Pyrromethene Research Articles

Highly photo-stable dye doped solid-state distributed-feedback (DFB) channeled waveguide lasers by a pen-drawing technique

Pyrromethene dyes doped polymeric channeled waveguide lasers with permanent DFB structures were fabricated via a novel pen-drawing technique with the patterned polydimethylsiloxane (PDMS) chips fabricated through a casting process as the substrates. With the high resolution dispensers, dye doped high viscosity pre-polymers were written into the PDMS grooves and the cross-section of the channeled waveguides could be controlled by both the polymer composition and the pen-drawing parameters. Highly stable laser output with 4.8 × 10(6) pulses of laser lifetime at 500 Hz of pump repetition rate has been obtained, which is suggested to be among one of the best results of pyrromethene 567 (PM567) up to date.

Dye‐Doped Polyhedral Oligomeric Silsesquioxane (POSS)‐Modified Polymeric Matrices for Highly Efficient and Photostable Solid‐State Lasers

AbstractHere, the design, synthesis, and characterization of laser nanomaterials based on dye‐doped methyl methacrylate (MMA) crosslinked with octa(propyl‐methacrylate) polyhedral oligomeric silsesquioxane (8MMAPOSS) is reported in relation to their composition and structure. The influence of the silicon content on the laser action of the dye pyrromethene 567 (PM567) is analyzed in a systematic way by increasing the weight proportion of POSS from 1 to 50%. The influence of the inorganic network structure is studied by replacing the 8MMAPOSS comonomer by both the monofunctionalized heptaisobutyl‐methacryl‐POSS (1MMAPOSS), which defines the nanostructured linear network with the POSS cages appearing as pendant groups of the polymeric chains, and also by a new 8‐hydrogenated POSS incorporated as additive to the polymeric matrices. The new materials exhibit enhanced thermal, optical, and mechanical properties with respect to the pure organic polymers. The organization of the molecular units in these nanomaterials is studied through a structural analysis by solid‐state NMR. The domain size of the dispersed phase assures a homogeneous distribution of POSS into the polymer, thus, a continuous phase corresponding to the organic matrix incorporates these nanometer‐sized POSS crosslinkers at a molecular level, in agreement with the transparency of the samples. The silicon–oxygen core framework has to be covalently bonded into the polymer backbone instead of being a simple additive and both the silica content and crosslinked degree exhibit a critical influence on the laser action.

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.

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.

Distributed-feedback laser actions in zirconia-ORMOSIL waveguides based on energy transfer between co-doped laser dyes

Laser dyes such as pyrromethene 567 (PM567), perylene red (P-red) and coumarin 540A (C540A) were doped into zirconia-organically modified silicate (ORMOSIL) materials prepared by low temperature sol–gel technique. Narrow line-width distributed feedback (DFB) laser actions were induced in the PM567 and/or P-red doped sol–gel planar waveguide. Tuning of the output wavelength was achieved by varying the period of the gain modulation generated by a nanosecond Nd:YAG laser at 532 nm. Compared with those of PM567 and P-red solely doped thin films, tuning range of C540A, PM567 and P-red co-doped sol–gel planar waveguide was greatly extended, from 564.5 nm to 635.1 nm.

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.

Design and Development of a New Pyrromethene Dye with Improved Photostability and Lasing Efficiency: Theoretical Rationalization of Photophysical and Photochemical Properties

In an attempt to develop a photostable and efficient pyrromethene compound for use in liquid dye lasers, three congeners of the commercially available pyrromethene 567 (PM567) laser dye were synthesized and their photophysical properties, lasing efficiencies, and photochemical stabilities were studied. In general the presence of an aryl group at C-8 of the pyrromethene chromophore increased the photostability. One of the congeners possessing a C-8 trimethoxyphenyl moiety showed significantly improved lasing parameters than PM567. Compared to PM567, the photochemical stability of the new dye was 2-fold, while it showed an equivalent lasing efficiency to that of PM567 at a significantly lower concentration. The increased photostability of these new dye molecules could be explained by theoretical calculation on their capacity to generate singlet oxygen ((1)O(2)) and probability of reaction with (1)O(2). Our calculations were in agreement with the experimental results and indicated that a systematic design of new derivatives of pyrromethene chromophore might lead to improved laser dye molecules.

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 80nm can be achieved. At the pump intensity of 1.0J/cm2, the laser output of co-doping perylene red decreases less than 30% after 30,000 pulses.

Highly photostable solid-state dye lasers based on silicon-modified organic matrices

We report on the synthesis, characterization, and physical properties of modified polymeric matrices incorporating silicon atoms in their structure and doped with laser dyes. When the silicon-modified organic matrices incorporated pyrromethene 567 (PM567) and pyrromethene 597 (PM597) dyes as actual solid solutions, highly photostable laser operation with reasonable, nonoptimized efficiencies was obtained under transversal pumping at 532nm. At a pump repetition rate of 10Hz, the intensity of the laser emission remained at the level or above the initial lasing intensity after 100 000 pump pulses in the same position of the sample, corresponding to an estimated accumulated pump energy absorbed by the system of 518 and 1295GJ∕mol for PM567 and PM597, respectively. When the pump repetition rate was increased to 30Hz, the laser emission of dye PM567 decreased steadily and the output energy fell to one-half its initial value after an accumulated pump energy of 989 GJ/mol. Dye PM597 demonstrated a remarkable photostability, and under 30Hz pumping the laser emission from some samples remained stable after 700 000 pump pulses in the same position of the sample, corresponding to an accumulated pump energy of 17300GJ∕mol. Narrow linewidth operation with tuning ranges of up to 31nm was obtained with both pyrromethene dyes when some of the samples were incorporated into a grazing-incidence grating oscillator.

Laser emission from mixtures of dipyrromethene dyes in liquid solution and in solid polymeric matrices

Laser emission from binary mixtures of different dyes both in liquid solution and incorporated into solid polymeric matrices, covering the spectral region from green to red, is investigated. Mixtures of two synthesized dyes, analogs of the commercial dye Pyrromethene 567 (PM567), allowed covering the spectral range from green to orange. Tuning ranges in solid state of up to 42 nm with good photostabilities were demonstrated. To extend the tuning range to the red, binary mixtures of the dyes Pyrromethene 597 (PM597)/Pyrromethene 650 (PM650), PM567/DCM, and PM597/DCM were also studied. In liquid solution, a mixture of dyes PM567 and DCM allowed for narrow-linewidth laser emission continuously tunable over a range of 85 nm. In solid-state, mixtures of dyes PM597 and PM650 allowed laser emission tunable over two separate spectral regions up to a wavelength of 619 nm.

Concerning the color change of pyrromethene 650 dye in electron-donor solvents

This paper studies the change in the color from violet to green of pyrromethene 650 (PM650) dye observed in certain N, N′-dialkyl-amides characterized by their high electron-donor ability and low proton-donor capacity. For this purpose, the photophysical properties of PM650 are registered in diluted solutions of several amides, including dimethylformamide/dioxane mixtures. The color change of PM650 is discussed on the basis of the formation of new hypsochromic absorption and fluorescence bands, which are assigned to the formation of new chromophoric species as consequence of a specific reaction between PM650 and the amide solvents. The influence of the ageing time of the sample and the temperature on the color change is also discussed. In some cases the ageing leads to the bleaching of the dye.

Synthesis, Structure, and Physical Properties of Hybrid Nanocomposites for Solid-State Dye Lasers

We report on the synthesis, structural characterization, physical properties, and lasing action of two organic dyes, Rhodamine 6G (Rh6G) and Pyrromethene 597 (PM597), incorporated into new hybrid organic-inorganic materials, where the organic component was either poly(2-hydroxyethyl-methacrylate) (PHEMA) or copolymers of HEMA with methyl methacrylate (MMA), and the inorganic counterpart consisted of silica derived from hydrolysis-condensation of methyltriethoxysilane (TRIEOS) in weight proportion of up to 30%. Lasing efficiencies of up 23% and high photostabilities, with no sign of degradation in the initial laser output after 100 000 pump pulses at 10 Hz, were demonstrated when pumping the samples transversely at 534 nm with 5.5 mJ/pulse. A direct relationship could be established between the structure of the hybrid materials, analyzed by solid-state NMR, and their laser behavior. An inorganic network dominated by di-/tri- substituted silicates in a proportion approximately 35:65, corresponding to samples of HEMA with 15 and 20 wt % proportion of TRIEOS, optimizes the lasing photostability. The thermal properties of these materials, together with the high homogeneity revealed by atomic force microscopy (AFM) images, even in compounds with high silica content, indicate their microstructure to be a continuous phase, corresponding to the polymer matrix, which "traps" the silica components at molecular level via covalent bonding, with few or no silica islands.

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.

Pyrromethene 597 고체 색소 레이저의 제작 및 출력 특성

We fabricated pyrromethene 597(PM597) solid-state dyes which were dissolved in PMMA(poly- methylmethacrylate) and characterized the lasing characteristics. The laser was end-pumped by a frequency doubled Q-switched Nd : YAG laser. We obtained the slope efficiency of at lasing wavelength of 585 nm. We demonstrated the laser lifetime to be more than 100,000 shots with output energy of 250 mJ and repetition rate of 4 Hz by adding singlet oxygen quencher DABCO(1,4-diazabicyclo [2,2,2]octane) to the solid-state dye.

Intramolecular Charge Transfer in Pyrromethene Laser Dyes: Photophysical Behaviour of PM650

Absorption and fluorescence (steady-state and time-correlated) techniques are used to study the photophysical characteristics of the pyrromethene 650 (PM650) dye. The presence of the cyano group at the 8 position considerably shifts the absorption and fluorescence bands to lower energies with respect to other related pyrromethene dyes; this is attributed to the strong electron-acceptor character of the cyano group, as is theoretically confirmed by quantum mechanical methods. The fluorescence properties of PM650 are intensively solvent-dependent. The fluorescence band is shifted to lower energies in polar/protic solutions, and the evolution of the corresponding wavelength with the solvent is analysed by a multicomponent linear regression. The fluorescence quantum yield and the lifetime strongly decrease in polar/protic solvents, which can be ascribed to an extra nonradiative deactivation, via an intramolecular charge-transfer state (ICT state), favoured in polar media.

Photophysical Properties of the Pyrromethene 597 Dye: Solvent Effect

UV−vis absorption spectroscopy and fluorescence (steady-state and time-resolved) techniques were used to study the photophysical properties of the pyrromethene 597 (PM597) dye in several solvents, which include a wide range of apolar, polar, and protic media. This dye presents a lower fluorescence quantum yield than the well-known PM567 dye because of an increase in the nonradiative deactivation rate constant. This is attributed to a loss of planarity in the excited state provided by the steric hindrance of the tert-butyl groups at positions 2 and 6 of the chromophore core. Such a geometrical change in the excited state leads to an important Stokes shift, reducing the reabsorption and reemission effects in the detected emission in highly concentrated dye solutions. The highest fluorescence quantum yield of PM597 is observed in polar media.

Pyrromethene 567 Dye as Visible Light Photoinitiator for Free Radical Polymerization

AbstractIn the present work we report on the photochemistry and photopolymerization activity of a new bimolecular photoinitiator system, which exhibits maximum sensitivity at 518 nm, consists of a sensitizer dye, pyrromethene 567 (PM567), and a radical generating reagent 3,3′,4,4′‐tetra(tert‐butylperoxycarbonyl)benzophenone (BTTB). The photosensitization of BTTB through the excitation of PM567 induces high polymerization rates, while different experiences have revealed that PM567 or BTTB, separately, are unable of initiating the polymerization of 2‐hydroxyethyl methacrylate (HEMA) over extensive periods of time at 40 °C, either in the dark or under irradiation. The polymerization efficiency of this photoinitiator system, PM567/BTTB, was analyzed following the bulk polymerization kinetics of monomer HEMA by differential scanning photo‐calorimetry. Photopolymerization rates and quantum yields were observed under isothermal conditions (40 °C) for continuous illumination polymerizations (at 518 nm) at different incident light intensities and different BTTB concentrations.Scheme of the photosensitization process of the bimolecular photoinitiator system of PM567/BTTB.magnified imageScheme of the photosensitization process of the bimolecular photoinitiator system of PM567/BTTB.

10 kHz repetition rate solid-state dye laser pumped by diode-pumped solid-state laser

We describe the operation of an all solid-state pulsed dye laser of high repetition rate (10 kHz) pumped by a diode-pumped laser. Three different active media in the form of coin-sized disks were investigated: the dye rhodamine 6G doped in a copolymer of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) [Rh6G/P(MMA:HEMA)], and the dye pyrromethene 567 (PM567) doped in copolymers of MMA with pentaerythritol triacrylate (PETA) and with pentaerythritol tetraacrylate (PETRA) [PM567/P(MMA:PETA) and PM567/P(MMA:PETRA)]. Pump radiation at 527nm was provided by a frequency-doubled diode-pumped Nd:YLF laser Q-switched at 10 kHz. Laser output was observed with an initial average power of 560 mW for Rh6G in P(MMA:HEMA), and with an initial average power of 430 mW for PM567 in P(MMA:PETRA) and 220 mW for PM567 in P(MMA:PETA). In the case of Rh6G/P(MMA:HEMA), the output decreased to about half the initial value after about 6.6 min (or about 4.0 million shots) due to dye degradation. The device constitutes a tunable, all solid-state, high repetition rate laser system possibly suitable for biomedical and dermatological applications.

Photophysical and lasing properties of new analogs of the boron-dipyrromethene laser dye pyrromethene 567 incorporated into or covalently bounded to solid matrices of poly(methyl methacrylate).

The photophysical, lasing and thermostability properties of newly synthesized analogs of the commercial dye pyrromethene 567 (PM567) have been measured in polymeric matrices of poly(methyl methacrylate) both when used as a dopant and when covalently bounded to the polymeric chain. These analogs have an acetoxy or a polymerizable methacryloyloxy group at the end of a polymethylene chain at Position 8 of the PM567 chromophore core. Clear correlations between photophysical and lasing characteristics are observed. Linking chain lengths with three or more methylene units give the highest fluorescence quantum yields (as high as 0.89) and lasing efficiencies (as high as 41%). The covalent linkage of the chromophore to the polymeric chain via the methacryloyloxy group improves the photostability of the PM567 chromophore.

Studies on laser action from polymeric matrices based on trimethylsilyl methacrylate doped with pyrromethene 567 dye

The lasing properties of pyrromethene 567 (PM567) dissolved in solid poly-trimethylsilyl-methacrylate (TMSMA) cross-linked with ethylene glycol dimethacrylate (EGDMA) and copolymerized with methyl methacrylate (MMA) have been investigated. The vol/vol proportion of the different comonomers in each copolymer formulation was systematically varied, and the effect of each composition on the laser action of PM567 was evaluated. The laser samples were transversely pumped at 534 nm with 5.5 mJ/pulse from a frequency doubled Q-switched Nd:KGW laser. Lasing efficiencies of up to 14% and good stability with no sign of degradation after 10,000 pump pulses at 1 Hz in the copolymer P(TMSMA:MMA 50:50) were demonstrated. Pumping this sample at 10 Hz, the laser emission of PM567 remained at 45% of its initial value after 40,000 pulses.