High efficiency dye laser with low fluorescence yield pyrromethene dyes: experimental and theoretical studies

A combined experimental and theoretical study of the photo-physical, laser properties and molecular structures of three relatively recent Pyrromethene (PM) class dyes, PM597, PM580 and PM567, have been carried out. Laser characteristics of these three PM dyes were compared with three other widely used Rhodamine (RH) class dyes, RH6G, RHB and KRS, using a narrow-band dye laser setup, transversely pumped by the second harmonic (532 nm) of a Q-switched Nd-YAG laser. In addition to generating comparative data of these dyes for optimal use in dye lasers, we observed that unlike the RH dyes, the PM dyes show high efficiencies and wide tunability, despite the low fluorescence yield and high rate of non-radiative decay. Particularly, PM597 dye, in spite of a very low quantum yield of fluorescence (Φ=0.42), high non-radiative decay rate, and a large distortion from planarity in its excited state, when used in a laser cavity it exhibited similar laser efficiency and a beneficially wider tuning curve in comparison to other two PM dyes. Theoretical studies were carried out applying density functional theory and time-dependent density functional theory (DFT/TDDFT) to obtain new information on ground and the first excited state geometrical parameters of the PM dyes. Good correlation between calculated molecular properties and experimental results was observed for the evolution of the longest wavelength absorption maximum.     

Comparative laser performances of pyrromethene 567 and rhodamine 6G dyes in copper vapour laser pumped dye lasers

Narrowband laser performances and photochemical stability of alcoholic solutions of pyrromethene 567 and rhodamine 6G dyes, under high-repetition rate copper vapour laser (at 510 nm), as well as, high-peak intensity Nd:YAG laser (at 532 nm) excitation have been investigated. We have observed that pyrromethene 567 dye solutions offer higher efficiency, wider tuning range, but lower photochemical stability and higher lasing threshold than that of rhodamine 6G dye solutions. An addition of about 100 mM DABCO, as a singlet oxygen quencher, in pyrromethene 567 dye solutions improved its photochemical stability close to that of rhodamine 6G. The observation of higher slope efficiency, in spite of higher threshold pump energy for pyrromethene 567 dye than that of rhodamine 6G dye solutions, was explained by a predictive model on gain characteristics of both dye solutions as a function of pump energy. PACS 42.55.Mv; 42.55.Rz; 42.70.Hj; 42.70.Jk     

Linear and cross-linked polymeric solid-state dye lasers based on 8-substituted alkyl analogues of pyrromethene 567

The lasing properties of analogues of the commercial laser dye pyrromethene 567 (PM567) incorporated (dissolved or copolymerized) into polymeric matrices have been studied using both linear and cross-linked methyl methacrylate-based copolymers with different degrees of functionalization. All synthesized dyes have the chromophore core of PM567 but with an ω-acyloxypolymethylene chain at position 8. In general, the new materials exhibited laser emission with higher efficiencies and much higher photostabilities than those containing the commercial dye PM567 under the same experimental conditions. Lasing efficiencies of up to 40% were obtained under transversal pumping at 534 nm. The highest photostabilities, with the laser output remaining stable or dropping by less than 15% after 100 000 pump pulses at the same position of the sample, were reached in cross-linked materials with dyes covalently linked to the polymeric chains. When the polymeric samples were incorporated into a grazing-incidence grating oscillator, narrow-line-width operation with tuning ranges of up to 40 nm was obtained. These results show that efficient and photostable solid-state dye lasers competitive with their liquid counterparts can be developed by adequate chemical modifications in the dye molecules, as well as by the selection of appropriate polymeric formulations.     

Highly efficient and photostable solid-state dye lasers doped with PM567 with the addition of Tinuvin770

Solid-state dye samples based on polymethyl methacrylate (PMMA) doped with pyrromethene 567 (PM567) with the addition of Tinuvin770 were prepared. The effects of a light stabilizer and concentration on the laser performances of the solid state dye PM567, including spectra properties, slope efficiency and photostability were investigated. The highest slope efficiency 66.6% was obtained in the sample (PM567:Tinuvin770 = 2.0:0.5). The addition of Tinuvin770 resulted in a dramatic enhancement of photo-stability. Pumping the samples at a rate of 5 Hz with a pulse energy as high as 100 mJ (the pump energy density was 0.26 J/cm²), the output energy dropped to half of its initial value after approximate 149500 shots and the normalized photostability reached 97.2 GJ/mol in the sample (PM567:Tinuvin770 = 2:5). All results have shown that a high efficient and photostable solid-state dye laser with the addition of Tinuvin770 can be obtained.     

Highly photostable solid-state dye lasers based on mixed pyrromethene 567 and coumarin 500

Solid-state dye samples based on polymethyl methacrylate (PMMA) co-doped with pyrromethene 567 (PM567) and coumarin 500 (C500) were prepared. The effects of C500 concentration on the performances of the solid state dye mediums, including spectra property, slope efficiency and photostability were studied. The highest slope efficiency 64.25% was obtained in the sample (PM567: C500 = 2: 8). Pumping the samples at a rate of 5Hz with a pulse energy as high as 100 mJ (the fluence was 0.26 J/cm²), the output energy dropped to half of its initial value after approximate 116130 pulses and the normalized photostability reached 75.48 GJ/mol in the sample (PM567: C500 = 2: 1). Our results have shown that it is possible to obtain a high-efficiency with a long-lifetime for a solid-state dye laser co-doped with PM567 and C500.     

Transient excited singlet state absorption in Rhodamine 6G

Transient excited singlet state absorption (ESSA) has been studied in Rhodamine 6G in ethanol using a nitrogen laser and nitrogen laser-pumped dye laser. Broad absorption with several submaxima and possible shoulders, which represent the vibrational structure, has been observed in Rhodamine 6G in the region, 4175–4640 Å. The position of the lowest vibrational level of the first excited singlet stateS ₁ has been determined from the crossing point of the long and short wavelength spectral wings of absorption and fluorescence respectively. The energy level scheme of the molecule has been obtained with the help of the absorption and fluorescence spectra recorded. The observed structure in ESSA has been tentatively interpreted to be due to transitions from the different vibrational levels ofS ₁ to one or more vibrational levels of the upper singlet electronic stateS ₄.     

Solid-state lasers based on copolymers of methyl methacrylate and 2-hydroxyethyl acrylate doped with pyrromethene 567 dye

Solid-state dye laser samples based on copolymers of methyl methacrylate (MMA) and 2-hydroxyethyl acrylate (HEA) doped with pyrromethene 567(PM567) were prepared. The highest slope efficiency 46.4% was obtained. With pump repetition rate of 10 Hz and intensity of 0.1 J/cm², the output energy of the sample based on P (MMA: HEA 16:4) remained up to 82.10% of its initial value after approximate 100000 shots. To our knowledge, the achieved photostability is the best under the same condition so far. Compared with the sample based on the monopolymer, the slope efficiency and photostability of copolymer-based solid-state dye samples were both enhanced. The results indicate that the high laser performance using solid-state dye samples based on copolymers of MMA with HEA as solid hosts can be achieved.     

Solid State Dye Lasers Based on Coumarin 440 and Pyrromethene 567 Codoped Polymethyl Methacrylate

Laser dye coumarin 440（C440） is codoped with pyrromethene 567 （PM567） into polymethyl methacrylate （PMMA） The effects of C440 concentration on the performance of the solid state dye medium, including spectra property, slope efficiency and photostability, are studied. When C440 is codoped with PM567 at the same concentration 1 × 10^-4 mol/L, the highest efficiency and photostability can be obtained. Compared with the medium based on pure PM567 doped PMMA, about 50% increase in slope efficiency and at least five-fold enhancement in the photostability are observed.     

Photoquenching parameters for commonly used laser dyes

Laser dyes which are commonly used in pulsed laser pumped dye laser (PLPDL) systems have been investigated. It is shown that photoquenching plays an important role in the pumping process of all laser dyes, determining the efficiency of the PLPDL. Molecular parameters, such as absorption cross sections at various pumping wavelengths and fluorescence lifetimes of theS _n (n>1) excited electronic states of laser dyes, have been determined utilizing the photoquenching technique.     

Enhanced laser performances based on energy transfer in multi-dyes co-doped solid media

Various coumarin dyes are co-doped with perylene red (P-red) and pyrromethene 567 (PM567) into vinyltriethoxysilane-derived solid media, respectively. Energy transfer among laser dyes has been observed, and the effect of coumarin dye concentration on the laser properties has been investigated. With the presence of coumarin dye and pyrromethene 567, enhanced laser performances based on energy transfer of perylene red have been exhibited. The laser efficiency can be improved by two-fold and broad tunable range as wide as 80 nm can be achieved. At the pump intensity of 1.0 J/cm², the laser output of co-doping perylene red decreases less than 30% after 30,000 pulses.     

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     

Solid-state dye lasers based on polymethyl methacrylate modified with methanol

Solid-state dye samples based on modified polymethyl methacrylate with methanol (MPMMA) doped with pyrromethene 567 (PM567) were first prepared. The effects of volume percentage of methanol on the laser performances of the samples, including spectra properties, slope efficiency and photostability were studied. The highest slope efficiency 66.39% was obtained in the sample (MMA:methanol = 16:4). Pumping the samples at a repetition rate of 5 Hz with a pulse energy as high as 100 mJ (the fluence was 0.26 J/cm²), the output energy dropped to half of its initial value after approximate 156720 shots and the corresponding normalized photostability reached 101.86 GJ/mol in the sample (MMA:methanol = 17:3). Our results indicate that it can obtain a high slope efficiency and good photostability for a solid-state dye laser using MPMMA as solid hosts.     

Photophysical properties and laser performance of rubrene

The potential of rubrene as a laser dye was investigated in deaerated solutions with a XeCl excimer laser as pump source. Laser tuning range, quantum efficiency and photostability as well as excited singlet state absorption (ESA) spectra were measured. The (S₁-S₂) absorption band strongly overlaps with the fluorescence spectrum and thus ESA constitutes an important loss factor in the lasing process while triplet absorption can be neglected in the wavelength region of interest. Laser performance of rubrene is superior compared to other polycyclic aromatic hydrocarbons which can be considered as model compounds of the lasing process in organic dyes.     

Saturated absorption experiments using a free running CW dye laser

The hyperfine structure of some new iodine lines has been observed over the tuning range of Rhodamine 6G (5800–6200 Å), using a free running, single mode cw dye laser. The resolution obtained in this experiment allowed to calculate the hyperfine constants of the excited state (³π₀⁺) of iodine with an accuracy of 2% for the quadrupole coupling constant and 50% for the magnetic one.     

High pulse energy output from tunable solid-state dye laser based on MPMMA doped with PM567

Tunable solid-state dye laser sample based on modified polymethyl methacrylate (MPMMA) with methanol co-doped with pyrromethene 567 (PM567) and Coumarin 440 (C440) was prepared. Tunable dye laser output wavelength from 546 to 594 nm was obtained in an oscillator-amplifier configuration. With the input seed laser energy being about 1.5 mJ, the highest dye laser output energy reached 113.9 mJ, and the corresponding conversion slope efficiency was 51.39%. To the best of our knowledge, the tuning range and narrow linewidth dye output energy is the best under the same condition so far. The linewidth for the seed laser and amplified laser were measured with the result of less than 0.2 nm. With the amplified medium being pumped at a repetition rate of 10 Hz with a pulse energy as high as 120 mJ (the fluence was 0.42 J/cm²), the laser output energy dropped to half of its initial value after approximate 43000 pulses.     

Solid Dye Lasers Based on 2-Hydroxypropyl Methacrylate and Methyl Methacrylate Copolymers

Polymers are a kind of attractive hosts for laser dyes because of their superior optical homogeneity, and high transparency in pumping and lasing range. Copolymers usually have higher damage threshold and better photostability than mono-polymers. Solid dye samples based on copolymer of methyl methacrylate （MMA） with 2-hydroxypropyl methacrylate （HPMA） doped with 1-, 3-, 5-, 7-, 8-pentamethyl-2, 6-diethylpyrromethene-BF2 （PM567） are prepared. Spectra and lasing properties of the samples are studied. Compared to the samples based on monopolymer polymethyl methacrylate （PMMA）, enhanced slope efficiency and photostability are obtained in the copolymers. The highest slope efficiency is 45.1%, and nearly one-fold increase of photostability is obtained. The longest useful lifetime of 4390 pumping pulses is presented with the pump energy as high as 183 mJ per pulse at repetition rate of 10 Hz. The results indicate that the laser performances of solid dye mediums can be greatly increased using copolymer of MMA with HPMA as host.     

Linearly polarised three-colour lasing emission from an evanescent wave pumped and gain coupled fibre laser

A novel Whispering--Gallery--Mode (WGM) fibre laser, emitting linearly polarised three-colour light, is demonstrated by pumping and gain coupling with evanescent waves. The pump light is longitudinally coupled into a bare optical fibre immersed in a dye solution of lower refractive index. The dye molecules around the bare fibre are excited by the evanescent waves of pump light when they propagate along the fibre in a total internal reflection. When the pump beam within the fibre is a meridian beam, the WGM lasing emission from the fibre laser is a linearly polarised transverse electric wave, while it is a mixed wave of the linearly polarised transverse electric and magnetic waves if the pump beam is a skew beam within the fibre. Because the excited molecules are located within the evanescent field of WGM, a good spatial overlap between the dye gain and the evanescent field leads to a high pumping efficiency and a longer gain distance along the fibre. Once the bare fibre is inserted into three glass capillaries filled with Rhodamine 6G, 610 and 640 dye solutions, respectively, WGM laser oscillations at the wavelengths of 567--575, 605--614 and 656--666~nm occur simultaneously, and a linearly polarised three-colour lasing emission is achieved in a single optical fibre.     

Efficient and highly photostable solid-state dye lasers based on modified dipyrromethene.BF2 complexes incorporated into solid matrices of poly(methyl methacrylate)

We report on the laser action of modified dipyrromethene.BF₂ complexes both dissolved in poly(methyl methacrylate) and copolymerized with methyl methacrylate. All recently synthesized dyes have the chromophore core of laser dye pyrromethene 567, differing in the substituent in position 8. The new dyes showed important and most significant increases in both lasing efficiency and photostability. When the laser samples were pumped transversely at 534 nm, laser emission was obtained with efficiencies of over 30% in most cases, to be compared with a lasing efficiency of 12% exhibited by reference dye pyrromethene 567 under the same experimental conditions. Some of the materials exhibited highly photostable laser action, with no sign of degradation in the laser output after 60000 pump pulses at the same position of the sample at a repetition rate of 10 Hz, whereas the laser emission of reference dye pyrromethene 567 dropped to zero after less than 40000 pump pulses. Received: 19 November 2002 / Revised version: 20 February 2003 / Published online: 9 April 2003 RID="*" ID="*"Corresponding author. Fax: +34-91/564-2431, E-mail: acostela@iqfr.csic.es     

Laser performance of pyrromethene 567 dye in solid matrices of methyl methacrylate with different comonomers

Laser performance of pyrromethene 567 (PM567) dye dissolved in pure poly(methyl methacrylate) homopolymer and its copolymers with 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1-vinyl-2-pyrrolidone, 2-phenoxyethyl acrylate, and 2,2,2-trifluoromethyl methacrylate has been investigated. The chosen monomers were selected to mimic solvents used in a previous study on the photophysical and lasing properties of PM567 in liquid solution in order to establish correlations between the lasing properties of PM567 in liquid and solid solutions. The vol/vol proportion of the different comonomers in each copolymer formulation was systematically varied, and the effect of each composition on the lasing properties of PM567 was evaluated. The laser samples were transversely pumped at 534 nm with 5.5-mJ pulses from a frequency-doubled Q-switched Nd:KGW laser. Lasing efficiencies of up to 30% and good photostabilities, with a drop of the initial laser output of 20% after 10000 pump pulses in some of the solid samples, were demonstrated. Received: 2 June 1999 / Revised version: 18 July 1999 / Published online: 3 November 1999     

A New Candidate Laser Dye Based 1,4-Bis[β-(2-Naphthothiazolyle)Vinyl]Benzene. Spectroscopic Behavior,Laser Parameters and Excitation Energy Transfer

A new candidate laser dye based 1,4-bis[β-(2-naphthothisolyl) vinyl] benzene (BNTVB) were prepared, and characterized in various organic solvents. The center polarity is less sensitive than electronic absorption. A red shift was noticed in the fluorescence spectra (ca. 40 nm) with increment in the solvent’s polarity, this means that BNTVB’s polarity appreciates upon excitation. The dipole moment of ground state (μ_g) and the excited singlet state dipole moment (μ_e) are determined from Kawski – Chamma and Bakshiev–Viallet equations using the disparity of Stokes shift with solvent polarity function of ε (dielectric constant) and n (refractive index) of the solvent. The result was found to be 0.019D and 5.13D for ground and exited state, in succession. DFT/TD-DFT manners were used to understand the electronic structures and geometric of BNTVB in other solvents. The experimental and theoretical results showed a good agreement. The photochemical quantum yield (Ф_c) of BNTVB was calculated in variable organic reagents such as Dioxane, CHCl₃, EtOH and MeOH at room temperature. The values of φ_c were calculated as 2.3?×?10^?4, 3.3?×?10^?3, 9.7?×?10^?5 and 6.2?×?10^?5 in Dioxane, CHCl₃, EtOH and MeOH, respectively. The dye solutions (2?×?10^?4 M) in DMF, MeOH and EtOH give laser emission in the blue-green region. The green zone is excited by nitrogen pulse 337.1 nm. The tuning range, gain coefficient (α) and cross – section emission (σ_e) of laser were also estimated. Excitation energy transfer from BNTVB to rhodamine-6G (R6G) and N,N-bis(2,6-dimethyphenyl)-3,4:9,10-perylenebis-(dicarboximide) (BDP) was also studied in EtOH to increase the laser emission output from R6G and BDP when excited by nitrogen laser. The dye-transfer power laser system (ETDL) obeys the Foster Power Transmission (FERT) mechanism with a critical transmission distance, R_o of 40 and 32 ? and k_ET equals 2.6?×?10¹³ and 1.06?×?10¹³ M^?1 s^?1 for BNTVB / R6G and BNTVB / BDP pair, respectively.