Organic Dyes in Laser Technology

Laser technology has been developed to a very high level since 1960. Significant advances have been made possible only by the use of organic dyes as optical shutters for the production of giant pulses. Ultrashort pulses in the picosecond range were first produced in 1966; their measurement was greatly facilitated by the use of organic dyes. Probably the most important recent advance in the laser field is the dye laser, which was first described in 1966, and in which the active medium is a solution of an organic dye.     

LASER MEDIATED RELEASE OF DYE FROM LIPOSOMES

Liposomes made from phospholipids and containing sulforhodamine dye (1-50 mM) have been irradiated with nanosecond and picosecond laser pulses. Individual liposomes were locally heated by laser absorption of dye dimers during a single laser pulse, and heating was sufficient to release the liposome contents. The extent of dye release produced by a single laser pulse was shown to be quantitatively dependent on several interdependent variables, including dye concentration, liposome size, laser excitation parameters and initial temperature of the dye-liposome system. Fluorescence lifetime data having three components have been obtained and analyzed in terms of three dye environments. Quantitative estimates support a photo-induced thermal mechanism for liposome lysis and release of its contents. These results may be useful for laser induced delivery of therapeutic agents or other applications of lasers in biological systems.     

Polymer-filled nanoporous silica aerogels as hosts for highly stable solid-state dye lasers

New hybrid solid-state dye laser materials based on highly porous silica aerogels have been synthesized. The open porous network of the aerogel was saturated with laser dyes dissolved in appropriate organic monomers, and polymerization took place inside the silica structure. The resulting polymer-filled nanoporous aerogel (PFNPA) was cast in a cylindrical shape, forming monoliths that were used as gain media in solid-state dye lasers. When the PFNPA incorporated pyrromethene dyes, highly photostable laser emission with good lasing efficiency was obtained. Under the demanding conditions of tightly focused transversal pumping with 532 nm, 5 mJ pulses at 10 Hz repetition rate, the commercial dye Pyrromethene 567 exhibited laser action with only a 10% drop in the laser output after 10(6) pump pulses in the same position of the sample.     

Fluorescent and laser properties of pyrromethene 567 (PM567) doped into multi-precursors derived gel glasses

In this work, the laser dye PM567 was incorporated into various organically modified silicate gel glasses (ORMOSILs) derived by methyltriethoxysilane (MTES) and vinyltriethoxysilane (VTES) precursors mixed in various ratios. The laser performances of PM567 doped into MTES–VTES-derived ORMOSILs including the laser slope efficiency, threshold and lifetime together with the spectroscopic properties were investigated. Blue-shifts of fluorescent peaks, extended fluorescent lifetime, improved laser efficiency and lifetime of PM567 doped into ORMOSILs derived by mixed precursors of MTES and VTES have been observed, which might related to the microstructures and micro-chemical environment of the dye in ORMOSILs.     

Photostability of Silylated Coumarin Dyes in Polyceram Hosts

Numerous silylated coumarin dyes have been incorporated within silica : polydimethylsiloxane Polyceram hosts using the sol-gel process to form crack-free, polishable monoliths. The use of silylated laser dyes allows for covalently bonding the laser dyes to their hosts. Photostability of the samples was evaluated by measuring the decrease in the dye absorption in the Polyceram upon ultraviolet lamp exposure and by monitoring the fluorescence intensity as function of pump pulses from a N₂ laser at 337 nm. Both methods showed a significant improvement in photo- and thermal-stability of the silylated dye Polyceram compared to that of the unsilylated dye Polyceram at a dye : Si mole ratio of 10^-4 : 1. The improved stability is attributed to the immobilization and higher degree of caging of the silylated dye Polyceram with respect to the unsilylated dye Polyceram.     

Investigation of optical nonlinearities of an azo dye using a 532nm diode-pumped Nd:YAG laser

Solid-state dye-doped polymers are attractive alternatives to the conventional liquid dye systems. In this paper, the third order nonlinear optical property of Sudan III, an azo dye in solvents and dye doped polymer films measured using the Z-scan technique is reported. Multiple diffraction rings were observed when the dye doped in both the liquid and solid media was exposed to a diode-pumped Nd:YAG laser at 532nm.     

UV Radiation Effects on SiO2 Gels Doped with Organic Dyes

Silica gels prepared by the sol-gel method with TEOS as a precursor and doped with the organic dyes rhodamine B, Na fluoresceine and eosine G were exposed to UV radiation pulses from a nitrogen laser. The absorption, luminescence and IR spectra were taken as a function of the exposure time. The absorption and the luminescence curves show successive maxima and minima. The same response is observed when the exposure procedure is repeated. These results are explained in terms of the cyclic filling and depletion of the long-lived triplet excited electronic state. At short exposure times, the data can be fitted with a Lorentzian curve and the corresponding parameters are given.     

Effective two-photon absorption cross section of heteroaromatic quadrupolar dyes: dependence on measurement technique and laser pulse characteristics

The linear and nonlinear optical properties of the heteroaromatic push-pull-push two-photon absorbing dye N-methyl-2,5-bis[1-(N-methylpyrid-4-yl)ethen-2-yl]-pyrrole ditriflate (PEPEP) are reported. The determination of the two-photon absorption (TPA) cross-section spectrum has been performed with different techniques: femtosecond TPA-white light continuum probe experiments, two-photon-induced fluorescence, and open aperture Z-scan measurements using both nanosecond and femtosecond laser pulses. The measured TPA cross sections and their wavelength dispersion show a marked dependence on the parameters of the laser pulses and on the measurement technique employed. These properties are discussed in terms of the different microscopic mechanisms that can contribute to the multiphoton absorption processes, with different weight depending on the measurement conditions and on the photophysical parameters of the dye.     

Picosecond time scale optical coherence experiments in mixed molecular crystals: pentacene in naphthalene

Picosecond time scale high-power pulse optical coherence measurements including photon echo and the stimulated photon echo are obtained with a mode-locked dye laser synchronously pumped by a double Q-switched and mode-locked Nd: YAG laser. Effects on coherence arising from excitation with gaussian laser pulses rather than square pulses are examined. Preliminary echo decay measurements are reported.     

SnO2/SiO2 and Sn/Sb-oxide/SiO2 gel-derived composites. Part 1: Structural evolution from a Mössbauer study

The lasing photostability of the red perylimide dye (RPD) in various solid matrices was measured under frequency-doubled Nd:YAG laser excitation. The RPD: composite glass laser intensity decayed to 50% of its initial value after approximately 20,000 pump pulses of 13 mJ/pulse. The output of RPD:ormosil glass and RPD:PMMA glass lasers decayed to 50% of their initial value after 1,200 and 1,000 pump pulses of the same energy, respectively. For rhodamine-6G:silica-gel and rhodamine-6G:ormosil glass lasers, the 50% decay occurred already after 1,000 and 300 pulses, respectively. The decay was non-exponential, suggesting that the dye bleaching was not a single-photon process. The average laser output decay rates increased linearly with the pump energy. Singlet-singlet excited state absorption of the RPD dye in the solid matrices was also measured between 550 and 730 nm. At ～600 nm the cross section was ～2×10^?16 cm²/molecule. The excited-state absorption competes with the lasing, and is a main factor that limits the laser efficiency.     

高分子固溶态染料激光材料的光学性质（Ⅰ）

引入极性交联剂(Ⅰ)改性的MMA-MA共聚物作基质,通过研究激光染料Rh6G在不同组成的基质中的吸收光谱、荧光特性和激光能量转换效率的关系,获得含Rh6G的固溶态材料。对材料的光学均匀性作了探讨,材料的激光输出特性达到同条件下的Rh6G乙醇溶液水平,显示了染料在固溶态中激光运转的可能性。     

Picosecond recovery dynamics of malachite green

Using sub-picosecond pulses from a mode-locked cw dye laser we have studied ultra-fast absorption recovery in the triphenylmethane dye malachite green after excitation to the first singlet. In methanol an exponential time constant of 2.1 ps is measured. As solvent viscosity is increased recovery becomes slower and a two component relaxation is evident.     

Optical properties of Rh 6G dye in liquid and solid polymer

Rhodamine 6G dye doped in liquid MMA (monomer) and solid polymer (PMMA) has been studied and its spectra compared with the one dissolved in n-BA solvent. The effect of temperature and laser power on the emissive characteristics of dye in polymer and in solvent has also been compared.     

溶剂挥发法制备掺杂激光染料的具有光致发光特性的介孔薄膜

本文采用溶剂挥发法制备了掺杂香豆素151的具有介孔结构的透明二氧化硅薄膜, 并对其荧光发光特性进行了研究.     

Structure induced by irradiation of femtosecond laser pulse in dyed polymeric materials

We investigated the structures induced by an irradiation of a near‐infrared (NIR) femtosecond laser pulse in dye‐doped polymeric materials {poly(methyl methacrylate) (PMMA), thermoplastic epoxy resin (Epoxy), and a block copolymer of methyl methacrylate and ethyl acrylate‐butyl acrylate [p(MMA/EA‐BA) block copolymer]}. Dyes used were classified into two types—type 1 with absorption at 400 nm and type 2 with no absorption at 400 nm. The 400‐nm wavelength corresponds to the two‐photon absorption region by the irradiated NIR laser pulse at 800 nm. Type 1 dye‐doped PMMA and p(MMA/EA‐BA) block copolymer showed a peculiar dye additive effect for the structures induced by the line irradiation of a NIR femtosecond laser pulse. On the contrary, dye‐doped Epoxy did not exhibit a dye additive effect. The different results among PMMA, p(MMA/EA‐BA) block copolymer, and Epoxy matrix polymers are supposed to be related to the difference of electron‐acceptor properties. The mechanism of this type 1 dye‐additive‐effect phenomenon for PMMA and p(MMA/EA‐BA) block copolymer is discussed on the basis of two‐photon absorption of type 1 dye at 400 nm by the irradiation of a femtosecond laser pulse with 800 nm wavelength and the dissipation of the absorbed energy to the polymer matrix among various transition processes. Dyes with a low‐fluorescence quantum yield favored the formation of thicker grating structures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2800–2806, 2002     

Spectral characteristics and nonlinear studies of crystal violet dye

Solid-state dye-doped polymer is an attractive alternative to the conventional liquid dye solution. In this paper, the spectral characteristics and the nonlinear optical properties of the dye crystal violet are studied. The spectral characteristics of crystal violet dye doped poly(methylmethacrylate) modified with additive n-butyl acetate (nBA) are studied by recording its absorption and fluorescence spectra and the results are compared with the corresponding liquid mixture. The nonlinear refractive index of the dye in nBA and dye doped polymer film were measured using z-scan technique, by exciting with He-Ne laser. The results obtained are intercompared. Both the samples of dye crystal violet show a negative nonlinear refractive index. The origin of optical nonlinearity in the dye may be attributed due to laser-heating induced nonlinear effect.     

Investigation on Spectroscopic and Laser Properties of Pyrromethene and Perylene Chromophores in Elastic Polymeric Hosts

In this work, two types of chromophore i.e. the pyrromethene and perylene families dyes were doped into elastic polymeric host materials based on polydimethylsiloxane (PDMS), which had been widely employed in various applications. The solubilities, spectroscopic and laser properties of these dyes doped into PDMS matrices were systematically investigated. Tunable laser output with high conversion efficiencies and low laser thresholds were observed and calculated. The laser longevity of pyrromethene dyes doped in PDMS matrices could exceed 1 × 10⁵ pulses through a fast self‐recovery on the laser output with the elapse of aging time. The efficient and stable laser output of the dopants and the flexibility of the PDMS host provided the feasibility of such gain media as mechanically tunable laser sources, which might be employed as cost‐effective components on integrated bio‐chips.     

Dual fluorescence of Methylene Blue encapsulated in silica matrix

Dynamics related to the optical effect of Methylene Blue (MB) dye molecules in solid host has been investigated. MB doped silica samples of varying concentrations are prepared by the sol–gel technique in acidic environment. Absorption and laser induced fluorescence spectra have been recorded for the samples. Interesting result of dual fluorescence at lower concentrations is explained. Attempt is done to study the dynamics of the dual fluorescence. These results may be useful for designing and developing solid-state optoelectronic devices.     

负载激光染料香豆素151的MCM-41粉体及其纤维的光学性质研究

通过结晶包覆的方法将激光染料香豆素151成功地负载到具有介孔结构的MCM-41粉体和纤维中,制备了具有光致发光特性的MCM-41粉体和纤维材料,并通过SEM,SAXRD,UV-Vis和PL进行了表征.     

Click assembly of dye-functionalized octasilsesquioxanes for highly efficient and photostable photonic systems

New hybrid organic–inorganic dyes based on an azide‐functionalized cubic octasilsesquioxane (POSS) as the inorganic part and a 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BDP) chromophore as the organic component have been synthesized by copper(I)‐catalyzed 1,3‐dipolar cycloaddition of azides to alkynes. We have studied the effects of the linkage group of BDP to the POSS unit and the degree of functionalization of this inorganic core on the ensuing optical properties by comparison with model dyes. The high fluorescence of the BDP dye is preserved in spite of the linked chain at its meso position, even after attaching one BDP moiety to the POSS core. The laser action of the new dyes has been analyzed under transversal pumping at 532 nm in both the liquid phase and when incorporated into solid polymeric matrices. The monosubstituted new hybrid dye exhibits high lasing efficiency of up to 56 % with high photostability, with its laser output remaining at the initial value after 4×10⁵ pump pulses in the same position of the sample at a repetition rate of 30 Hz. However, functionalization of the POSS core with eight fluorophores leads to dye aggregation, as quantum mechanical simulation has revealed, worsening the optical properties and extinguishing the laser action. The new hybrid systems based on dye‐linked POSS nanoparticles open up the possibility of using these new photonic materials as alternative sources for optoelectronic devices, competing with dendronized or grafted polymers.