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.     

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.     

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 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.     

Enhanced laser characteristics of pyrromethene 650 using modified PMMA as solid hosts

Solid-state samples based on modified polymethyl methacrylate (MPMMA) with methanol doped with the dye pyrromethene 650 (PM650) are prepared.The effects of a volume percentage of methanol on the laser characteristics of the sample,including spectra properties,slope efficiency,photostability and tunable properties,are investigated.The broadband dye laser output wavelength is around 655 nm and a highest slope efficiency of 32.23% is achieved.Pumping the samples at a repetition rate of 5 Hz with a pulse energy of as high as 100 mJ (the fluence is 0.26 J/cm 2),the longest lifetime (168000 shots) is obtained in the sample (MMA:methanol=18:2),and the corresponding normalized photostability reaches 109.19 GJ/mol.When the sample (MMA:methanol=18:2) is placed in a Shoshan-type oscilla-tor,the narrow-linewidth operation is a continuous tuning range (up to 64 nm).The results indicate that the laser characteristics of solid-state dyes can be greatly enhanced by using modified PMMA with methanol serving as the solid host.     

Environment effects on the lasing photostability of Rhodamine 6G incorporated into organic-inorganic hybrid materials

The effect on the lasing photostability of Rhodamine 6G (Rh6G), and the rigidity of a hybrid inorganic-organic matrix by controlled addition of di-, tri- and tetrafunctionalized alkoxides has been evaluated. The dye was incorporated into hybrid matrices of (2-hydroxyethyl methacrylate) (HEMA) or vol/vol copolymers of methyl methacrylate (MMA) and HEMA with different weight proportions of polycondensated dimethyldiethoxysilane (DEOS), methyltriethoxysilane (TRIEOS), and tetraethoxysilane (TEOS). The laser samples were transversaly pumped at 534 nm at 5.5 mJ/pulse and up to a 10 Hz repetition rate. The dependence of the laser photostability on organic-inorganic composition, pH of the medium, and thermal treatment of the samples was studied. Good stability, with a drop of the initial laser output of only 13% after 10000 pump pulses at 10 Hz in a thermally postcured (HEMA-15 wt%TRIEOS) matrix was obtained. Careful control of the synthesis process is required to reach the necessary photostability for a solid-state dye laser based on hybrid matrices to become competitive with liquid dye lasers. PACS 81.05.Lg; 81.05.Zx; 81.20.Fw; 42.55.Mv; 42.55.Rz; 42.60.Lh; 42.62.b; 42.70a; 42.70-Hj; 42.70.Jk     

Efficient lasing action from Rhodamine-110 (Rh-110) impregnated sol-gel silica samples prepared by dip method

Rhodamine-110/sol-gel samples are prepared by sol-gel technique using dip method. Concentration dependent photophysical studies of these samples have indicated about the least possibility of aggregate formation. The lasing action of Rh-110 in silica samples is studied as a function of dye concentration. An efficient laser emission is observed when the samples are transversely pumped at 337.1 nm and 1.5 Hz repetition rate using a nitrogen laser (400 μJ energy/pulse and 4 ns pulse duration). The maximum of 166% laser efficiency of dye doped sol-gel samples compared to Rhodamine-6G (Rh-6G) in methanol is achieved. The photostability is also measured by using N₂ laser at 1 Hz and it is found nearly 165 pulses. The possible reasons for the photodegradation of the dye molecules are discussed in detail.     

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.     

PM567-Doped solid dye lasers based on PMMA

Polymers are a kind of attractive hosts for laser dyes due to their high transparency in both pumping and lasing ranges and superior optical homogeneity. In this paper solid dye samples based on polymethyl methacrylate (PMMA) doped with different concentrations of 1, 3, 5, 7, 8 -pentamethyl-2, 6-diethylpyrromethene-BF$_{2 }$ (PM567) are prepared. The absorption, fluorescence and lasing spectra of the samples are obtained. Wide absorption and fluorescence bands are obtained and a red shift of the maxima of the lasing emission spectra is observed. With the second-harmonic generation of Q-switched Nd:YAG laser (532\,nm, $\sim $20\,ns) pumping the samples longitudinally, the slope efficiencies of the samples are obtained. There is an optimal dye concentration for the highest slope efficiency when the pumping energy is lower than some typical value ($\sim $250\,mJ), and the highest slope efficiency 35.6{\%} is obtained in the sample with a dye concentration of $2\times10^{ - 4}$\,mol/L. Pumping the samples at a rate of 10Hz with a pulse energy as high as 200\,mJ (the fluence is 0.2\,J/cm$^{2})$, the output energy drops to one-half of its initial value after approximate 15500 pulses and the normalized photostability is 5.17\,GJ/mol. A kind of solid dye laser which could have some applications is built.     

Photo-physical properties and amplified spontaneous emission of a new derivative of fluorescein

The synthesis of new high-performance dyes and the implementation of new ways of incorporating the organic molecules into the solid host matrices have produced a great deal of activity in the field of solid-state dye lasers. In this article, the new laser dye, 2-(6-allyl-3-oxo-3H-xanthen-9-yl)-benzoic acid ethyl ester [AXBE] has been synthesized, and its chemical structure was confirmed by ¹H NMR, ¹³C NMR, IR and elemental analysis. This new dye was covalently bonded with methyl methacrylate (MMA) and 2-hydroxy ethyl methacrylate (HEMA) copolymer backbone and evaluated as the active medium of the solid-state laser dye. Its optical properties were experimentally investigated. Amplified spontaneous emission (ASE) and photostability were studied by pumping the dye sample with 355 nm (8 ns) pulsed Nd-YAG laser.     

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.     

Spectroscopic and lasing properties of Xanthene dyes encapsulated in silica and polymeric matrices

The photo-physical properties of Xanthene dyes: Basic Rhodamine Yellow (BRY), Rhodamine590perchlorate (R590p), SulforhodamineB (SRB) doped in tetramethylorthosilicate (TMOS) and poly-methylmethacrylate (PMMA) are observed. The various parameters viz. full-width at half-maxima (FWHM), peak emission wavelength, quantum yield and excited state lifetime at different concentrations ranging from ∼0.05 to ∼1 mM of the dye under excitation by Copper Vapor Laser (CVL) of high repetition rate (∼5.6 kHz) of are investigated. In order to identify photostability in dyes, normalized photostability has been studied and found that silica gel samples containing dye are more stable than that of polymeric samples. This has been further understood in terms of number density of unbleached dye molecules that infers that photobleaching of dye molecules is not prominent at higher concentrations in glassy solid matrices. Pump intensity dependent optical gain of the samples has also been reported and efforts have been made to study the efficiency of solid-state laser samples in a cavity for the performance of the dye laser.     

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     

Nonlinear optical absorption and NIR to blue conversion in highly stable polymeric dye rod

A simple method for preparing transparent crack-free solid polymeric matrices is presented. Different dopants may be hosted in the polymeric matrix. The method is applied to prepare Glycidyl-methacrylate polymeric rods doped with solutions of coumarin 500 laser dye (ethanol and chloroform). The solvent??s effect has appeared as a shift in the absorption and photoluminous spectral bands of the laser dye in the solid polymeric host. The prepared solid samples showed nonlinear optical response on excitation with 532?nm of nanosecond laser pulses using the open aperture z-scan technique. Each sample shows different nonlinear behavior in response to the irradiating laser beam. The theoretical fitting of the experimental data indicates that the dominant mechanism of nonlinear absorption is the two-photon absorption process. Visible amplified spontaneous emission is reported in both polymeric dye rods by NIR pumping. High photostability is reported for the samples.     

Time-resolved thermal lens study on the heat dissipation effects in solid polymeric matrices used as laser dyes

A dual-beam pulsed-laser time-resolved thermal lens (TRTL) has been used to study the heat dissipation effects in solid polymers employed as laser dyes. The laser-dye samples studied are polymer solutions of rhodamine 6G (Rh6G), namely homopolymers of methyl methacrylate (MMA) and copolymers of methyl methacrylate and 2-hydroxyethyl methacrylate (HEMA) with MMA:HEMA compositions 1:1 and 7:3 vol./vol., where the dye is either dissolved or modified and copolymerized with methacrylate monomers. The long-term stability of the laser material is independent of the thermal diffusivity of the samples, as determined by the TRTL technique. This suggests that the rate of heat dissipation does not play a major role in the photostability of the samples. In contrast, the TRTL experiments have revealed permanent changes in the optical properties of the polymers when subjected to a large number of laser pulses. This is explained in terms of permanent plastic deformation of the matrices. Received: 19 June 2002 / Revised version: 1 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Dedicated to Prof. S.E. Braslavsky on the occasion of her 60th birthday. This work was presented at the V Congreso de Fotoquímica, Torremolinos, Spain, 2001 RID="**" ID="**"Corresponding author. Fax: +34-93/205-6266, E-mail: s.nonell@iqs.es     

<Emphasis Type="Italic">Z</Emphasis>-scan measurement of optical nonlinearity in solid-state dye doped media

Nonlinear refraction in various polymethyl methacrylate (PMMA) solid hosts when doped with fluorescent organic dyes, commonly used as a laser active medium, has been studied. The observed thermal lensing effect arising from optical nonlinearity, results from non-radiative energy transfer from the dye molecules to the solid matrix and is, therefore, strongly dependent on the thermal properties and material parameters of the polymeric host. The non-linear index of refraction, n₂, for each sample of dye doped polymeric host, has been measured employing the standard Z-scan technique. These measured values of n₂, have been used to determine the extent of variation in the index of refraction with varying temperature, dn/dT, for the various host materials. Estimation of dn/dT is critical in determining the extent of thermal lensing in the dye doped solid-state medium, that in turn determines the spatial quality and divergence of the generated laser beam delivered by a dye doped solid-state laser system. PACS 42.55.Mv; 42.65.Jx; 42.70.Jk     

Gain studies of coumarin 307 dye doped polymer laser

Solid state dye doped polymer is an attractive alternative to the conventional liquid dye solution. In this paper the laser characteristics of coumarin 307 (C307) doped polymethyl methacrylate rods modified with dioxane are studied under nitrogen laser excitation in a transverse pumping configuration and the variation of gain of the dye in solid medium for different pumping powers is studied. The photobleaching of dye doped polymer rod is also studied.     

Highly efficient and photostable solid-state dye lasers based on modified copolymers doped with PM567

Solid-state dye samples based on modified copolymers of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) with methanol doped with PM567 were first prepared. The volume proportions of methanol have great effects on the laser's characteristics including spectra, lasing output and thermal properties. The highest slope efficiency of 64.25% was achieved in the sample MP (MMA:HEMA = 85:15 + 10% methanol). 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 maximum lifetime of 278,000 shots was obtained in the sample MP (MMA:HEMA = 85:15 + 15% methanol), and the corresponding normalized photostability reached 180.7 GJ/mol. The obtained ten-shots damage thresholds were as high as 6.7 J/cm². The results indicate that the laser properties of solid-state dyes can be greatly enhanced by using modified copolymers of MMA and HEMA with methanol as solid hosts.     

Gain studies of Coumarin 503 dye-doped polymer laser

Solid-state dye doped polymer is an attractive alternative to the conventional liquid dye solution. In this paper, the laser characteristics of Coumarin 503 (C503) doped polymethyl methacrylate (PMMA) rods modified with ethyl alcohol (EtOH) are studied under nitrogen laser excitation in a transverse pumping configuration and the variation of gain of the dye in solid medium for different pumping powers is studied. The gain of Coumarin 503 in solid medium is compared with the gain of Coumarin 503 in liquid medium and it is found that the gain of the dyes in the solid environment is less than that in the liquid environment. The photobleaching of dye in polymer medium under nitrogen laser excitation is also studied by keeping the rod in a fixed position and by rotating the rod about its cylindrical axis. It is found that the photobleaching rate is faster when the rod is in a fixed position.     

Highly photostable laser solution and solid-state media based on mixed pyrromethene and coumarin

A substantial increase in the photostability of pyrromethene 567 laser dye solutions and in solid polymer media has been achieved by the addition of coumarin C540 laser dye. Up to five times increase in photostability of pyrromethene 567 in solid and two times in solution has been observed. The enhanced photostability is attributed to reduction in the effectiveness of in situ oxygen degradation of pyrromethene by the addition of the coumarin.