New organic–inorganic hybrid matrices doped with rhodamine 6G as solid-state dye lasers

We report on the laser action of rhodamine 6G (Rh6G) incorporated into new hybrid organic–inorganic monolithic materials. The synthesis of these materials proceeded via the simultaneous sol-gel process of the inorganic part (tetraethoxysilane or tetramethoxysilane) and the free-radical polymerization of an organic monomer part (2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate and a 1:1 v/v copolymer of this monomer with methyl methacrylate). The wt. % proportion of the alkoxide was systematically varied in each organic formulation, and the effect of each organic–inorganic composition on the lasing properties of Rh6G was evaluated. The laser samples were transversely pumped and the influence on the laser action of dye concentration, pump wavelength and pump repetition rate was analyzed. Lasing efficiencies of up 26% and good stabilities, with a 90% drop in the initial laser output of up to 12000 pump pulses at 2.5 Hz, were obtained when the samples were pumped at 355 nm with 5.5 mJ/pulse from the third harmonic of a Q-switched Nd:YAG laser. Received: 31 July 2002 / Revised version: 14 October 2002 / Published online: 20 December 2002 RID="*" ID="*"Corresponding author. Fax: +34-91/564-4853, E-mail: ogarcia@ctp.csic.es     

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

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

Opto-acoustic study of tinuvin-P and rhodamine 6G in solid polymeric matrices

Laser-induced opto-acoustic calorimetry has been used to examine the thermo-elastic properties of two polymer matrices doped with tinuvin-P and the radiation-less decay processes of rhodamine 6G (Rh6G) in them. The matrices assayed were methyl methacrylate (MMA) homopolymers P(MMA), and methyl methacrylate and 2-hydroxyethyl methacrylate (HEMA) copolymers P(MMA:HEMA). A slight difference in the thermo-elastic properties of the polymers, namely their adiabatic expansion coefficients, has been detected and found to correlate with the long-term stability of the laser material. This suggests a key role of the heat-dissipation processes in the photostability of these polymeric materials. On the other hand, the fluorescence quantum yield of Rh6G is shown to vary with the polymer-matrix composition in a way consistent with its lasing efficiency. The Rh6G absorption and fluorescence quantum yield also change dramatically upon increasing its concentration, which suggests the co-existence of different Rh6G forms with different photophysical properties. Received: 10 February 2000 / Revised version: 12 June 2000 / Published online: 10 January 2001     

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

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

Effect of Tm concentration on the tunability of the YLF laser in the 1.9 µm region

We describe the continuous-wave (cw) operation of a LiYF₄ laser based on crystals doped with different concentrations of Tm³⁺. We observed the fluorescence spectra from the upper laser level when the crystal is placed inside the laser resonator, in the same optical environment of the coherent emission. We measured the laser intensity as a function of pump power and obtained a 24% slope efficiency by selecting a suitable orientation of the crystal. Using all this information, we were able to demonstrate laser tunability at 1.9 µm in a 50 cm^–1 wide interval.     

Measurement of nonlinear properties and optical limiting ability of Rhodamine6G doped silica and polymeric samples

The third order nonlinear optical properties of Rhodamine6G (Rh6G) doped silica and polymeric samples have been investigated using single beam z-scan technique under excitation by the second harmonic of Nd:YAG laser beam (532 nm). The nonlinear refractive index, nonlinear absorption coefficient, real and imaginary parts of third order nonlinear susceptibility in the samples of silica and poly-methylmethacrylate (PMMA) matrices are measured. Thermal contribution to the nonlinear refractive index in case of undoped silica samples has been calculated in order to have better accuracy of the material response contribution to third order nonlinearity. The comparative study of the optical limiting performance of Rh6G doped silica and polymeric samples show that Rh6G doped silica is relatively superior for optical limiting applications.     

Synthesis of 3-dimensional periodic nanostructures in an interference field of UV laser light

In 2000, Campbell et al. (Nature 404:53, 2000) have shown that three-dimensional periodic nanostructures can be obtained from UV laser interference irradiation of photoresist for 6 nanosecond single pulse. We have developed a similar experiment for photolytic gas phase decomposition and for photopatternable organic–inorganic hybrid resins. Different steps in results, presently reported, were first to determine the characteristics of both the 3D interference pattern and interferometer to be associated to a CVD reactor and second to verify the mechanical stability of the set up confirmed with the structuration of a siloxane based methacrylic resins by UV polymerization and finally to grow periodic nanostructures by photolytic gas phase decomposition of chromyl chloride. The experimental results obtained so far indicate that, depending on the electromagnetic energy density, a vapor phase decomposition of chromyl chloride leads to periodic arrays of either Cr–O amorphous or Cr₂O₃ particles on glass and (001)TiO₂ substrates at room temperature.     

Development and characterization of Yb-Er laser glass for high average power laser diode pumping

A new strong erbium laser glass (SELG) based on a boro-alumo-phosphate composition is reported. We discuss the synthesis and chemical properties together with spectroscopic and thermo-mechanical data. The new glass composition shows excellent laser performance and withstands high-average power pump radiation. We present laser results at 1.54 μm from flashlamp and laser pumping. In tests with laser-diode pumped Q-switched Er-Yb microchip lasers, we have achieved up to 150 mW of average output power and generated 1.2 kW in peak power. Co²⁺:MgAl₂O₄ was here used as the saturable absorber. Received: 21 December 2001 / Revised version: 14 April 2002 / Published online: 8 August 2002     

Low-Threshold Conjugated Polymer Distributed Feedback Lasers on InP Substrate

We demonstrate a low threshold polymer solid state thin-film distributed feedback （DFB） laser on an InP substrate with the DFB structure. The used gain medium is conjugated polymer poly[2-methoxy-5-（2-ethylhexyloxy）-l, 4- phenylenevinylene] （MEH-PPV） doped polystyrene （PS） and formed by drop-coating method. The second order Bragg scattering region on the InP substrate gave rise to strong feedback, thus a lasing emission at 638.9nm with a line width of 1.2nm is realized when pumped by a 532nm frequency-doubled Nd：YAG pulsed laser. The devices show a laser threshold as low as 7n J/pulse.     

Spectral Hole-Burning of Eu^3＋：Y2SiO5 Crystal at 16 K

By using an Ar^＋ ion laser, a tunable Rh 6G dye laser （linewidth 0.5cm^-1） pumped by the second harmonic of a YAG：Nd laser and a Coherent 899-21 dye laser as light sources and using a monochromator, a phase-locking amplifier and a computer as the data detecting system, we detect the optical properties of Eu^3＋-doped Y2SiO5 crystal. Persistent ,spectral hole burning （PSHB） are observed in the Eu^3＋ ions spectral lines （^5 Do-T Fo transition） in the crystal at the temperature of 16K. For 15mW dye laser burning the crystal for 0.1 s spectral holes with hole width about 80 MHz both at 579.62nm and at 579.82nm are detected and the holes can remain for a long time, more than 10h.     

Passive Q-switching at 1.54 μm of an Er–Yb: GdCa4O(BO3)3 laser with a Co2+: MgAl2O4 saturable absorber

We report, for the first time to our knowledge, efficient passive Q-switching of the 1.54-μm laser transition in an Er–Yb-doped crystalline medium. The laser configuration is a compact microchip design that is suitable for a range of practical applications such as range finding and lidar. The slope efficiency of 11.6%, pulse duration of 5–6 ns and average output power of 88 mW are all comparable with standard Er–Yb:glass lasers.     

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

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

Experimental observation and numerical simulation of guided modes in Nd:YLiF4 channel waveguides produced by carbon ion implantation

We report on, to our knowledge the first time, the channel waveguide formation in Nd:YLiF₄ laser crystal produced by 6 MeV carbon ion implantation. The guided modes are observed by using an end‐face arrangement. We construct the two‐dimensional (2D) refractive index profile of the channel waveguide cross section, which is based on the related planar waveguide index distribution as well as the rectangular shape of the waveguide cross sections. The modal intensity distribution is numerically calculated by using the beam propagation method according to the reconstructed index profile, which shows a reasonable agreement with the experimental result. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

New approaches for the fabrication of photonic structures of nonlinear optical materials

We revisited two different strategies to fabricate 1D photonic crystals of nonlinear optical dielectric materials based on ultrafast laser ablation of the surface of an RbTiOPO₄ crystal, and selective etching of ferroelectric domains of the surface of a periodically poled LiNbO₄ crystal. We evaluated their behaviour as Bragg diffraction gratings. We also presented the recent advances we developed in a new procedure of fabrication of 2D and 3D photonic crystals of KTiOPO₄ (KTP) grown on the surface of a KTP substrate by liquid phase epitaxial means within the pores of a silicon macroporous template. Optical, structural, morphological, and compositional characterization for the photonic crystals produced through this technique are presented.     

Polarized and time-resolved measurements of excited-state absorption and stimulated emission in Ti:YAlO3 and Ti:Al2O3

Pump-induced excited-state absorption (ESA) in the whole range of pump wavelengths prevents effective laser action of Ti:YAlO₃. The time-resolved measurement of this absorption allows the separation of excited-state absorption and losses due to transient colour centres. The influence of polarization on the ESA of Ti:YAlO₃ is only weak, as it is expected for a charge-transfer transition. No significant stimulated emission (SE) could be measured in the whole fluorescence region. In comparison, Ti:Al₂O₃ shows a broad SE spectrum corresponding to the tuning range of this laser material. The strongest SE was measured for Ec, which is the preferred polarization for laser action of Ti:Al₂O₃. Below 350 nm the long-wavelength edge of an ESA band was found.     

Laser modes in organic solid-state distributed feedback lasers

We report on the laser modes in optically pumped solid-state lasers using an electroluminescent organic semiconductor as the active medium. Mechanically flexible distributed-feedback lasers are fabricated by depositing a thin film of an active material onto a nano-patterned polyester substrate either via spin-coating of a soluble ladder-type poly(p-phenylene) or via vacuum co-sublimation of small organic molecules. The different surface texture resulting from the fabrication process causes different feedback mechanisms. In both lasers higher lateral modes give rise to a broadening of the laser spectra at higher pumping levels. Received: 7 August 2000 / Revised version: 12 September 2000 / Published online: 8 November 2000     

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

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

Laser action in a cw diode-pumped Nd:Ca3Sc2Ge3O12 crystal

CW diode-pumped laser operation of Nd³⁺ in Ca₃Sc₂Ge₃O₁₂ (CaSGG) single garnet crystal has been demonstrated for the first time. We measured an 18% slope efficiency and 2.7-nm tunability with two different laser cavities. A spectroscopic characterization of our sample has also been performed including the absorption cross section in the 800-nm region and the emission cross section and radiative lifetime of the upper laser level. Received: 7 December 1999 / Revised version: 6 February 2000 / Published online: 27 April 2000     

Producing ORMOSIL scaffolds by femtosecond laser polymerization

Structures with different geometries and sizes were built via direct femtosecond laser writing, starting from new organic/inorganic hybrid monomers based on hybrid methacrylate containing triethoxysilane, in addition to urethane and urea groups. Multifunctional oligomer of urethane dimethacrylate type was chosen as comonomer in polymerization experiments because dimethacrylates give rise to the formation of a polymer network, having a number of favorable properties including biocompatibility and surface nanostructuring. Free standing polymeric structures were designed and created in order to be tested in fibroblast cells culture. Investigations of the cellular adhesion, proliferation, and viability of L929 mouse fibroblasts on free-standing laser processed scaffolds were performed for different scaffold designs.     

Er3+/Yb3+ Codoped Phosphate Glass Fibre with Gain per Unit Length Greater Than 3.0dB/cm

We experimentally study a novel fibre with high gain per unit length based on the homemade erbium--ytterbium codoped phosphate glass. The gain and noise characterizations with different pump powers at different wavelengths are investigated. The 1.8-cm-long fibre, dual-pumped by two single mode 980-nm fibre-pigtailed laser diodes, provides a gain per unit length greater than 3.0dB/cm and a noise figure less than 6.5dB. The gain saturation behaviour at 1535nm is obtained and the saturation output power (3dB compression) is greater than 5dBm.