key role of the heat-dissipation processes in the photostability of these polymeric materials. On the other hand, the fluorescence quantum yield of Rh6G is shown to vary with the polymer-matrix composition in a way consistent with its lasing efficiency. The Rh6G absorption and fluorescence quantum yield also change dramatically upon increasing its concentration, which suggests the co-existence of different Rh6G forms with different photophysical properties. Received: 10 February 2000 / Revised version: 12 June 2000 / Published online: 10 January 2001