Tunable Laser Applications Solid-State Organic Dye Lasers

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Tunable Laser Applications

F.J. Duarte

Solid-State Organic Dye Lasers

Publication details https://www.routledgehandbooks.com/doi/10.1201/b19508-4 F.J. Duarte Published online on: 09 Feb 2016

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The publisher does not give any warranty express or implied or make any representation that the contents will be complete or accurate or up to date. The publisher shall not be liable for an loss, actions, claims, proceedings, demand or costs or damages whatsoever or howsoever caused arising directly or indirectly in connection with or arising out of the use of this material. Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 References 3.2 levels first ofexcited S the singlet electronic state shown Figure 3.1 in visible with pumped or ultraviolet vibrational . When higher light, complex rather the dyean organic of energy levelof is diagram simplified structure A asolid solvent into dissolved matrix. organic molecules an are in or incorporated extended systems of conjugated by containing doubleized adye bonds. In laser, these physics, spectroscopy, industry. chemistry, and and medicine to awide to of fields, range applicability different from basic science, their suchas in resulted has lasers of these versatile nature The pulses. generation of ultrashort possible molecules of bandwidth makes these the gain large the tunability, and and wavelength-selective cavity elements laser allows the operation in narrow-linewidth of introduction The infrared. ultraviolet the near covering from range the to the averagehigh powers. of dyes Hundreds measurably, lase have to demonstrated been yield to energies and pulse ability high excitation inherent exhibit and an sources, continuous-wave of and awide pulsed with variety both emit pumped be can forms, flexibility operational unique visible[1,2]. of their because radiation Dye can lasers mid-1960s,From the dye of have coherent lasers sources tunable attractive been 3.1 3.3 3.1 CONTENTS lowest level vibrational of S excited the relaxation, fast dye radiationless the in After molecules accumulate lated. lation of S lower the from level radiative depopu the with Competing transition. laser of the of the ground electronic state S state electronic ground of the level this emission levels depopulates Laser higher-lying into vibrational–rotational © 2016 Group, by Taylor LLC & Francis Organic dyes fluorescent high moleculesmolecular Organic weights, are with character

3.2.4 3.2.3 App 3.2.2 Mate Introduction 3.2.1 3 INTRODUCTION lications

1 rials ...... , there are radiationless transitions into the lower the into transitions T radiationless state triplet are , there Poly Sili Orga Orga Angel Costela, I. García-Moreno, and Sastre R. Lasers Dye Organic Solid-State ...... con-Modified Organic Matrices Organic con-Modified mers with Nano- and Micro-Particles and Nano- with mers . nic–Inorganic Hybrid Materials nic–Inorganic Polymersnic ...... 1 , which constitutes the upper level upper , which the constitutes transition. laser of the . 0 ...... Finally, remove processes nonradiative molecules ...... 1 of the dye of the popu molecules are ...... 1 . This . This 160 146 146 165 143 167 143 171 171 - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 144 handle large volumes large handle toxic continuous addition, of sometimes messy liquids. In and to ous inconveniences need the to related evidenced by liquiddye the mainly lasers, seri of Nevertheless,approach waslasers. never the because satisfactory this fully media for cooled bydyeity and simply usingthe aflowstandard system,became qual optical high with solvents,organic obtained be active whichcan the in medium quickly [5]. emission laser rather faded the that liquidsolutions Thus, of dyes in were low, dye result the the with and molecules fast experienced photodegradation, for of operation dyes lasing solidefficiencies butments werethe state, the the tried in ing, respectively. arrange pumping and of materials next Over avariety the decade, [3] by Snavely and Peterson and 1968 in [4] pump flashlamp and laser pulsed with dyesolid-state (SSDLs) lasers by were Soffer demonstrated McFarland1967 in and dye the moleculesfirst solid the into hosts, and were incorporate to made attempts days early From the developmentof media. the laser as impact cant of dye lasers, dyes solid that phases liquidand have it orphase, gas the liquid, is in asignifi made solid, dyes Figure 3.2. Although the in in lase have to demonstrated illustrated been overlap,consist as continuum, fluorescenceof a broad spectra and absorption and fluorescentlines different the Thus, mechanisms. duecontinuum line-broadening to domain. time nanosecond the in not appreciablepopulation fast triplet system enoughup an are build to crossing rates inter usual the excitation because pulsed pulses under nanosecond with important not very losses quenchers. triplet are These of quantities appropriate small by adding reduced be losses triplet can or even The lasing process. the inhibiting halting band, overlap bands absorption cause considerable lasing triplet–triplet the losses the if lower the could and populates intersystem crossing state process triplet metastable FIGURE 3.1 © 2016 Group, by Taylor LLC & Francis The levelsThe Figure 3.1 shown in schematically closely spaced are enough forma to

Sche matic energy-level diagram for a typical dye molecule. for energy-level atypical matic diagram Ex S S S 0 1 2 citation Singlet states Emission In crossing tersystem Nonradiative quenching Absorption Tr iplet states Tunable Laser Applications Tunable Laser T T 1 2 ------Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 Chapter 8. in applications of described dye medical are and lasers Chapter 4, in discussed are SSDL red. oscillators the to narrow-linewidth green region the from spectral the in using dyes emission with obtained results on the mainly concentrate weThus, shall implementation of term. SSDL practical short the to could lead the opments in that thosedevel be on field. The the will in focus art of the state the SSDLs outline and solution. dyes same liquid of in the performance the from far still are solid state in obtained Much blue results the less donein work the dyesregion, with and been has emitting region. spectral red to green the in dyes with haveresults emitting obtained been promising These competitive liquidcounterparts. fully their with SSDLs are that in resulting are fordyes laser as hostmaterials matrices organic silicon-modified or nanoparticles, silica dispersed with media polymeric hybrid materials, inorganic approaches involving years, recent of use new the formulations, polymeric organic– wereadvances toward development made the SSDLs tunable of [2,10]. practical, In result, as a field,significant and, ofthe in activity deal agreat 1990s witnessed field the in dyes laser of SSDLs.The [7–9]arenaissance performance spurred [5,6] resistance laser-damage higher with synthesisof new the and rials high- development 1990s early SSDL the the in and approach, of improved host mate outside use laboratory. the their dye restricted these systems has laser and dye/solvent large which, together the with cost of and size the increases reservoirs, design of the cells, complex and solutionofpumps the circulation bulky and requires solution. 567 methanol in FIGURE 3.2 Solid-State Organic Dye Lasers Dye Organic Solid-State © 2016 Group, by Taylor LLC & Francis In this chapter, we this developments overview recent In present an main of the of consideration of the further problems by posed liquiddyeThe stimulated lasers

Absorbance 0.00 0.03 0.06 0.09 0.12 0.15 0.18

UV 4 8 2 560 520 480 440 /VIS absorption and fluorescence spectra of the laser dye pyrromethene dyelaser the pyrromethene of spectra fluorescence and absorption /VIS bopinFluorescence Absorption Wa velength (nm) 600

Intensity (a.u.) 145 - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 below the brittle-fracture point, improving the laser resistance by several resistance of laser orders the improving point, below brittle-fracture the molecular-weight polymer of to the additives. elastic limit induced the It reduces cization external called be which for can improved search the materials, two to approaches in led different and material of the resistance laser the enhance anew opened way This to matrix. of the properties viscoelastic on the depended step. polymerization the conditions during thermal the and rate control polymerization of the strict requires polymerization, during oped devel anisotropy intrinsic the avoiding polymer or ofminimizing matrix, the mity unifor Optical materials. the of preparation the in microfiltration sonication, and such of use distillation, as processes generalized the from polymers came organic threshold improvements inclusions.ing of laser-damage the significant in first The foreign and absorb impurities such molecular as material, the in absorbing centers ago, of decades was presence due the to on SSDL, studies early three the in used positioned candidates forpositioned developing candidates efficientand stable SSDLs. are well- advanced andmaterials polymerichybrid properlyformulations modified [5,10].materials From work that doneapparent over it last decade, is becoming the hybrid organic–inorganic polymers, and transparent glasses, inorganic to crystals, of solventsdyes: molecular gelatin, or organic atlow mixtures from temperature, fabrication technology.appropriate development the tion and or design of dyes desirable characteristics, of the with the selec- the properties, required the with of solid matrices optimization design and the are problems for addressed the to be lasers, opmentsolid-state tunable of materials classes devel different of dyes with the organic desirable. in is also Thus, material stability. photochemical and Asimple technologyfor matrix doping the thermal good and lasing wavelengths, radiation, and laser to pump threshold damage high ATERIALS alow with atboth quality level optical high molecules transparency are of scattering, host as for used be to lasing dye on asolid matrix imposed basic requirements The 3.2 146 effects due to the relativelyeffects due the to values high of ∂ lensing well as low thermal to due as the to power-damage matrix, of threshold the forprocesses, photodegradation to SSDL related tions of materials polymersare as - or viscoelasticity. limita composition, main weight, molecular The microstructure, way acontrolled volume, in such relevant free as chemical modifying characteristics, inexpensive to refractive in index;the ease adaptability and fabrication techniques; of duevariation microscopic to medium avoid to gain the in interference important dyes; organic with compatibility tion: goodchemical excellent homogeneity, optical applica- this in attractive very them make exhibit that some features materials These Polymers solid as hosts for have lasingdays dyes early tried the of been from SSDLs. o 3.2.1 © 2016 Group, by Taylor LLC & Francis There was soon enough evidence to establish that the resistance to laser damage damage laser to was resistance soonenough the evidenceThere that establish to materials polymeric the in by radiation caused laser damage of the part A great Over the years, a variety of materials have been tried as solid as hosts for have lasing tried of been materials avariety years, Over the

M . External plasticization polymer of is achieved the low- different by. External adding r g anic P o l ymers n / ∂ in these media [11]. media these T in Tunable Laser Applications Tunable Laser internal plasti internal and - - - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 red, depending on the substituents on the chromophore. They are ionic and highly highly ionic and substituents chromophore. are on on They the the depending red, ( and referencesand therein). dyes dipyrromethene.BF These are by Boyer 1980s late coworkers 1990s early the ([17] and and characterized during and region was over synthesized absorption lasing spectral triplet–triplet the reduced stable dyes laser was vigorously anew aresult, As class pursued. of dyes laser with more efficientand obtain to aiming of research aline dyes notwithstanding, mine - rhoda with solid state in obtained results promising solid The state. the in laser solution. wereobvious they Thus, any developan to choicein first attempt a dye werelow-red give to known excellent region liquid spectrum, of in results the laser [16]. covalently chains polymeric chromophore was the to linked Rh6G when the 12,000 pulses to lifetime useful of the 1996, increase in an strated, Costela approach, Using demon et al. macromolecule chains. dye this the and group excited the between interaction no direct in resulting chain, main polymeric the from chromophoreis ofdistant dye group the the into pendant molecule,rated the so that double polymerizable the incorpo chromophore and bonds the between introduced [16]. photostability laser is when group the aspacing effect is more important This in increase is not emission, converted into acorresponding with that energy pump for open dissipation, polymer the along backbone, are the absorbed ofchannels the additional polymer of chain, the dye the polymer host. is apart the When pation in dissi dye of the thermal destruction due poor to thermal the be to seems matrices polymeric into of dye when mechanism incorporated degradation important One polymer. of the chain of main covalently the chromophoreto the ity arises binding 240 GJ/mol). (up photostability to copolymerbut normalized formulation the superior exhibited efficiency, higher demonstrated materials MPMMA conditions, the experimental cal carried out by Giffin et al et out by Giffin carried were MPMMA or in MMA and copolymers of either in HEMA incorporated Rh6G is down value). 50% to of of its initial performance laser Comparativeon the studies mole per input energy of of dye total mol, molecule terms in output when energy the at 337 nm [13]. samples of was 4500 pulses the lifetime useful (20 GJ/ the case, this In pumping transversal under (MMA) methyl and methacrylate (HEMA) methacrylate dissolved acopolymer (Rh6G) 6G in of 2-hydroxyethyl dyeusing the rhodamine by Costela et al plasticization approach was of followed repetitionrate 3.33 Hz.a pump internal The output) laser the in a50% was produce drop 15,000 pulses that of pulses ber at pump samples of (defined- the photostability num as or normalized lifetime useful The at532 nm. longitudinally dyes pumped and late) rhodamine with doped (MPMMA) poly(methyl of modified matrices with methacry 40%–60% efficienciesrange the in comonomers [13]. acrylic basic aliphatic with compound matrix problem overcome be of plasticization: can the copolymerization by using internal leach out and over effects. This unpredictable with migrate time, can and matrix mer [12].magnitude low-molecular-weight The additives have poly the somein mobility Solid-State Organic Dye Lasers Dye Organic Solid-State © 2016 Group, by Taylor LLC & Francis Figure 3.3 At the beginning of the 1990s, the rhodamine dyes, yel emissionthe with in rhodamine 1990s, of the the beginning At the hosts for as used possibil lasing dyes, polymers interesting are organic the When By Maslyukov approach, former using the [14] et al. 1995, in demonstrated, lasing ), with emission covering the spectral region from the green-yellow region the from ), emission with covering spectral the to the . , who, 1995, in also action efficiency with laser demonstrated of 21% in 1999. in [15]. identi under pumped, longitudinally When 2 (PM.BF 2 ) complexes 147 ------Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 we proceeded to synthesize new synthesize to PM.BFwe proceeded Next, operation. laser the composition optimized that structure and parameters mer poly on the chosen information formulations, polymeric gather to carefully into them of solvents, incorporate to avariety in proceeded lasing properties and cal photophysi their We characterizing PM dyes by after began using commercial and, polymers. appropriate into when incorporated lasing properties dyes their probe and new, dipyrromethene the to step was extendto cal research our high-performance combination [10]. matrix/dye best the in results lymer formulation that A next logi out showed by group copo our for optimum that dye each is an carried there studies particular, In medium. of the properties viscoelastic on the depended photostability polymer into hosts, lasing efficiencies dyes whenand the that, were incorporated effectiveness the reduces oxygen of situ in of PM567marin degradation [19]. 350 GJ/mol, C540A dye, laser achieved cou was as also by addition of coumarin the of PM567, photostability the in increase repetition rate. A substantial of up to 2 Hz of 270 photostability GJ/mol, at a anormalized to corresponding 550,000 pulses, of PM567 was DABCO with dissolved additive. lifetime the PMMA useful as in The at pumping 60%–70%efficienciesrange the for 532 nm in longitudinal were obtained this way,In the same. about lasing efficiencyconversion the laser while remained clo (DABCO) (2,2,2) of octane dye photostability was the present, PM567 doubled, dyes (PM) [18]: pyrromethene the singlet when the oxygen quencher 1,4-diazobicy quenchers of singlet oxygen bywith incorporating solid solutions liquidand the in of solutions [17]. problem showed 1999, colleagues dealt could and be In this that Ahmad oxygen with reactions dyescal these relatively makes and air-saturated in unstable (Figure 3.3 photochemi to ), vulnerable which them renders structure their in groups for efficiency daysand benchmark photostability those considered the in [10]. most widely the some employedhosts, of outperform and them dye, laser Rh6G, solid into liquidsolution in when both incorporated and goodperformance with solvents, dyes These lase haveto including demonstrated MMA. alcohols and been andregion, coefficients manyexhibit solubility in good actionover the laser spectral dyes, laser polar yields have and low triplet fluorescence high quantum extinction 148 FIGURE 3.3 C © 2016 Group, by Taylor LLC & Francis 2 H As pointed out, by the mid-1990s, studies with rhodamine dyes had demonstrated dyes demonstrated out,had by mid-1990s, pointed the As rhodamine with studies aromatic dyes of presence amine is the dipyrromethene of disadvantage the One 5 ; Bu: CH

3 (CH Mole 2 ) cular structures of some commercial dipyrromethene.BF of commercial some structures cular 3 . R 2 PM PM PM Dy 580 597 567 NN e FF B 2 8 complexes with that demonstrated and n-Bu t-Bu Et R 6 R Tunable Laser Applications Tunable Laser 2 complexes. Et: ------Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 Solid-State Organic Dye Lasers Dye Organic Solid-State the degree of cross-linking beyond this point will result in the dye the result in molecules beyond being will point this of cross-linking degree the completely be will occupiedby dye. the Increasing matrix polymeric the able within monomer, volume free avail the - cross-linking of concentration the For acertain yield the the emissiondye. of of quantum increase asignificant to vented, leading decay nonradiative aresult, of As excited freedom. dyemolecular molecules is pre vibrational and reduction volume which asignificant rotational of induces decreases, polymer-free the increases, material the in of cross-linking degree the As linking. polymer-free is the volume, ofmaterials cross- by whichdegree is controlled the dye of the polymeric in lasing performance governing the parameter important an controlled. It that was found carefully were material final of the rigidity ity and vol./vol. different monomers in methacrylic [20]. way, proportions this In polar the and acrylic cross-linking and of anumber with linear copolymers ofand MMA SSDLs. polymeric in toward performance laser improving directed strategy obligatory reference any an in material this make of PMMA resistance laser high relatively and formulations developed, excellent the because transparency optical pivotal was chosen the component the as monomers in (Figure 3.4). MMA acrylic - meth and acrylic different with of copolymers of MMA avariety or into PMMA the samples of flat surface [19]. lateral onto the into The dyes incorporated were afrequency-doubled from pulses Nd:YAGnanosecond laser, 532 nm) focused being (typically radiation pump the with was transversal, geometry Pumping surface. flat a lateral cylinder ofdefining the acut with axis along length, the in mm 10 available dyes. laser commercially the outperformed that obtained could be chromophore, new the dyespyrromethene in modifications chemical appropriate (PETA), and pentaerythritol tetraacrylate (PETRA). tetraacrylate (PETA), pentaerythritol and triacrylate pentaerythritol (TMPTMA), trimethacrylate trimethylolpropane (TFMA), rylate methac 2,2,2,-trifluoroethyl 2-hydroxyethyl (HEMA), (MMA), methacrylate methacrylate FIGURE 3.4 © 2016 Group, by Taylor LLC & Francis In a first study, afirst dyeIn commercial PM567dissolved was in homopolymer PMMA and diameter in mm 10 solid rods, samples were the studies, typically our In O

MMA O O Mo O TMPTM lecular structures of some monomers used in solid-state dye methyl lasers: solid-state in used of monomers some structures lecular O O O AP O O O O HEM O O AT O O ET AP O OH OH O O O O ET FM O O O RA A O FF O F O 149 - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 and as a result the thermal degradation of the dye is enhanced. This interpretation interpretation This dye of the degradation is enhanced. thermal aresult the as and not fast enough, are heat as medium sipation the to for released energy channels the - dis the repetitionrate, athigh that rate.It seems degradation the so does increases, at10 Hz repetitionrate were pump when obtained radation, repetitionrate.Thus, the Table 3.1, in results the whereas ofat arepetitionrate 5 Hz, which show faster deg was obtained shown of pulses number Figure 3.5 pump outputin the with laser the of 90 GJ/mol. absorption evolution value the after It that should noticed initial be of at70%dye of PM567 its 95:5) remained dissolved COP(MMA-PETRA in matrix mole per energy pump of dye absorbed molecule,accumulated emission laser from relative the of agiven monomersfying in proportions of copolymer. the terms In TMPTMA. containing matrix lower the in than PETA is containing polymer. of PM567 photostability matrix the aresult, As in a hydroxyl its structure in group, which should a more polar result in incorporates net), macromolecular resulting of points the and cross-linking the segments between plasticitypolymer local of resulting of(i.e., mobility the the increased increased an PETA hand, which other in isresults acrylic, the On of cross-linking. degree same vol./vol. same the in MMA with ratio, they determine when copolymerized that so PETA. and functionalized, triple monomers Both are monomers TMPTMA the containing matrices in obtained results the from appreciated be can solid matrix atom (Figure 3.4).carbon same the to attached chains double polymerizable four (PETRA) lateral in bonds PETA) and (TMPTMA, monomers having three cross-linking with ofmers MMA for solid solutionsparameters of dye PM567 copoly and homopolymer in PMMA Table 3.1, in effect is illustrated This lasing performance. relevant which lists laser dye- the optimizes that of cross-linking degree optimum given an be dye, will there for Thus, any formed. be deleterious will effect operation, on laser their gates, with aggre higher and volume, free dimers and excluded shrinking the from partially 150 © 2016 Group, by Taylor LLC & Francis b a 564 COP(MMA-PETRA 95:5) COP(MMA-PETA 95:5) COP(MMA-TMPTMA 95:5) PMMA Material Laser Parameters TABLE 3.1 and Cross-Linked Copolymers (COP) Copolymers Cross-Linked and

illustrates the effect on the lasing photostability of the dye of the lasing effectphotostability of on the the modi illustrates Figure 3.5 involved complexityThe mechanisms ofaction of laser the dyes the a in in ciency. Dyeconcentration1.5 tial intensityI Intensity ofthelaseroutputafternpumppulsesinsameposition thesamplereferredtoini- λ tively. FWHM,fullwidthathalfmaximum. max : peakofthelaseremission;ΔλFWHMEff: energy-conversion effi - 0 , I n (%) a

for Dye PM567 PMMA in Homopolymer Dissolved =

(I n /I 0 )

100. λ −3 max M. Pumpenergy andrepetitionrate:5.5 mJ and10 Hz, respec- 564 568 562 a (nm) Δλ a (m Eff (nm) 6 5 7 5 Tunable Laser Applications Tunable Laser a 18 21 12 19 (%) I 30 000 80 12 16 20 (%) b - - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 of substitutions at the 8 position of the PM567 molecule while maintaining the four the of substitutions 8position at the PM567 of the molecule maintaining while anumber effect of we approach, the introducing action [25,26]. studied this Pursuing laser the enhance can core molecular substituents the in adequate that and structure, molecular on their depend photophysical their lasing properties that and strated laser. dye a stable narrowband seed PM580to obtain with used doped could be MPMMA at low when intensity,Thus, operating laser pump dye a solid-state on sample based 47.5% to put decreasing energy at1 Hz. 20,000 shots output value of after its initial Solid-State Organic Dye Lasers Dye Organic Solid-State by 0.48 J/cm by over shots when constant pumped of almost 20,000 562.5 nm, emission remained the wavelength operating laser intensity. pump and emission wavelength central At the of 42.7%, 66.0% and on the respectively depended [24]. performance lifetime The slope with emission efficiencies laser was demonstrated, narrowband and broadband [23]. both pumping methanol, with MPMMA into With dye PM580 incorporated additive 5 Hz under methanol modifying organic with HEMA and ofmers MMA of 180.7 GJ/mol photostability normalized forcopoly PM567 modified into doped 1 Hz. than higher rates significantly repetition for pumping increases material of the accumulation into heat deflection spectroscopy [21,22].photothermal the that demonstrated These studies by excitation energy pump of aconsequence sample the as the was characterized in generated heat dissipate to the of material each capability which the in lasers, polymericthe of dye effect on the in of heat stability studies load on was confirmed 1.5 Dye concentration: PETRA. and of MMA copolymers dissolved in FIGURE 3.5 5, 4745–4763, 2003. Reproduced by permission of the PCCP Owner Societies.) Owner PCCP 5, of the 4745–4763, by permission Reproduced 2003. Phys., Chem. Phys. al., et A. Costela, 532 nm (From rate. 5 Hz at 5.5 mJ repetition with pulses © 2016 Group, by Taylor LLC & Francis Earlier studies to improve the lasing performance of the PM of dyes the demon had to improve studies lasing performance the Earlier Recently, coworkers Jiang and have slope efficiency demonstrated of 51.63%and

Laser output (%) 100 20 40 60 80 0

0004,0 60,000 40,000 20,000 0 2 at 1 Hz. Increasing the pump fluence pump to the Increasing 1.43 J/cm at1 Hz. No rmalized laser output as a function of the number of pump pulses for PM567 pulses of pump number of the afunction as output laser rmalized Number ofpulses COP(MMA-PETRA 98:2) COP(MMA-PETRA 95:5) 80,000 2

resulted in the out the in resulted ×

10 −3 M. Pumping at at M. Pumping 100,000 151 - - -

Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 meric chains ( chains meric covalently poly the to linked chromophores at10 Hzthe with pulses repetitionrate level 100,000 pump initial atabout the after of 20%, emission laser but remained the at 88% value. of its initial remaining emission laser still at 10 Hz the with pulses repetition rate, 95,000 pump mole per energy pump of dye absorbed moleculeaccumulated of 180 GJ/mol after 3.8 an 95:5)] Figure in TERP[P5MA-(MMA-PETRA We for material estimate clearly shows covalently improvement the in an material. bonded photostability in figure The homopolymer into PMMA. PM567 and incorporated material, same the model dye dissolved corresponding the covalently in polymer matrix, the to linked evolutionthe of of pulses number amonomer pump output the with laser dye of the Figure 3.8 pulses. compares 10% 60,000 pump by less than stable after or decreased for output shows remained laser whichetition the rate.Figure 3.7 materials those position rep same sample of ata10 Hz the the in pulses 15% 100,000 pump after by less stable than or dropped output remained laser some the of In them, chains. covalently polymer the to linked chromophores the with materials cross-linked shown Table in formulations are 3.2 polymeric different into dyes these with relevant incorporated obtained results conditions was 30% [27]. experimental same the Some under most of and the als with dyemateri efficiency the same PM567 in obtained maximum the whereas to the polymeric chains. polymeric the to monomer the dyes whereas (P matrices, tively). model dyes The (P polymethylene nmethylenes, with monomeric dyes in chain resulting P atpositiongroup 8was by replaced amethacryloyloxypolymethylene acetoxy or an of methyl PM567 which analogues the in we (Figure 3.6) synthesized particular, In 1,methyl the in 3, groups 5, ethyl positions 7positions 6. in the and groups 2and and 152 FIGURE 3.6 methylene (dyes groups one with or three groups PAr were P model compounds their © 2016 Group, by Taylor LLC & Francis With dyes PAr With dyes P p -(methacryloyloxypolymethylene)phenyl or p

Mole Table 3.2 n Ac P and n cular structures of modified dipyrromethene.BF of modified structures cular Ac PAr and PM PnAc P1ArnAc PnMA P1ArnMA 567 ) [28]. n n Ac, and analogues in which the substituents which atposition the in Ac, analogues 8 and n Ac PAr and MA, lasing efficiencies MA, 40% of to up were obtained, -Me -(CH R -(CH n MA, the lasing efficiencies the MA, were lower, the order of 2 2 ) ) (C n (C n OCOMe OCOCMe=CH H H . The highest photostabilities were reached in were in photostabilities highest reached . The 2 2 FF ) ) n n n R OCOMe B OCOCMe=CH n 8 MA and PAr and MA Ac) were dissolved polymeric different in NN 2 2 -(acetoxypolymethylene)phenyl n MA) were covalently bonded 1,3 1,3 1,3,5,10,15 1,3,5,10,15 - n Tunable Laser Applications Tunable Laser n MA and PAr and MA 2 complexes. Me: CH n Ac, respec Ac, n MA and and MA 3 . - - - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 monomer proportion. Pump energy and repetition rate: 5.5 mJ/pulse and 10 Hz, respectively. and 5.5 mJ/pulse rate: repetition and energy Pump proportion. monomer MMA- indicated the with terpolymers producing chains, covalently polymeric to dyes linked MMA-monomer: model dyes dissolved in copolymer; P dyes model copolymer; dissolved in MMA-monomer: Solid-State Organic Dye Lasers Dye Organic Solid-State ber of newly synthesized dipyrromethene.BF of newlyber synthesized FIGURE 3.7 copolymers of MMA, after 60,000 pump pulses at the same position of the sample. P sample. position of the same the at pulses 60,000 pump after of MMA, copolymers © 2016 Group, by Taylor LLC & Francis b a Material Laser Parameters TABLE 3.2 EPP0A(M-EA9:) 6 8101 87 80 28 34 87 80 27 5 10 23 5 563 563 38 COP(PAr3MA/MMA) 5 COP(PAr1MA/MMA) 87 566 9 112 TERP[P10MA-(MMA-PETA 95:5)] 562 P10Ac/COP(MMA-PETRA 95:5) 565 37 TERP[P10MA-(MMA-HEMA 7:3)] 28 P10Ac/COP(MMA-TFMA 7:3) 4 TERP[P5MA-(MMA-PETA 95:5)] 5 TERP[P5MA-(MMA-TFMA 7:3)] P5Ac/COP(MMA-HEMA 7:3) 569 565 COP(P3MA-MMA) TERP[P3 MA-(MMA-TMPTMA 95:5)] TERP[P3 MA-(MMA-HEMA 7:3)] COP(P3 MA-MMA) P1Ac/COP(MMA-PETRA 95:5) PAr

P1MA/MM Dye concentration:1.5 × 10 intensity Intensity ofthe dye laser output after n λ 100 120 max 20 40 60 80 n 0 : peakofthelaseremission;ΔλFWHMEff: energy conversion efficiency. MA) Dyes in Copolymers (COP) Terpolymers Dyes in Copolymers MA) and (TERP) P3MA/MMA

A I 0 ,

P10MA/MM I n (%) Percent intensity (referred to initial intensity) of the laser output from anum from output intensity) laser of the initial to (referred intensity Percent

= (

P15MA/MM I n a / for Model (P for Model

P1A I A 0 ) ×

c/MMA:HEA 7:

P1A 100. Pumpenergy andrepetitionrate:5.5 mJ10 Hz,respectively. −3

c/MMA:PE M. FWHM,fullwidthathalfmaximum. A

P3A

P3MA/MMA:TMPTMA 95:5 pump pulses in the same position of the sample referredto initial c/MMA:HEMA 7:3 TRA 95:5 n Ac, PAr Ac, (nm) λ 5 16 20 9 50 9 555 40 558 83 75 8 39 36 561 100 6 107 5 34 565 568 27 6 12 569 591 max P5Ac/MMA:TMPTMA 91:1 2 a

dyes incorporated into linear and cross-linked cross-linked and linear into dyes incorporated n (nm) Ac) (P Monomeric and Δλ 3 a

P5MA/MMA:PE P10MA/MMA:TMPTMA 99:1 n (%) Eff MA-MMA-monomer: monomer monomer MA-MMA-monomer: a

P10MA/MMA:PE TA 95:5 I 60,000 ()I (%) Laser Output n

TRA 95:5 MA, 100,000 133 96 96 — — — — 70 — — — — — b (%) n 153 Ac/ - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 in terms of reabsorption/reemission effects and spectral broadening of the S of the broadening spectral effects and of reabsorption/reemission terms in explained could be feature unusual This band. emission laser spectral the in appear nm by separated 10–14 fluence, pump two and peaks interaction, dye–matrix [30]. structure, solid matrices polymeric on dye matrix Depending concentration, model of monomeric compounds, into logues, and dye both PM567 incorporated of energy pump 950 GJ/mol absorbed accumulated [29]. an to corresponding rate, at30 Hz repetition pulses 400,000 pump at67% output after remaining initial of the new lasing efficiency exhibited dyeof this MMA with of 37% emissionthe laser with 154 transition. The short-wavelength The transition. homogeneous usual the to emission corresponds 6of PM567and dye R: (Figure 3.3 Et-CH , with methacryloyloxypolymethylenepolymerizable positions to were 2 groups attached one methacryloyloxypolymethyleneporating atposition group dye 8in PM567, two of (Figure 3.9). incor instead case, chains polymeric the chromophoreto this the In (c). two bonds through (b) bond one or through polymer same the to covalently bonded chromophore same the and FIGURE 3.9 dye and PM567 PMMA. dissolved in matrix, same the 95:5, dye model MMA-PETRA composition P5Ac with dissolved in matrix lently polymer to FIGURE 3.8 © 2016 Group, by Taylor LLC & Francis Bichromatic laser emission was obtained from some- aforementionedof from the ana Bichromatic emission laser was obtained Further improvements in photostability were obtained by double cross-linking of by double improvements were obtained photostability cross-linking in Further

Laser output (%)

100 20 40 60 80 (a) Rep Evo 0 0002,0 40,000 20,000 10,000 0 lution of the normalized laser output of monomer dye P5MA linked cova of linked dye monomer output P5MA laser normalized lution of the resentation of dye molecules D dissolved into a polymeric framework (a), framework of dye a polymeric D dissolved into molecules resentation DD DD 30,000 (b) Number ofpulses PM567/PM 50,000 MA TERP (P5MA-MMA-PE 60,000 P5Ac 2 OCOC(Me) /C OP(MMA-PE 70,000 (c) Tunable Laser Applications Tunable Laser 00090,000 80,000 D = TRA) TRA) D CH 2 ). copolymer The 100,000 0 –S - 1 -

Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 S CF 640, LDS698, LDS722, LDS730) incorporated into different linear, cross-linked, LDS698, cross-linked, 640, LDS722, linear, different into LDS730) incorporated rhodamine region B, red, (sulforhodamine perylene red-edge emissionthis with in dyes of commercial on photosensitive a variety based time, same about the materials of 102 GJ/mol photostability slope with ized efficiency of 13.5% At obtained. was pumping, Under normal longitudinal MPMMA. into dye LDS698 incorporated biological systems [43]. Fan et al wavelengths lightatthese of the penetration deep in low and ecules, lightscattering, lower ofapplications the because autofluorescence and autoabsorption of biomol [42]), at650 nm lies in biological reductionsignal the background significant of and low-loss second ness the to fibers polymer window optical of typical window that (a window the region (600–750 nm), what termed is often spectral within red-edge the ofenergy 12,300 GJ/mol (Figure 3.10). pump accumulated an to corresponding repetitionrate, tion sample of at30 Hz the posi same the in pulses level 500,000 pump initial atthe after output remaining 7:3 for copolymer, PM597recorded laser dissolved MMA–HFMA the with an in was photostability highest pumping. The transversal under were(PM597) obtained Solid-State Organic Dye Lasers Dye Organic Solid-State but CF end with group in Figure 3.4 as ), five(PFMA, Figure 3.4 (TFMA, tions of monomers three with different propor volumetric MMA to adding content fluorine was varied, total the atom fluorine which inthe [41].prepared, were matrices organic Fluorine-modified (99 kcal/mol), of C–H that than relatively lowand well as the as of size polarity small (116 kcal/mol) a result of bondas of energy C–F the analogues, rinated higher being nonfluo with compared resistance chemical enhanced and stability thermal high in results [40].polymerthe matrix in atoms of presence fluorine structure The their into PM597incorporated haveby atoms using polymersfluorine demonstrated with been hydroxyethyl [39]. methacrylate) matrices (PHEMA) efficient in and photostable resulted poly(2- in emission laser pairs rhodamine and on PM based cassettes in processes transfer Energy was PMMA. material matrix two PM dyes one donor acceptor and [38].mophoric systems incorporating The [37] PM chlorinated dyes, multichro and in or by processes using transfer energy toward [36]Emission displaced longer wavelengths diiodinated from was obtained boxylate [34,35]. or cyano respectively, matrices groups, PMMA into incorporated for derivatives of PM567 atoms PM597 whichreplaced fluorine and were in by car at10 Hz pumping transversal were 100,000 pulses repeated under demonstrated than [31–35]. efficiencies of particular, In over with 50% stableemission laser for more efficiency between and photostability new agoodbalance with dyes family of this to rise giving PM substituents chromophoresystem have adequate with tried, been short-wavelengthof the mode. advantageously shoulder competes vibrational that atthe with gain so that dominate, inhomogeneous broadening and when reabsorption/reemission emission appears © 2016 Group, by Taylor LLC & Francis 0 –S Some efforts have been made recently to extend the tuning range of range SSDLsSome have to extend to tuning efforts recently made the been Improvements in the lasing properties of gain media based on dyes based PM567 media of gain and Improvements lasing properties the in the of structure the of molecular anumber Over modifications of years, recent 2 –CF 1 transition and dominates atlow dominates dye long-wavelength and transition The concentration. . The potential advantages of emission in this spectral region are the near the region are spectral advantages of emissionthis potential in . The 2 –CF 3 ) fluorine atoms. Lasing Lasing atoms. efficiencies) fluorine of to up (PM567) 35% and 42% 2 –CF 3 with end group end with group Figure 3.4 in as ), seven and (HFMA, [44] demonstrated laser emission at 650 nm from . [44] from emission laser at 650 nm demonstrated optical optical 155 ------Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 30 min irradiation time at 1 kHz (1.8 at1 kHz time irradiation 30 min 150 mW to output decreased laser The (52%was obtained. power) initial of the after 95:5), 290 mW average power (37% lasing efficiency) wavelengthpeak at of 550 nm [49]. of repetitionrate up 1 kHz to and With PM567 dissolved COP(MMA-PETA in of acopper-vapor line green average the with atan laser power of up 800 mW to longitudinally them pumped and matrices, polymeric into or PM567 incorporated consisting of dyes thick, Rh6G 2 mm disks, formof coin-sized the samples in laser solid we Thus, pulses. prepared rate high-repetition in applied be to energy laser the would require anomalies, vascular other and of port-wine stains or treatment 575 750 nm to (Table 3.3 Figure 3.12 and ). at 532 nm with 3.5 mJ pulses. 532 nmat 3.5 mJ with 156 0.15 cm of order ofable the linewidths with resonator, emission laser wastunable obtained tun grating agrazing-incidence were in placed 3920 GJ/mol. materials these When of 3.3 dye photostability was [44], LDS698 in Table in normalized reported the results the with For comparison for is shown somerate materials. of graphically the repetition evolution at10 Hz of pulses number pump output the with laser of the of clarity, sake For the Figure 3.11 actual in , the at532 nm. pumping transversal dyes for 20% styryl 46% from to chromophores, under the ranged for xanthene the position same sample. of efficiencies the the Lasing in pulses 100,000 pump after intensity) (with photostability laser initial to emission, laser and of respect the peak Table 3.3 in , which shows on lasing efficiency, data summarized Some are results and synthesized designed [45–48]. andwere silylatedmatrices polymeric fluorinated, 7 Dye concentration: rate. repetition 30 Hz at monomers fluorinated with FIGURE 3.10 © 2016 Group, by Taylor LLC & Francis Some potential important applications of therapy SSDLs, such photodynamic important as Some potential

−1 Laser output (%) and a tuning range of range continuously up 70 nm, to covering region atuning the from and 100 25 50 75 0

0,0 0,0 300,000 200,000 100,000 0 Evol ution of the normalized laser output of PM597 in copolymers of MMA of MMA copolymers of PM597 output in laser normalized ution of the 30 Hz PM 597 Number ofpulses

10 6 shots) 32 mW to and (11% initial of the C A: MMA-HF B: MMA-PF C: MMA- Tunable Laser Applications Tunable Laser TF 400,000 MA 7:3 MA 7:3 MA 7:3 A B

× A

10 −4 500,000 M. Pumping M. Pumping - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 with permission.) with Mat. edge. Adv. Funct. spectral red dyethe at for laser state solid reliable Moreno, Materials al., I.et 12 ns, Figure 3.19 see 10 Hz, 5.5 mJ/pulse, of and TMSPMA, respectively.. (García- Structure 532 nm, are rate 8:2). energy, repetition TMSPMA and wavelength, duration, pulse Pump 9:1), 7:3), COP(MEMA-PETRA (c) in and 640 TFMA LDS722 COP(HEMA- (b) in rhodamine FIGURE 3.11 Solid-State Organic Dye Lasers Dye Organic Solid-State Laser Properties Laser TABLE 3.3 b a Dye D708CPHM-MPA73 3 010690–750 650–720 620–660 605–655 100 55 79 95 20 23 36 730 21 674 640 COP(HEMA-TMSPMA7:3) 618 COP(HEMA-TMSPMA8:2) PHEMA 8 COP(HEMA-PETA 9:1) Note: 4 COP(MMA-TFMA7:3) 4 LDS730 6 LDS722 5 COP[(HEMA-MMA LDS698 Rh640 6 PerRed SulRhB linked, Fluorinated, Silylated and Polymeric Matrices LDS698, LDS722, LDS730 and Incorporated Linear, into Different Cross- © 2016 Group, by Taylor LLC & Francis

intensity I Intensity ofthelaseroutputafternpumppulsesinsamepositionsamplereferredtoinitial c: dyeconcentration;λ 2009. 19. 2009. 2547–2552. Wiley-VCH Copyright Verlag &Co. GmbH Reproduced KGaA.

Structure of TMSPMA, seeFigure 3.19. 0 c , I a

(M) n ×

(%)

10 Evo 4

Laser output (%) =

a 100 120

(I lution of the normalized laser output of (a) output COP(MMA- laser in red perylene normalized lution of the of Sulforhodamine B, Perylene Red, Rhodamine 640, Red, B, Rhodamine Perylene of Sulforhodamine 20 40 60 80 n 0 max /I 7:3)-PETRA 9:1] 0 0004,0 00080,000 60,000 40,000 20,000 0 ) × 100. Pumpenergy andrepetitionrate:5.5 mJ10 Hz,respectively. : peakofthelaseremission;Eff: energy-conversion efficiency. Material Number ofpulses (nm) λ 6 15 635–695 55 575–645 21 99 660 46 608 max a

(%) Eff a

(b) 100,000 (a) (c) I (%) 100,000 b

range (nm) Tuning 157 Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 158 power) after 70 min operation (4.2 operation power) 70 min after permission.) With LLC. Publishing Lett Phys. Appl. al., et A. Costela, from (Reprinted rate. repetition a copper-vapor 1 kHz with at laser when pumped media polymeric different FIGURE 3.13 of only. for viewing ease Table 3.3shown are in lines solid . The FIGURE 3.12 MMA and MAA (methacrylic by acid) was Kytina demonstrated [51]. MAA et al. and MMA The acopolymer into of Bdye incorporated on rhodamine based 605–635 nm, range about 7.8 min value after (Figure 3.14 initial the half to power) [50]. decreased shots).about 4.0 of million case PM567/COP(MMA-PETRA the 95:5), In output the (or 1:1) about 6.6 min value after COP(MMA-HEMA initial the half to decreased frequency-doubled Nd:YLF (emission laser at527 nm), output power the of Rh6G/ Q 10 kHz, to adiode-pumped, by was source pump increased usingrate as repetition pump the of When time. for periods short was obtained at6.2 kHz 1 W © 2016 Group, by Taylor LLC & Francis A high-repetition rate (16 kHz) laser emission, tunable in the wavelength the kHz) emission, in laser tunable (16 rate A high-repetition

Output power (mW)

100 150 200 250 300 50 Tuna Evol 0 01

5756 Laser emission (a.u.) ution of the output power as a function of time of PM567 and Rh6G in in of Rh6G PM567 of and time power output a function ution of as the ble laser emission over the red-edge spectral region from the materials materials the from region spectral over emission red-edge ble laser the 020304 06256 00

× Wa

10 0675 50 velength (nm) 6 shots) (Figure 3.13). power Output of up to Time (min) 0 ., 79, 2001. 452–454, 2001, Copyright AIP PM PM RH6G/P (MMA-HEMA1:1) 567/P (MMA-PE 567/P (MMA 7007 06 70 60 50 Tunable Laser Applications Tunable Laser 5750 25 -T FM TA A 7:3) 95:5) 80 -switched, Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 (2003), with permission from Elsevier.) from (2003), permission with laser, 359–363, solid-state Copyright by diode-pumped dye pumped laser solid-state rate tion Solid-State Organic Dye Lasers Dye Organic Solid-State repetition rate. (Reprinted from Opt. from (Reprinted rate. repetition Nd:YLF an with 10 kHz at (second laser when pumped harmonic) media polymeric different FIGURE 3.14 © 2016 Group, by Taylor LLC & Francis [54]. The laser medium consisted of a thin film (thickness between 50 and [54].between 50 film 100 (thickness of consisted athin medium laser The role played by excited-state photodegradation. in reactions important an emission, indicating of rate stimulated the in increase by an stantially DABCO and [53].PETRA sub was found rate reduced be to photodegradation The amounts of small incorporating matrix PMMA amodified of in PM567 dispersed thickness) 3 mm diameter,62% efficiencydisks amplifier in (25 mm was observed at616 nm of 500 [52].650 asingle-pass gain (PM650) rendered PMMA in Up to sample of dye thickness 7 mm pyrromethene diameter, A25 mm reported. been has cavity laser of output mirror. the transmission output power dye of the 70% to value) laser of its initial was about 2 h for optimized copper-vapor the with pumping (decrease of time the operation laser), maximum the cycle 1/6 10 s (1 min operation, pause). (no mode pumping pause in permanently In 3% within accuracy, stable acyclic for in 4 h, duty remained with mode operation laser. efficiency Lasing of 15% (outputpower outputThe laser 1.5 W) obtained. was a copper-vapor from of transverselyat afrequency 42 Hzradiation with pumped and 20 mm) was rotated thickness (94 mm diameter, disk-shaped medium polymer gain liquid solvent dye geometry. laser (50–100 Hz) and dye was The disk rotated laser (DVD) resonator design was The afolded substrates. cavity, conventional derived from dissolved of aphotopolymer versatile disc Rh6G in two between sandwiched digital In 2006, acontinuous-wave 2006, In (CW) SSDL 565 from 615 nm tunable to was reported dyes amplifier laser as pyrromethene solid host of use incorporating PMMA The

Output power (mW)

100 200 300 400 500 600 Ev 0 olution of the output power as a function of time of PM567 and Rh6G in in of Rh6G PM567 ofand time powerolution output afunction as of the 0 04 51 01

Number ofshots(millions) Commun 81 52 PM PM Rh6G/ P(MMA-HEMA1:1) Time (min) 567/ P(MMA-PETRA 95:5) 567/ P(MMA-PETRA 567/ P(MMA-PE ., 218, repeti 10 M.al., et K. kHz Abedin, 2162 0 53 35 30 25 TA 95:5) 02 40 4 μ 159 m) m) - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 laser, could be integrated in acompact housing 60 in dimensions with laser, integrated could be output over laser CW without noticeable hours power loss. device, The including pump profile with an M with profile mode over circular anearly 3 GHz, and 30 nm, tunability of width less than a spectral output power An was of PMMA. 800 mWpolymer 575 nm host material around with was larger ness disk of significantly the (3 mm),the dye the and perylene orange, was power [55]. recently was time presented stability improved the thick design, the In device improved showing more excellent sophisticated An and both long- short- and was lasing operation achieved before 30 min irreversibleone disk, photodegradation. was 550 mW threshold Lasing stage unit. translation slope and efficiency 2%. Using (100–300 axis rotation to the perpendicularly translated 160 a priori a hybrid polymers are inorganic–organic Silicate-based o 3.2.2 dyes [58]. next the couple In of lasing slope years, efficiencies of 60% and 79% sol–gelfor dyes but phases, laser not wet xanthene for dried in and pyrromethene cases. all modest in sol–gel in glass. Nevertheless, Rh6G and lasing efficienciesand photostabilities were for efficiency polycomin andperylene photostability were orange be to found glass sol–gel combinations most of host. inorganic promising glass dye The the hostin and best dyes performed pyrromethene and ionic rhodamine hosts,the whereas organic partially in performance dyes perylene nonpolar found the They better had that PM567, hybrid and hosts. inorganic, organic, in orange perylene and red, perylene of dyes Rh6G, study of performance laser comparison out [57] adirect King carried 1995, 1980s, late approach. In and showed apromising the be to and Rahn this out in usingwere sol–gel carried techniques prepared matrices inorganic–organic silanes (ORMOSILs).modified ceramics (ORMOCERs) fied or organically modi organically called way usually this are in obtained Materials obtained. be to choice a wide with of range the properties conditions reaction of allows the materials well possibility oforganic:inorganic as ratios different selecting as The radicals. free or photochemically, via thermally is initiated, step, polymerization second organic network by is inorganic formed polycondensationinitial a alkoxide. silicon of In the An reaction. atwo-step in obtained networks are inorganic and organic both method, dye laser the is formed. polymering incorporating interpenetrat an and or heating, by ultraviolet irradiation is started polymerization monomer,polymerizable catalyst or photoinitiator. and asubsequent In step, organic dye, laser asolution in bulk containing the molecules organic with by immersing of monomers [56]. polymerizable cross-linking combination organic with by sol–gel in precursors processing organosilane from prepared are hybrid materials polymers. organic These common with compared properties mechanical and thermal backbone, present they improved Si–O–Si inorganic since, due their to matrices, laser © 2016 Group, by Taylor LLC & Francis In 2002, Ahmad and colleagues demonstrated high efficiency high and photostability demonstrated colleagues and Ahmad 2002, In and inorganic into from emissionon dyeslaser incorporated studies first The this alkoxides.In silicon modified organically from obtained be also Hybrids can is filled of asol–gel matrix inorganic structure porous one the approach, In r g anic 2 better than 1.4 was obtained. The excellent 1.4 The than power was provides obtained. better stability – I nor g anic H ybrid M ateria l s μ Tunable Laser Applications Tunable Laser m/s) by motor- a combined good candidates for good candidates

4 0

2 0 cm 3 . - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 Solid-State Organic Dye Lasers Dye Organic Solid-State ples of 4 mm thickness at a pump fluence atapump of 0.1 J/cm thickness ples of 4 mm of of upphotostabilities to 53% 24 GJ/mol sam with were normalized with obtained of 180,000 pulses. lifetime tions, PM567 aslope exhibited xerogel efficiency in and a useful 80% matrix of [60]. condi repetitionrate at10 Hz pulses irradiation 1.8 mJ with Under same the when pulses, 210,000 pump pumped value after to 50%sion initial of the dropped fluence of 0.1 J/cm of fluence pump photostability, and of repetitionrate 2 Hz atapump 50 GJ/mol normalized in for PM567532 nm cavities. lifetime laser useful was The 60,000 pulses, optimized in [60]. (PM597) ces at pumping under efficiencies longitudinal These were obtained (PM567) [59] host matrices ORMOSIL into technique hybrid and xerogel matri for dyeswere reported PM567 PM597, and respectively, sol–gel the via incorporated DEOS. 3.15 FIGURE (20 mJ/cm 1 mJ asreflector and coupler. a output 50% broadband reflector by Pumped a full cavity laser consisting of optimized an in placed samples and glass ORMOSIL into forhave dyes obtained PM567, been PM597, respectively, Rh6G, and incorporated slope the efficiencyincreased [61]. of PM567 marginally only was by a 2, factor increased whereas of matrix efficiency in ORMOSIL perylenered of dye slope the concentration, coumarin optimized an By with red perylene codoping organic part was composed of MMA or MMA–HEMA. The synthesis route of the synthesisroute of the The or MMA–HEMA. of was composed MMA part organic weight (TMOS) (Figure 3.15) different The in tetramethoxysilane proportions. and (TEOS) components, Forwe tetraethoxysilane inorganic used hybrid materials. organic–inorganic into dyes incorporated pyrromethene and of rhodamine formance [62].glass composite into dye when the was incorporated to 22,000 pulses which increased © 2016 Group, by Taylor LLC & Francis With dye perylene red incorporated into ORMOSIL matrices, slope efficiencies matrices, ORMOSIL into With dye incorporated red perylene Under transversal pumping, slopeUnder efficiencies transversal of 32% [62], 43%,and20% [56] Beginning in 2002, our group carried out a detailed investigation outper laser adetailed on the carried group our 2002, in Beginning 2 ) pulses, the useful lifetime of PM597 in ORMOSIL was 12,000 pulses, of was PM59712,000 pulses, ORMOSIL lifetime in useful the ) pulses,

Mo CH CH lecular structure of inorganic alkoxides TEOS, TMOS, TRIEOS, and and TRIEOS, TMOS, TEOS, alkoxides of inorganic structure lecular 2 , in samples of 4 mm thickness [59]. thickness samples of, in 4 mm For PM597,- emis laser the 3 3 CH CH Methyltrietho 2 2 Tetraetho O O (TRIEOS) Si OCH OCH Si CH OCH (TEOS) 3 2 2 xy OCH 2 CH CH OCH xy CH silane silane 3 3 3 2 2 CH CH 3 3 CH 3 CH Dimethyldietho CH Tetrametho 3 2 O O 2 (TMOS) Si (DEOS) CH CH OCH OCH Si and 2 Hz repetition rate [59]. repetitionrate 2 Hz and 3 3 3 3 xy OCH OCH silane xy silane 2 3 CH 3 161 - - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 domains less miscible with the organic components, which is detrimental to the the to components, which organic less is detrimental miscible the with domains inorganic broad inducing chains, reactive positions, rapidly to leads linear growing [65–67]. new of DEOS, these hybrid only two with matrices sition structure and actioncompo the the laser asystematicof on influence study of the performed dimethyldiethoxysilane (DEOS) (Figure 3.15), we difunctional and and (TRIEOS) methyltriethoxysilane were compounds trifunctional inorganic which the in matrices hybrid we idea, prepared this TMOS. Pursuing and ones, TEOS tetrafunctionalized usual of the instead alkoxides double-selecting triple-functionalized pounds, and com inorganic of the functionality component the is by inorganic decreasing the of or even proportion the increasing, maintaining, while materials of the rigidity Apossible the way materials. resulting of the decrease to fragility and rigidity (Figure 3.16). position same sample of the the in pulses 60,000 pump 70% value after of its initial at remained and output stabilized laser the decrease, initial an was 26%, after and, 5% with content [64]. matrices of in TEOS lasing efficiencytion The was optimized composition. matrix organic inorganic– the dye of controlling the destruction by photochemical carefully the in increase the and material dissipation the in of thermal enhancement the between dye/hybrid of system, must the reached photostability be a compromise the optimize Thus,to materials. these in polymeric flexibilitythe chains and of microstructure dependent on the highly be can process is atleast bimolecular, the mechanism cal photochemi the because addition, reactivewhich In these couldprocesses. boost medium, of acidity the remanent the in increase an to leads material oxide the in alk inorganic of the proportion the in increase An material. the present in species active or any other polymer chains oxygen, the from groups impurities, and radicals, dye nearby with react molecules,active (radicals, triplets) species turn, which, in dye of the afraction to leads molecules converted radiation into being pump The dye. of the degradation photochemical role the in plays important an matrix the in component inorganic of presence the emission. laser ity the of It the that is clear or stabil lifetime efficiency and useful both in decrease adrastic sample result in [63]. repetitionrate sample at10 Hz the the in alkoxide of the proportions Higher position same of the in pulses 100,000 pump after weresome obtained oscillations, efficiencies albeitof 26% to up andemissionwith laser no with sign degradation, of sitions 10%–15% with (wt%) of at532 nm, With laser pumping TEOS. proportions compo at peaking component, inorganic the of proportion the with increase ity first lasing efficiencythe photostabil and the both medium, gain as is used Rh6G When material. resulting of the properties laser substituent alkoxideon of the group the the lateral the evidencingof size influence of on TEOS, the based materials the in transversal. arrangementwas surface), a flat pumping cut the defining and alateral with rods samples of was previously as (10 the geometry monomers. The described organic of the copolymerization radical free the component during inorganic of the hydrolysis–condensation simultaneous and situ in on the was based hybrid materials 162 © 2016 Group, by Taylor LLC & Francis The presence of the inorganic component in the hybrid matrices increases the the increases hybrid component matrices the in inorganic of presence the The - opera laser dye the medium, PM567 pyrromethene the gain as wasWhen used was than significantly worse hybrid matrices of TMOS-based lasing stability The Tunable Laser Applications Tunable Laser

10 mm mm ------Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 materials, 656–661, Copyright (2003), with permission from Elsevier.) from (2003), Copyright permission 656–661, with materials, hybrid new organic-inorganic into 567 dye incorporated of pyrromethene properties of laser Chem from 10 Hz, respectively. (Reprinted Solid-State Organic Dye Lasers Dye Organic Solid-State formance of dyes in sol–gel glass and organic–inorganic hybrid materials. Thus, Thus, hybrid materials. of dyesformance sol–gel organic–inorganic in and glass stable over emission laser remained at 30 Hz the pulse, 100,000 pulses repetition rate. ( ofpulses 5.5 mJ with by at10 Hz pumping was pulses obtained emission stable over 100,000 pump samples, laser behaviorIn some with strong fluctuations.fluorinated irregular rather emissiona this althoughpolymers,exhibited nonfluorinated in was demonstrated rate drop of onlydrop 10% 10 after ciencies of up 37% to dye with PM567 were obtained [68,69]. emission a with Laser dye. alaser incorporating polymeric formulations adequate with filled be conditions, can appropriate under network of low density, three-dimensional inorganic which, amorphous an forms als materi these sibleof (20–100 nm) mesopores pore structure The air.open with filled extremely by an porosity (80%–99%) high - easily acces with characterized glasses sponge-like aerogels. on silica are based These properties mechanical and optical solidinto hosts,improved with we thermo- new next hybrid synthesized materials Figure 3.17 15% with matrices TRIEOS, ). PM597 content 20% and (in with of TRIEOS), (in matrices Rh6G with obtained position same sample of at10 Hz the the in was pulses repetitionrate 100,000 pump output after laser the in no with decrease operation scale. Laser nanometric at the morphological without uniformity, separation phase and structural better with rial amate in results hand, other on the samples. of TRIEOS, the transparency optical PM567 (1.5 3.16 FIGURE © 2016 Group, by Taylor LLC & Francis Over recent years, some more attempts have improve to someOver per more years, attempts made laser recent been the When using silica aerogels filled with fluorinated modified polymers, effi lasing polymers, modified with using aerogels silica fluorinated When filled dyes laser of improve the photostability when incorporated the Trying further to

−3 Laser emission (%) Nor 100 M) in hybrid matrices. Pump energy and repetition rate: 5.5 mJ/pulse and and 5.5 mJ/pulse rate: repetition and energy Pump matrices. hybrid in M) 20 40 60 80 Figure 3.18 0 malized laser output as a function of the number of pump pulses for pulses of pump number of the afunction as output laser malized 0 6 pulses in the same position same sample of at10 Hz the the in pulses repetition 0002,0 30,000 20,000 10,000 ; compare with Figure 3.16). with ; compare By 3.5 mJ/ with pumping Number ofpulses . P(HEMA-MMA 1:1+5%TEOS) P(HEMA-MMA 1:1+10%TEOS) Phys . Lett. 00050,000 40,000 , 369, Costela, A. et al., Enhancement , 369, Enhancement al., et A. Costela, 60,000 163 - - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 J. et al., I. García-Moreno, from permission with efficiency: 23%. lasing (Reprinted Initial pulse. (a)TRIEOS: 15% 10 Hz, (b) and (c) 15% and 5.5 mJ/ 30 Hz, energy: and Pump 5% 30 Hz. and 164 for PM567 (1.5 3.18 FIGURE (6 FIGURE 3.17 375–378, Copyright (2006), with permission from Elsevier.) from 375–378, permission with (2006), Copyright aerogels, silica on fluorinated-polymeric based materials O. optical Efficient al., et García, Chem. from respectively. 10 Hz, (Reprinted and 5.5 mJ/pulse rate: etition rep and energy aerogel. Pump silica 7:3) without COP(MMA:TFMA matrix (b) and organic © 2016 Group, by Taylor LLC & Francis

× Phys.

10 −4

Chem.

Laser output (%) 1:1) of proportions of wt% P(HEMA-MMA different with matrices hybrid in M) Laser output (%) 100 120 100 120 20 40 60 80 20 40 60 80 0 0

0004,0 60,000 40,000 20,000 0

B No

10 rmalized laser output as a function of the number of pump pulses for PM597 pulses of pump number of the afunction as output laser rmalized rmalized laser output as a function of the number of pump pulses pulses of pump number of the afunction as output laser rmalized −3 M) incorporated into (a) silica aerogel filled with the copolymer copolymer the (a) into with aerogel filled silica incorporated M) Number ofpulses Number ofpulses C B Tunable Laser Applications Tunable Laser 80,000 80,000 (b) (a)

Phys. A 100,000 100,000

Lett. , 427, - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 exhibit a drastic decrease in quantum yield at concentrations higher than 10 yield than higher atconcentrations quantum in decrease exhibit adrastic samples aluminosilicate sodium hand, other the On dye is increased. concentration yields (up quantum high 87%), to efficiency in when decrease no with substantial dye xerogels silica glasses.The the dispersion in in results aluminosilicate sodium Solid-State Organic Dye Lasers Dye Organic Solid-State makes these materials interesting candidates for biological candidates interesting applications. materials these makes xerogels silicate of the ability of the hostconcentrations to dye high and operation, of stable 2 m during rather at10 Hz remained emission linewidths the repetitionrate, pulses with pumping were ahalf-life with transverse of not under high, 6560 pulses As a result, only the sodium aluminosilicate samples containing 2.1 samples containing aluminosilicate sodium only aresult, the As is based on SiOis based were developed Rh6G [71]. by et al. Queiroz de incorporate designedto cally first The covalent dye of the bonding GMA. to to polymer host, attributed the pumping)in was reached 15 mJ/pulse and at 10 Hz pulses 30,000 pump (decrease value emission ofbility 30% to after the of its initial photosta- hosts. higher Nevertheless, the were photostabilities and notgood, the as sol–gel in (37.6%) glass than hybrid in matrix tently higher polymer (33.2%) and lasing efficiency The consis was - at532 nm. pumping transversal under obtained was Relatively TEOS. efficiencies high (of to up 48%the were material) in hybrid polymerwas glycidyl used The (GMA), methacrylate component inorganic the and was evaluated [70]. materials hybrid different itsbehavior laser hosts, the and in polymer, into sol–gel organic–inorganic Bwasand glass, incorporated rhodamine FIGURE 3.19 TMSPMA, and HEMA, of Figure 3.19) MMA, terpolymers into (TMSPMA, and 3-(trimethoxysilyl)propyl with or HEMA copolymersinto of MMA methacrylate dyes PM567 atoms.silicon Following we approach, PM597 and incorporated this of presence the due the to properties but improved with thermal synthesis procedure, arelatively plasticity and which organic, means would remain more simplematrix the Thus, structure. their into incorporated directly atoms silicon with compounds would organic use to be materials advantages ofcombined inorganic polymer and Apossible the way parts. inorganic avoid to and problems maintaining these while inhomogeneity by optical caused organic refractive between indextimes mismatch and some difficult, material final of the polishing and mechanization makes that own problems,ent their such acomplex as fragility lengthy synthesisprocess, and - pres compounds these hybrid materials, the with obtained goodresults Despite the s 3.2.3 well with Rh6G concentrations of concentrations up 10 to well Rh6G with xerogels silicate the action, while laser hostexhibited worked per formulaunit Rh6G © 2016 Group, by Taylor LLC & Francis Two specifi new mesoporous sol–gel materials approaches to obtaining different i l icon

Mo 2 and phenyl-modified and silica mesoporous xerogel, uses second the and - M lecular structure of 3-TMSPMA. monomer structure lecular odified CH 2 CH CC O 3 O r g anic O TMSP M CH 2 atrices MA −3 CH M. Although emission photostabilities photostabilities emission Although M. 2 CH 2 OCH OCH Si 3 3 OCH 3

10 −5 moles of of moles −4 165 M. M. - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 after 100,000 pump pulses at 30 Hz (accumulated energy: at30 Hz 3137 GJ/mol). pump pulses 100,000 pump after lasing efficiencyvalue initial The 90%the at of was 42%,the outputremained and 577 to over from was [74]. tunable displaced 585–625 nm range 607 nm, the matrix, emission dye,mophore, laser resulting of the the COP(HEMA:TMSPMA in 7:3) acetoxymethyl an substituentmol. PM597 atposition By the chro incorporating 8in mole per absorbed of energy pump dye accumulated molecules to an ofing 17,300 GJ/ position same (Figure 3.21 sample of at30 Hz the repetition rate the in - ), correspond 1:1), pulses 700,000 pump emission laser dye stable of the after the PM597 remained COP(MMA:TMSPMA 1:1) two matrices, selected In COP(HEMA:TMSPMA and Figure 3.17b of energy pump 2472 GJ/mol. accumulated an to c), and corresponding at30 Hz (Figure 3.20; with pulses 100,000 pump repetitionrate compare stable after emission but laser remained one formulations ofmuch the the all more stable, in and Dye PM597 content was highest of the (Figure 3.20). samples with silicon the in drastic which output, was laser rather the in PM567 decrease asteady exhibited PM597,and dye the respectively. 30 Hz, to increased repetitionrate pump the When by system mole the absorbed per of dye molecules of 518 1295 GJ/mol and for PM567 energy pump PM567 accumulated both PM567 an to and dyes. corresponds This position same sampleof the for the in pulses 100,000 pump output laser after the formulations were repetitionrate, found no with sign in of degradation At 10 Hz cavities. laser nonoptimized in at532 nm pumping PM597with transversal under lasing efficiencies with matrices, of 34%to up organic with PM567and to up 42% novel [72,73]. materials of these properties laser and photophysical, study to the structural, proceeded and 166 Dye concentration: 1.5 Dye concentration: (c)PM597 in 5:5:10). 7:3) COP(HEMA:TMSPMA (d) and TERP(MMA:HEMA:TMSPMA PM567 (a) in 3:7) COP(MMA:TMSPMA 7:3), (b) and COP(HEMA:TMSPMA for dye and FIGURE 3.20 tion rate: 3.5 mJ/pulse and 30 Hz, respectively. (Reprinted from Costela, A. et al., J. al., et A. Costela, from respectively. (Reprinted 30 Hz, and 3.5 mJ/pulse rate: tion Phys © 2016 Group, by Taylor LLC & Francis A highly photostable laser operation was obtained with the silicon-modified silicon-modified the with photostable wasA highly operation obtained laser ., 101, 073110, permission.) With LLC. Publishing 2007, 2007. AIP Copyright

Nor Laser output (%) 110 130 10 30 50 70 90 malized laser output as a function of the number of pump pulses for dye pulses of pump number of the afunction as output laser malized 0

× 0004,0 00080,000 60,000 40,000 20,000 0

10 −3 M (PM567) and 6 and M (PM567) Number ofpulses

10 −4 M (PM597). Pump energy and repeti and energy Pump M (PM597). Tunable Laser Applications Tunable Laser (d) (b) (a) (c) 100,000

Appl. - -

Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 Solid-State Organic Dye Lasers Dye Organic Solid-State content to increase the thermal conductivity of the polymer resulted in reduced dye conductivity reduced in polymer of resulted the thermal the content increase to PM567. with ity as photostabil of the enhancement same the proportionally in sample resulted PMMA asolid to addition of dye microparticles the the of was 365 GJ/mol. When Rh6G, energy pump absorbed atotal to corresponding 600,000 pulses, to lifetime tional - opera the in increase an in results DABCO addition of both The microparticles and microparticles. for samples containing 400,000 to without microparticles 200,000 from conversion the increase to value isseen initial of efficiency half its to to fall The laser beam exhibited near-TEM exhibited beam laser The scheme, pumping conversion laser longitudinal efficiencies of 63% were obtained. dye laser as a Using and Rh6G PMMA. in dispersed uniformly nanoparticles silica of consisted solid matrix homogeneity The previouscal media. composite than gain inorganic, solid-state gain media that exhibit that lower media gain solid-state inorganic, | James[75,76] and Recently, Duarte aclass organic– of demonstrated dye-doped, 3.2.4 matrix. organic for sample dye positionsilicon-modified of the PM597 in same FIGURE 3.21 doped with aPM567 with doped dye of concentration 3.4 long when using samples 8 mm enhanced: samples of was greatly the tostability 0.2 β samples containing lar, PMMA liquid solutions [77]. investigated and particu been has by In Ahmad materials detail. in discussed ( at 2 Hz repetition rate and pump fluence pump and of repetitionrate 0.16 J/cm at 2 Hz © 2016 Group, by Taylor LLC & Francis ∼

1. In Section 2.3, it was shown that the use of polymeric hosts with a certain silicon silicon Section 2.3,In it wasof use shown acertain hosts polymeric with the that The effect of incorporating dielectric-oxide microparticles into both solid host both into microparticles dielectric-oxide effect ofThe incorporating μ 3 times the diffraction limit). In Chapter 4, the use of these media in SSDL in media is of use these the limit). Chapter 4, In diffraction the 3 times m, doped with PM567 and Rh6G, were prepared. In these conditions,pho the these In were PM567 with prepared. doped Rh6G, m, and Laser output (%) P 100 120 140 o 20 40 60 80 0 l ymers

0,0 0,0 0,0 400,000 300,000 200,000 100,000 0 No rmalized laser output as a function of the number of pump pulses in the the in pulses of pump number of the afunction as output laser rmalized

PM w MMA- it 597: 6 h N TMSP

× ano

10 MA 1:1 –4 - M and -alumina microparticles with diameter less than less than diameter with microparticles -alumina Number ofpulses 00 M profile with a beam divergence beam with a profile of 1.9 mrad icro Repetition rate:30 -P

× artic

10 ∂ − n/ 4 l 0,0 600,000 500,000 es M and longitudinal pumping pumping longitudinal M and ∂ T| values improved and opti 2 , the number of for number pulses , the Hz 700,000 167 - - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 8.5 87:13), COP(MMA:8MMAPOSS mer after unchanged emission laser remained the dyes [78,79].60% With efficienciesas high for as PM567 intodyecopoly a doped pyrromethene and for rhodamine both for solid dye-doped matrices, date to different physical and properties. mechanical, thermal, enhanced with hybrid network) (Figure 3.23 organic–inorganic placegiving to an polymer chains, the to directly bonded be POSScages will polymerizable, the are groups functional (1 nm) should avoid,nanoparticles inhomogeneities. principle, any optical the in If POSS the size of reduced The POSS-modified systems. the of properties final the thus and compatibility the defining medium, the and ligand organic the between R (Figure 3.22).ligands, of number substituents and interactions control the type The value after just 1 value after initial the of efficiency an vided to one-third of dropped emissionthe 39%,laser and ofenergy 4768 GJ/mol. no with POSSpro dye same PMMA in the acomparison, As pump absorbed accumulated estimated an to pumping, corresponding transversal In this way, this In universal kind gain of POSSsolutions dye-doped asa defined could be conditions ( experimental same solutions the under meric pumped solvents organic effectiveness pure the to in poly597) respect and with recorded B, LDS772, 567, LDS730) pyrromethene (perylene nonpolar red, and pyrromethene sulforhodamine 640, rhodamine (Rh6G, polar both dyes families, of different very action of laser B). the was found of enhance to presence POSSnanoparticles The (SiO and up made core of inorganic oxygensilicon awell-defined cage-like with ture (POSS) was exploredanes [78]. have compounds - These acompact hybrid struc oligomeric on silsesquiox polyhedral based nanoparticles incorporating matrices abovementionedcome the problems. approach of the implementing Thus, polymer level atmolecular over might incorporated silica with synthesisof materials and Section 3.2.4 in James discussed showed and design the that of results Duarte The for polishing. inappropriate which eventually soft materials renders temperature, transition glass the in by polymer adecrease backbone the wascon in accompanied of presence sili content, silicon the the with increased photostabilities the although and cies were some somewhat with hybrid materials, lower obtained those than nonsilylated of those to the polymers. respect with Nevertheless, lasing efficien the way, this In degradation. dye-lasing the were photostabilities enhanced significantly 168 FIGURE 3.22 © 2016 Group, by Taylor LLC & Francis Surprisingly, these enhanced properties led to the best laser performance reported reported performance laser best to the led properties Surprisingly, enhanced these

× 1.5

10 ) n 5 externally surrounded by nonreactive or reactive organic polymerizable surrounded externally pulses at 30 Hz repetition rate ( repetitionrate Hz at30 pulses

Struc

10 ture of octameric POSS.R of octameric ture 5 pulses at the lower atthe pulses of repetitionrate 10 Hz ( R R O Si Si O R R O O iSi Si Si O O O O iue 3.24 Figure Si Si

= O

R H or org H or O O R Si O R R anic group. anic , curve A) and 5.5 mJ/pulse mJ/pulse A), curve 5.5 and Tunable Laser Applications Tunable Laser Figure 3.24 Figure 3.25 , curve , curve ) [80]. ------Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 Solid-State Organic Dye Lasers Dye Organic Solid-State consequence of scattering processes [80,81]. processes ofconsequence scattering dispersion of POSSnanoparticles The of POSSsystems dye-doped wasable adirect improvement performance laser the in application ofsystems point an view. from laser of these up now, to limitations one most of important the represented which has overcome has imposed action that laser dye/host specificity the the optimize to media Society.) Chemical [2008], American O. J. al., et García, from permission with 5.5 mJ/pulse.(Reprinted energy: 10 Hz. at Pump pumped (b) PMMA and pure 30 Hz at for sample dye position of87:13) the PM567 (a)same in: COP(MMA:8MMAPOSS pumped FIGURE 3.24 MMA. silsesquioxane) oligomeric and (octa[propyl polyhedral methacryl] 3.23 FIGURE © 2016 Group, by Taylor LLC & Francis Detailed experimental and theoretical studies seem to indicate that the remark the that indicate to seem studies theoretical and experimental Detailed

No Sch Laser output (%) rmalized laser output as a function of the number of pump pulses in the the in pulses of pump number of the afunction as output laser rmalized 100 120 140 160 ematic representation of copolymer network formed by 8MMAPOSS by 8MMAPOSS formed network of copolymer representation ematic 20 40 60 80 0 0,0 0,0 600,000 400,000 200,000 0 (b) Number ofpumppulses

Phys.

Chem.

C , 112, 14710–14713, Copyright 2008. 800,000 O O O O O O MMA CH O O 1,000,000 (a) 3 O O 8MMAPOSS Si Si O O O Si Si O O O O O Si Si O O O Si Si CH O O O 3 O CH O O O O O 2 169 - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 5 170 with PM657 dye simply dissolved in the POSS-containing matrix; lasing efficiency PM657with matrix; dye simply dissolved POSS-containing the in level same atthe previously remained hybrid dye, demonstrated lasing performance By 13% with using acopolymer of MMA with weight doped of ratio 8MMAPOSS aderivative and of component. PM567 organic part the inorganic as the POSS as dyes on azide-functionalized newwe based hybrid synthesized organic–inorganic [83]. cores inorganic rigid on their groups rescent dyes particular, pendant as In design usto led new hybrid photonic systemson POSSlabeled fluo with based andliquid solid [78–80]. phases both in enhanced is significantly POSS materials intensity feedback incoherent called random process lasing the to phenomenon central a feedback, extra providing an thus media, gain elongating inside the lightpath the helps that lasing by scattering optical aweak sustain POSS particles size, the meter dyes,laser nano despite allow emission, coherentaddition and their laser but, in with level at amolecular that, when doped highly homogeneous defines materials was:13 wt%. 1.5 Dye concentration was nanoparticles of 8MMAPOSS proportion the POSS, with matrices solid solutions and the In LDS730). (LDS722, PHEMA and SulfRhB), 1:1 G,Rh640, (Rh6 MMA:HEMA red), copolymer (PM567, was PMMA PM597, matrices LDS730). perylene polymeric of composition the The (PM567, solutions (LDS722, were liquid ethyl acetate ethanol PM597, the in and red) perylene solvents The pulses. 5.5 mJ maximum, half at width half 6 ns with 532 nm at pumping versal solution liquid (a) in (b) trans samples solid under in and nanoparticles bars) of 8MMAPOSS FIGURE 3.25 © 2016 Group, by Taylor LLC & Francis

The unique chemical and optical properties exhibited by POSS nanoparticles by exhibited POSS nanoparticles properties optical and chemical unique The 10 (b (a) ) −4 Laser e ciency (%) Laser e ciency (%) 20 40 60 20 80 40 60 M (Rh640, perylene red), 6 perylene M (Rh640, 0 0 PM PM

567P La 567P ser efficiency of different dyes in the presence (black bars) and absence (gray (gray absence and (black bars) presence the dyesin different efficiency ser of [82]. way, this In systemson dye-doped action in laser based the 57R6 Rh640 Rh6G M597 57R6 Rh640 Rh6G M597

10 −4 −3 M (PM597), and 8 and M (PM597), M (PM567), 4 Liquid solution Solid samples SulfRh SulfRh BP

× BP

10 erylene

× −4 re erylene

10 Tunable Laser Applications Tunable Laser d M (Rh6G, SulfRhB, LDS722), SulfRhB, M (Rh6G, re −4 d M (LDS730). M D72LDS730 LDS722 D72LDS730 LDS722 lasing with with lasing or - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 with pump power pump with density of 54 mW/cm pumping additives, transversal under 8MMAPOSS with PM567 PMMA pure in polymers. or grafted dronized for den with devices,tive optoelectronic competing of photonic materials sources - new as may alterna used be POSSnanoparticles hybrid systemson dye-linked based new repetitionrate.These of pulses 5.5 mJ/pulse at30 Hz 400,000 pump tion, after was now stable, without 56%,- any sign output of remained laser degrada the and REFERENCES radiation. of laser tunable coherent, sources practical stable, cheap, friendly, user and offerliquiddye to alternative as apromising lasers of liquid dyeto that have lasers developed. been improved These SSDL systems, improved comparable over new and dyes last decade, hoststhe performance with and chapter, technologyof use.for shown As SSDLs the this any practical greatly in has handicap lems systems by exhibited for these insurmountable were years many an prob photodegradation but the environments, medical and forate industrial in use outside use laboratory. the their much SSDLsseriously more appropri are restricted Chapter 8. in detail applications ment lesions. of considered in of dye vascular medical are The lasers therapy, photodynamic dermatology, cancer in treat the medicine, in and cules, and applications biology, in of biological kinetics reaction biomedical studying mole sciences, life dye the have In lasers found have utilized. lasers successfully been examples of are fields applied in which remote sensing,dye photochemistry and able high-resolution spectroscopy. tool in molecular and atomic separation, Isotope invalu an them made has visible the spectrum spanning radiation narrow-linewidth PPLICATIONS fieldstechnology.and sciencein tunable, providingof capability coherent, Their many in flexibilityin applications of resulted operational dye has unique lasers The 3.3 Solid-State Organic Dye Lasers Dye Organic Solid-State with 8MMAPOSS additives. 8MMAPOSS with competitive highly matrices of those the with on purely based materials polymeric of media characteristics lifetime operating result in can substances tion initial of the - purifica proper that demonstrating 8MMAPOSS, incorporated matrix whenas the level same atthe long-term remained the operation of polymerization, initiator and methylmethacrylate initial of purification careful with media PMMA into porated lasing efficiencies initial the were pulses. Although lower,the dyewhen incor was after the 50% at 140,000 pump there efficiency finally levelbilizing and remaining sta- irradiation, minutes of first the lasing efficiencyduring etition the dropped rate,

1990. Principles F. Laser (Eds), W. Dye J. L. Duarte, and Hillman Encyclopedia of Modern Optics Modern of Encyclopedia (Eds), Du A arte, F. J. and A. Costela, Dye lasers. In R. D. F. R. Bayvel In D. Guenther, L. Dye and lasers. G. Steel, J.arte, Costela, A. and 2 . Nevertheless, at 10 Hz pumping under rep , pp. 400–414, Elsevier,, pp. New 400–414, York, 2004. , A cademic, New York,cademic, 171 ------Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4

172

29: 3585–3586, 1990. 3585–3586, 29: Opt. 1, Appl. Part from 2,6,8-position trisubstituted 1,3,5,7-tetramethylpyrromethene-BF trisubstituted 2,6,8-position from Pa Commun. 7089–7094, 1992. 7089–7094, Series, American Chemical Society, Washington, DC, 1991. Society, DC, Washington, Chemical American Series, Optics for Nonlinear (Eds), Materials Stucky G. D. and J. Sohn, S. Marder, R. E. In materials. optical for nonlinear matrices as glasses Eng Opt. Lett Phys. Appl. dyes polymethyl methacrylate, in Lett Phys. Appl. lasers, So Zi O’ Pe Pa Soong, Laser dye spectroscopy of pyrromethene-BF some dyeSoong, spectroscopy Laser 39: 6522–6523, 2000. 6522–6523, 39: Opt. Appl. media, dye gain laser solid-state Du Devices and Materials Photonic and Electronic Advanced of S.H. Nalwa (Ed.), Handbook Co Pa tamethylpyrromethene-BF . 13: Electron 503–507, 1983.Sov. J. Quantum for lasers, materials Anew polymers: of class optical M. Prokhorov, A. Transparent and Dy 60: 383–389, 1995. 383–389, B60: Phys. Appl. 6G, Rhodamine with doped methyl methacrylate and of 2-hydroxyethyl oncopolymers based dye methacrylate lasers Solid-state Sastre, R. and Co 1518, 1995. 1518, 1516– 34: Opt. active Appl. poly(methylelements, modified methacrylate)-doped with Ma 46: 1941–1945, 1999. 1941–1945, 46: Optic. J.lasers, Mod. dye solid state co-polymer brightness, high T. G. photostability, high Efficient, Haskell, Gi 80: 3167–3173, 80: Phys. J. Appl. monomers, methacrylic with dyes copolymerized 1996. 6G Rhodamine on modified based dye lasers Solid-state Sastre, R. and Santa-María, Co Pa Electron. 38: 6337–6342, 1999. 6337–6342, 38: Opt. Appl. late), 567-doped poly(methyl of pyrromethene methacry consisting dye lasers solid-state in Ah Phys. Chem. Phys. Chem. developments, Phys. Ah Duc Co Opt. Appl. dye of lasers, polymeric analysis stability and characterization Photothermal Technol. Laser Opt. coumarin, and pyrromethene onmixed based media solid-state and tion nk, J. I., B. Dunn, R. B. Kaner, E. T. Knobbe, and J. McKiernan, Inorganic sol-gel Inorganic T. J. B. E. J. R. and McKiernan, Kaner, I.,nk, B.Knobbe, Dunn, vlopoulos, T. action M.-L. G., Soong, Laser and J. Boyer,H. Thangaraj, K. M. Shah, vlopoulos, T. G., J. H. Boyer, K. Thangaraj, G. Sathyamoorthi, M. Shah, and M.-L. and vlopoulos, T. M. Shah, G., J. G. Boyer, H. Sathyamoorthi, Thangaraj, K. vlopoulos, T. J. and Boyer, H. from G., M. Shah, action 1,3,5,7,8-pen laser Efficient Prog. Quant. dyes,vlopoulos, T. Prog. laser improved of with Quant. dye G., lasers Scaling terson, O. G. and B. B. Snavely, Stimulated emission from flashlamp-excited organic organic O. B. G. B. and terson, Snavely, flashlamp-excited from emission Stimulated Connell, R. M. and T. M. and R. T.Connell, Areview, applications: for Saito, Plastics high-power laser ffin, S. M., ffin, W. J. A. I. D. and Wadsworth, T. McKinnie, G. Woolhouse, J. Smith, ffer, B. H. and B. B. McFarland, Continuously tunable, narrow-band organic dye organic narrow-band ffer, B. B.tunable, Continuously B. and H. McFarland, stela, A., F. Florido, I. García-Moreno, R. Duchowicz, F. Amat-Guerri, J. M. Figuera, J. M. Figuera, A., Duchowicz, F. R. F.stela, I.García-Moreno, Amat-Guerri, Florido, stela, A., I. García-Moreno, and R. Sastre, Materials for solid-state dye lasers. In In dye for lasers. solid-state Materials Sastre, R. and A., I.García-Moreno, stela, stela, A., I. García-Moreno, J. M. Figuera, F. Amat-Guerri, R. Mallavia, M. D. Mallavia, R. F. J. M. A.,Figuera, I.García-Moreno, stela, Amat-Guerri, stela, A., I. García-Moreno, and R. Sastre, Polymeric solid-state dye lasers: Recent dye Recent lasers: solid-state Polymeric Sastre, R. and A., I.García-Moreno, stela, arte, F. J., A. Costela, I. García-Moreno, and R. Sastre, Measurements of Measurements F. Sastre, R. and J.,arte, I. García-Moreno, Costela, A. umaev, M., K. Manenkov, A. A. P. A. V. Maslyukov, G. A. Matyushin, S. Nechitailo, mad, M., M. D. Rahn, and T. and Singlet oxygen M., quenching M. D. King, A. dyemad, Rahn, and triplet-state mad, M., solu T.mad, laser D.-K. photostable King, A. Highly J. Ko, and Lee, B. Cha, H. slyukov, A., S. Sokolov, S. Popov, Nyholm, and K. M. Kaivola, dye laser Solid-state howicz, R., B. Scaffardi, A. Costela, I. García-Moreno, R. Sastre, and A. Acuña, Acuña, A. and Sastre, R. I.García-Moreno, Costela, A. howicz, R., B. Scaffardi, 39: 4959–4963, 2000. 4959–4963, 39: , Volume Diego, 7, San CA, 2001. 4, Academic, Chapter 34: 445–448, 2002. 34: 445–448, . 22: 393–399, 1983. 26: 193–224, 2002. 70: 425–427, 1989. 425–427, 70: . 10: 266–267, 1967. 2 Opt. derivative, Opt. 2,6-disulfonate complex its disodium and 5: 4745–4763, 2003. 4745–4763, 5: . 12: 1968. 238–240, , pp. 541–552, ACS Symposium Tunable Laser Applications Tunable Laser 2 complexes, 31: 31: Opt. Appl. 2 complexes: ∂ n / ∂ in T in - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 Solid-State Organic Dye Lasers Dye Organic Solid-State

18: 1841–1845, 2001. 1841–1845, B18: Am. Soc. J. Opt. plexes, 108: 3315–3323, 2004. 3315–3323, A108: dyes, Chem. J. laser Phys. photostable cient and 42: 1029–1035, 2003. 1029–1035, 42: Opt. Appl. rates, pump excited different at dye materials of laser polymeric analysis Photothermal Duc Al alkyl analogues of pyrromethene 567, 2005. 993–1006, B80: Phys. of pyrromethene Appl. analogues alkyl on8-substituted based dye lasers solid-state polymeric cross-linked and Linear Sastre, 17: Mat. 2007. Adv. Funct. 3088–3098, media, solid and liquid in action laser the BODIPY Dye PM567 the in enhancing changes Structural et al., Arbeloa, López Ga Li effects on laser action of the 1,3,5,7-tetramethyl-2,6-diethyl of the action pyrromethene–BF onlaser effects 1962, 2011. 1962, PM567,with doped copolymers Commun. Opt. on modified based lasers Ji Ga Arbeloa, et al., 8-Phenyl-substituted Dipyrromethene. BF Dipyrromethene. 8-Phenyl-substituted al., et Arbeloa, 101: 113110, 2007. 113110, 101: Phys. J. Appl. media, polymeric solid into rated dyes incorpo dipyrromethene from emission laser Bichromatic al., et Arbeloa, López Al 1302–1306, 2011. 1302–1306, 50: Opt. 580, Appl. pyrromethene with doped methanol with polymethyl methacrylate Ji Li Org. Lett. BODIPY dyes, Org. 3-Acetamido and of 3-Amino behavior laser and photophysical properties, Synthesis, al., et Infantes, L. Costela, A. ties of dipyrromethene-BF ties proper photophysics lasing between and Correlations F. and Sastre, R. Amat-Guerri, Lóp Photobiol. Sci. Photobiol. Photochem. matrices, polymeric solid BODIPYsolutionin dyes liquid and in stituted of 8-polyphenylene-sub studies emission laser Photophysical al., et and Arbeloa, López Al Ba 2010. Eur. J. 16: Chem. 14094–14105, effects, substitution BODIPY by asymmetric using of function and properties optical Controlling al., et Pérez-Ojeda, M. E. Infantes, L. Du 4195–4205, 2013. 23: Mat. Adv. Funct. BODIPYs media, solid and of liquid commercial in properties emission the Boosting versus fluorines: Carboxylates al., et I.Esnal, García-Moreno, Du García-Moreno, A. Costela, et al., First highly efficient and photostable E andphotostable efficient highly First al., et Costela, A. García-Moreno, 20: 2646–2653, 2014. Eur. J. 2646–2653, 20: Chem. rods, andsolid-state films, thin difluoro-4-bora-3a,4a,-diaza- Pé Du 1: Express. 243–251, Mat. dyes, 2011. Opt. laser BODIPY diiodinated from materials photonic andphotostable efficient Moreno, Highly 6335–6350, 2012. 6335–6350, dyes, Eur. laser J. Org. photostable Chem. highly BODIPYs:and efficient Chlorinated Surprisingly al., et Arbeloa, T. I.López Arbeloa, ang, Y.,ang, dye solid-state andphotostable efficient Y. Fan, R. D. Highly and Chen, Xia, ang, Y.,ang, Y.onmodified Fan, R. D. Tunable based and Chen, laser Xia, solid-state ang, F.,ang, Y. Sun, Z. H. Zeng, Yao, Yuan, Z. Xu, Eight-position Z. substitution and ras, M., J. Bañuelos Prieto, M. Pintado-Sierra, F. López Arbeloa, I. García-Moreno, I.García-Moreno, F. Arbeloa, López M., J. M. Pintado-Sierra, ras, Bañuelos Prieto, rez-Ojeda, M. E., C. Thivierge, M. Martín, A. Costela, K. Burgess, and I.García- and Burgess, K. Costela, A. M. Martín, Thivierge, M.C. E., rez-Ojeda, varez, M., F. Amat-Guerri, A. Costela, I. García-Moreno, C. Gómez, M. Liras, and R. R. and M. Liras, Gómez, C. I.García-Moreno, Costela, A. M., F.varez, Amat-Guerri, varez, M., A. Costela, I. García-Moreno, F. Amat-Guerri, M. Liras, R. Sastre, F. Sastre, R. M. Liras, F. I.García-Moreno, M., Costela, Amat-Guerri, A. varez, varez, M., A. Costela, I. García-Moreno, F. Amat-Guerri, M. Liras, R. Sastre, F. Sastre, R. M. Liras, F. I.García-Moreno, M., Costela, Amat-Guerri, A. varez, ñuelos Prieto, J., A. R. Agarrabeitia, I. García-Moreno, I. López Arbeloa, A. Costela, Costela, A. Arbeloa, I.López I.García-Moreno, J.,ñuelos Agarrabeitia, Prieto, R. A. rcía-Moreno, I. F. Amat-Guerri, M. Liras, A. Costela, L. Infantes, R. Sastre, F. Sastre, R. Infantes, L. Costela, A. M. Liras, I.F.rcía-Moreno, Amat-Guerri, rcía-Moreno, I., A. Costela, L. Campo, R. Sastre, F. Amat-Guerri, M. Liras, F. M. Liras, López F. Sastre, R. Campo, Amat-Guerri, L. I.,rcía-Moreno, Costela, A. rán-Sampedro, G., A. R. Agarrabeitia, L. Cerdán, M. E. Pérez-Ojeda, A. Costela, I. Costela, A. Pérez-Ojeda, M. E. Cerdán, L. G., Agarrabeitia, R. A. rán-Sampedro, rán-Sampedro, G., I. Esnal, A. R. Agarrabeitia, J. Bañuelos Prieto, L. Cerdán, I. Cerdán, J. L. Bañuelos Prieto, Agarrabeitia, R. A. G., I.Esnal, rán-Sampedro, rán-Sampedro, G., A. R. Agarrabeitia, I. García-Moreno, A. Costela, J. Costela, A. Bañuelos, I.García-Moreno, G., Agarrabeitia, R. A. rán-Sampedro, ez Arbeloa, T., F. López Arbeloa, I. López Arbeloa, I. García-Moreno, A. Costela, Costela, A. I.García-Moreno, T., Arbeloa, ez Arbeloa, I.López F. Arbeloa, López howicz, R., B. Scaffardi, A. Costela, I. García-Moreno, R. Sastre, and A. Acuña, Acuña, A. and Sastre, R. I.García-Moreno, Costela, A. howicz, R., B. Scaffardi, 7: 802–813, 2008. 2 299: 315–321, Lett. Phys. dyes solution, Chem. in 1999. s -indacene (BODIPY) as dye lasers in the liquid phase, phase, liquid the in dye as lasers (BODIPY) -indacene 9: 4183–4186, 2007. 4183–4186, 9: 2 complexes as highly effi complexes highly as - and C - and 284: 1959– 284: 2 com -4,4- 173 - - - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 174

BODIPY cassettes, BODIPY multichromophoric in transfer energy from action laser Unprecedent al., et Ojeda, Xi 8: 3133–3141, J. 8: 2013. Asian Chem. pair, rhodamine on a BODIPY and based of cassettes Y.and properties laser Photophysical and Xiao, Ga 111: 1508–1516, 2007. 1508–1516, 111: C. Chem. J. Phys. polymericmaterials, fluorinated new in of BODIPY chromophores physical properties and Laser al., et Bañuelos Prieto, Ga Fluoropolymers Ie Ra 97: Phys. 073517, J. Appl. waveguides, and 2005. dispersions, polymer solutions, thin-film in properties gain signal and pump Collinear amplification: for optical 640 of Rhodamine Acharacterization al., et Morgan, 1550–1551, 2008. 1550–1551, visible the dyesin fluorescent tunable Um Fa 16: 2008. Express. 9804–9810, Opt. polymethyl methacrylate, fied 10618, 2009. 10618, 10611– B113: Chem. J. Phys. 640, by rhodamine photosensitized materials red-edge Ga 12784, 2009. 12784, 17: Express. 12777– Opt. materials, polymeric doped of Perylene-Red action laser Ga 2552, 2009. 2552, 19: 2547– Mat. Adv. edge, Funct. spectral red the dye at for laser state solid reliable Ga 219: Chem. 2011. A: 265–272, Photobiol. J. Photochem. dyelaser, solid-state and stable efficient Ahigh matrices. polymeric B doped Ma 79: 452–454, 2001. 452–454, 79: Lett. Phys. Appl. by acopper-vapor pumped laser, dye lasers solid-state polymeric High-repetition-rate Co 84: 4902–4904, 2004. stability, 4902–4904, 84: Lett. Phys. Appl. Commun laser, Opt. solid-state by diode-pumped dye pumped laser solid-state rate repetition 10 al., et Coutts, kHz Ky Ab 77: B. Phys. 577–584, 2003. Appl. amplifiers, able laser La 44: 7814–7822, Opt. Appl. dye 2005. lasers, of solid-state photostability the in rate Role stimulated-emission of the K. Dasgupta, Ra Lett. Bo 19: 26382–26393, 2011. 19: 26382–26393, Express. Opt. Br Polym. Adv. Polym. Technol. technology, sol-gel by combined polymer obtained materials hybrid oninorganic-organic based Re Modern (Ed.), J. In Scheirs Modern applications. for architectural A., R. Fluoropolymers zzi, n, R., Y. Xia, and D. Chen, Solid state dye lasers based on LDS 698 doped in modi in 698 onLDS doped R.,based n, dye Y. D. lasers Solid state and Chen, Xia, onemann, R., E. Thiel, and P. cw dye Bolívar, and laser, High-power solid-state Thiel, R., E. Haring onemann, ao, Y., D. Zhang, X. Qian, A. Costela, I. García-Moreno, M. Martín, M. E. Pérez- M. E. M. Martín, ao, Y., I.García-Moreno, Costela, A. D. Qian, X. Zhang, - tun as use their dyes and of solid-state S. Y.m, Characterisation M. J. and Damzen, y, N. K., A. V. S. Kumar, S. S. Chattopadhyay, Kundu, Mayekar, and S. Sinha, isfeld, R., Weiss, A. T. Yariv, E. lasers Saraidarov, Solid-state Ishchenko, A. A. and mon, M. C., M. Ariu, R. Xia, D. D. Xia, R. N. Bradley,C. C. M. C.,mon, M. Ariu, M. S. Reilly, Marinelli, C. Opt. Continuous-wave dye Thiel, laser, Opt. E. solid-state R., U. and Lemmer, rnemann, stela, A., I. García-Moreno, R. Sastre, D. Sastre, W. R. Webb, A., E. C. I.García-Moreno, stela, and Coutts, tina, I.G., V.tina, power improved dye with High polymer Lips, K. laser G. Kytin, and rtzia-Rivero, L, H. Yu, J. Bañuelos, I. López Arbeloa, A. Costela, I. García-Moreno, I.García-Moreno, Yu, H. Costela, A. L, J. Arbeloa, Bañuelos,rtzia-Rivero, I.López rcía, O., R. Sastre, D. del Agua, A. Costela, I. García-Moreno, F. López Arbeloa, J. F. Arbeloa, I.García-Moreno, Costela, O., A. López D.rcía, Sastre, del R. Agua, rcía-Moreno, I., A. Costela, M. Pintado-Sierra, V. Martín, and R. Sastre, Efficient Efficient Sastre, R. and V. Martín, M. Pintado-Sierra, I.,rcía-Moreno, Costela, A. rcía-Moreno, I., A. Costela, M. Pintado-Sierra, V. Martín, and R. Sastre, Enhanced Enhanced Sastre, R. and V. Martín, M. Pintado-Sierra, I.,rcía-Moreno, Costela, A. rcía-Moreno, I., A. Costela, V. Martín, M. Pintado-Sierra, and R. Sastre, Materials Materials Sastre, R. and M. Pintado-Sierra, V. I.,rcía-Moreno, Costela, A. Martín, edin, K. M., M. Álvarez, A. Costela, I. García-Moreno, O. García, R. Sastre, D. Sastre, R. W. O. García, I. García-Moreno, Costela, A. M., K. M. Álvarez, edin, rtin, V., A. Costela, M. Pintado-Sierra, and I. García-Moreno, Sulforhodamine Sulforhodamine I.García-Moreno, and V.,rtin, M. Pintado-Sierra, Costela, A. ezawa, K., Y. Nakamura, H. Makino, D. Citterio, and K. Suzuki, Bright, color- Bright, Suzuki, K. D. and Citterio, ezawa, Makino, H. K., Y. Nakamura, 31: 1669–1671, 2006. , pp. 271–300, Wiley, John 1997. Chichester, Chem. Commun. Chem. . 218: 359–363, 2003. 15: 291–301, 2004. 47: 11513–11515, 2011. 11513–11515, 47: − 130: 130: Soc. Chem. J. Am. region, near-infrared Tunable Laser Applications Tunable Laser - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 Lasers Dye Organic Solid-State

8260–8271, 1995. 8260–8271, 34: Opt. Appl. poly(methylsol-gel, and host media, polycom, methacrylate) ormosil, Ra 35: 1473–1476, 2002. 1473–1476, 35: dyes sol-gel laser in phases, pyrromethene and ofity xanthene Ah Opt. Mater. Opt. ORMOSILs, in dyesof doped laser Ya 2213–2218, 2003. 2213–2218, 42: Opt. dye for laser, Appl. solid-state sol-gel hybrid Stable doped materials Boilot, Nh Ya Phys. B Phys. Appl. ORMOSILs, into of dyes co-doped performance laser dyes onthe coumarin ous Opt. Mater. Opt. Ya 387: 496–501, 2004. 387: 496–501, Lett. Phys. Chem. dye lasers, solid-state for materials organic-inorganic hybrid doped and stable efficient Co 369: 656–661, 2003. 369: 656–661, Lett. Phys. Chem. hybrid materials, new organic-inorganic into 567 dye incorporated of pyrromethene properties laser Co 78: 2004. B. Phys. 629–634, Appl. materials, hybrid ganic organic-inor into incorporated 6G of Rhodamine photostability lasing onthe effects Co dye lasers, J. dye lasers, for solid-state of nanocomposites hybrid physical properties and structure, Synthesis, 80: 749–755, B80: Phys. Appl. 2005. materials, hybrid of dye-doped performance laser the in network inorganic of the ence Co 375–378, 2006. 375–378, 427: Lett. Phys. aerogels, Chem. silica onfluorinated-polymeric based materials optical 2005. B109: 4475–4480, Chem. J.lasers, Phys. dye solid-state stable highly aerogelsas hosts for silica Polymer-fillednanoporous Co Ga Ga 101: 129–135, 2010. 129–135, B101: Phys. Appl. host matrices, solid Bin of Rhodamine Al 113: 113508, 2013. 113: Phys. 113508, sol-gel new J. mesoporous Appl. in hosts, incorporated 6G host-guest systems: Rhodamine luminescent in dye for aggregation reducing Strategies de Q de 101: 073110, 2007. 073110, 101: Phys. J. Appl. matrices, organic onsilicon-modified based dye lasers solid-state stable Co Su 113: 8118–8124, 2009. 8118–8124, 113: A Phys. J. Chem. matrices, polymeric solid in solutions and liquid in properties lasing BODIPY dye of the PM597: New al., et F. analogues Photophysical and Arbeloa, López Co 86: 537–545, 2007. B86: Phys. Appl. matrices, organic dye silicon-containing 597 laser in of pyrromethene Photophysical characterization -Shamiri, H. A. S. and M. T. H. Abou Kana, Laser performance and photostability photostability and performance Laser M. T. S. A. H. and Kana, Abou H. -Shamiri, sdorf, T.,sdorf, Tyagi, A. D. et al., Costela, A. del Agua, Sastre, R. Penzkofer, A. O. García, ng, Y., M. Wang, G. Qian, Z. Wang, and X. Fan, Laser properties and photostabilities photostabilities ng, Y., and properties Wang, M. Wang, Laser Z. Fan, X. and G. Qian, ng, Y., Rong, J.H. Y. Z. Zou, G. D. Qian, Wang, M. Q. and Wang, of vari Influence riv, E. and R. Reisfeld, Lasing properties of pyrromethene dyes sol-gel in glasses, of pyrromethene riv, Reisfeld, R. properties and Lasing E. hn, M. D. and T. A. King, Comparison of laser performance of dye in molecules performance of laser M. D. T.hn, and Comparison King, A. stela, A., I. García-Moreno, C. Gómez, O. García, L. Garrido, and R. Sastre, Highly Highly Sastre, R. and Garrido, L. O. Gómez, C. García, A., I.García-Moreno, stela, stela, A., I. García-Moreno, C. Gómez, O. García, and R. Sastre, Enhancement of Enhancement Sastre, R. and O. Gómez, C. García, A., I.García-Moreno, stela, stela, A., I. García-Moreno, C. Gómez, O. García, and R. Sastre, Environment Environment Sastre, R. and O. Gómez, C. García, A., I.García-Moreno, stela, stela, A., I. García-Moreno, O. García, D. del Agua, and R. Sastre, Structural influ Structural Sastre, R. and D. del Agua, O. García, A., I.García-Moreno, stela, stela, A., I. García-Moreno, C. Gómez, O. García, R. Sastre, A. Roig, and E. Molins, Roig, A. Molins, E. Sastre, R. and O. Gómez, C. García, A., I.García-Moreno, stela, stela, A., I. García-Moreno, D. del Agua, O. García, and R. Sastre, Highly photo Highly Sastre, R. and O. D. García, A., del Agua, I.García-Moreno, stela, stela, A., I. García-Moreno, M. Pintado-Sierra, F. Amat-Guerri, R. Sastre, M. Liras, M. Liras, Sastre, R. F. Amat-Guerri, M. Pintado-Sierra, A., I.García-Moreno, stela, rcía-Moreno, I., A. Costela, A. Cuesta, O. García, D. del Agua, and R. Sastre, Sastre, R. and D. del Agua, O. García, Cuesta, A. I.,rcía-Moreno, Costela, A. rcía, O., R. Sastre, D. del Agua, A. Costela, I. García-Moreno, and A. Roig, A. and Efficient I. García-Moreno, O., Costela, A. D.rcía, Sastre, delR. Agua, ung, T. H., T. M. Canva, T. N. Dao, A. F. D. J. Hung, Brun, A. and P. Chaput, mad, M., T. A. King, D.-K. Ko, B. H. Cha, and J. Lee, Performance and photostabil and M., T.mad, D.-K. King, A. Performance J. Ko, and Lee, B. Cha, H. ueiroz, T. B., M. B. S. Botelho, L. De Boni, H. Eckert, and A. S. S. de Camargo, S. A. S. T. Camargo, de and ueiroz, B., Eckert, H. Boni, M. B. De S. L. Botelho, 86: 309–313, 2007. 13: 1999. 49–54, Phys. Chem. B109: 21618–21626, Chem. Phys. 2005. 24: 621–628, 2004. 621–628, 24: Phys. J.D: Appl. Phys. 175 - - - - - Downloaded By: 10.3.98.104 At: 16:35 29 Sep 2021; For: 9781315265995, chapter3, 10.1201/b19508-4 176

457– 461, 2007. 461, 457– 43: Opt. Appl. 4088–4090, 2004. media, Opt. Lett. media, gain polymer-nanoparticle Du Du 112: 14170–14173, 2008. 14170–14173, C112: Chem. J. Phys. copolymers, onPOSS based materials Ga Commun. Opt. micro-particles, of dielectric-oxide addition the with polymers Ah 2009. 3307–3316, 19: Mat. Adv. Funct. lasers, solid-state andphotostable efficient for highly matrices polymeric (POSS)-modified silsesquioxane oligomeric polyhedral Dye-doped Sa 2009. Mat. Adv. emission, for laser solutions: POSS Nanomaterials doped Co 47: Elect. 907–919, J. Quantum 2013. IEEE experiment, and insights Theoretical materials: hybrid in dye-doped feedback to non-resonant due efficiencyenhancement Ce 94: 443–450, 2009. B94: Phys. 443–450, Appl. multiple by scattering, strong induced Ta Pé Lett. Phys. Mayer, Chem. T. and 567 matrices, solid N. Kopylova, in of pyrromethene Lasing Va 2011. Eur. J. 17: Chem. systems, photonic andphotostable 13258–13268, efficient for highly octasilsesquioxanes assembly of Click dye-functionalized J. Chiara, Moreno, and L. rez-Ojeda, M.B. E., Trastoy, J. I.García- Bañuelos, Costela, A. rez-Ojeda, Arbeloa, I.López stre, R., V. Martín, L. Garrido, J. L. Chiara, B. Trastoy, al., et Costela, A. J. Chiara, L. O. García, Garrido, R., L. V.stre, Martín, keda, S. and M. Obara, Extremely selective modal oscillation of random lasing lasing of random oscillation selective modal Extremely M. Obara, S. and keda, liev, N. R., R. Telminov, E. T. Solodova, A. N. Ponyavina, E. M. Gadirov, R. G. V. rdán, L., A. Costela, I. García-Moreno, V. Martín, and M. E. Pérez-Ojeda, Laser Laser Pérez-Ojeda, M. E. and V. I.García-Moreno, Costela, L., A. Martín, rdán, stela, A., I. García-Moreno, L. Cerdán, V. Martín, O. García, and R. Sastre, Dye- Sastre, R. and O. V. García, Cerdán, L. Martín, A., I.García-Moreno, stela, rcía, O., R. Sastre, I. García-Moreno, V. Martín, and A. Costela, New laser hybrid hybrid New laser Costela, A. and V. O., I.García-Moreno, rcía, Sastre, R. Martín, arte, F. J. and R. O. James, Spatial structure of dye-doped polymer nanoparticle gain gain nanoparticle polymer of dye-doped F. structure J.arte, O. R. Spatial James, and dye-doped, F. J.arte, O. R. incorporating Tunable James, and lasers solid-state mad, M., Enhanced photostability of photoluminescent dye-doped solutions and solutions and dye-doped of photoluminescent photostability M., Enhanced mad, 588: 184–187, 2013. 184–187, 588: 28: 2088–2090, 2003. Tunable Laser Applications Tunable Laser 21: 4163–4166, 4163–4166, 21: 271: 271: