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     

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     

Spectroscopic properties and amplified spontaneous emission of a new derivative of fluorescein

The new laser dye, 2-(6-acryloyloxy-3-oxo-3H-xanthen-9-yl)-benzoic acid ethyl ester [AOXBE] has been synthesized. Its chemical structure was confirmed by ¹HNMR, IR, MS and elemental analysis. This new dye was covalently bonded with methyl methacrylate (MMA) and 2-hydroxy ethyl-methacrylate (HEMA) copolymer backbone. Its optical properties were experimentally investigated. Amplified spontaneous emission (ASE) and photostability were studied by pumping the dye polymeric sample with a 355 nm (8 ns) pulsed Nd:YAG laser. PACS 42.55.Mv; 42.70.Hj; 42.70.Jk; 42.55.Px     

Solid-state dye lasers based on polymethyl methacrylate doped with pyrromethene 650

Solid-state dye samples based on polymethyl methacrylate (PMMA) doped with different concentrations of the dye PM650 were prepared. With SHG of Q-switched Nd:YAG laser (532 nm, ∼15 ns) pumping the samples longitudinally, the fluorescence, lasing spectra and slope efficiencies of the samples were obtained. The highest slope efficiency 27.49% and laser output energy 22.0 mJ was achieved in the sample with a dye concentration of 2.0 × 10⁻⁴ mol/L. To our knowledge, the results are the best under the same condition so far. The maxima of output lasing spectrum is about 653.5 nm. Our results have shown that using solid-state samples doped with PM650 can extend the dye laser wavelength to the red.     

Effect of laser treatment on the optical properties of poly(methyl methacrylate) thin films

In this work, the effect of laser pulse treatment on the optical properties of poly(methyl methacrylate) (PMMA) films has been studied experimentally. The second harmonic of a pulsed Nd:YAG laser at 532 nm and 6 ns pulse width with 10 Hz repetition rate was used to modify the surface of red-BS-dye-doped PMMA films. Samples were ablated with 50 and 100 laser pulses. Optical reflectance and transmittance spectra were obtained in the range of 200–2000 nm. The optical properties of the films were influenced by the pulse number significantly. The oscillator and dispersion energies of the films were determined using the Wemple-Didomenico model. The optical band gap energy was extracted using the Tauc method. Results show that the optical parameters of the films were changed significantly after laser treatment.     

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

Solid-state dye samples based on modified copolymers of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) with methanol doped with PM567 were first prepared. The volume proportions of methanol have great effects on the laser's characteristics including spectra, lasing output and thermal properties. The highest slope efficiency of 64.25% was achieved in the sample MP (MMA:HEMA = 85:15 + 10% methanol). Pumping the samples at a repetition rate of 5 Hz with a pulse energy as high as 100 mJ (the fluence was 0.26 J/cm²), the maximum lifetime of 278,000 shots was obtained in the sample MP (MMA:HEMA = 85:15 + 15% methanol), and the corresponding normalized photostability reached 180.7 GJ/mol. The obtained ten-shots damage thresholds were as high as 6.7 J/cm². The results indicate that the laser properties of solid-state dyes can be greatly enhanced by using modified copolymers of MMA and HEMA with methanol as solid hosts.     

Tunable narrow linewidth laser output from PM567 doped nematic liquid crystal under holographic pumping

LC cell injected the mixture of dye pyrromethene 567 (PM567) and nematic liquid crystal (NLC) by capillary action was prepared. Holographic pumping with a Nd:YAG laser (532 nm, 1 Hz, 10 ns) to form gain distributed feedback in the cell, tunable laser output from the cell was investigated. Through changing the intersection angles of the two coherent light beams from 46° to 50°, the tuning range we obtained is about 37 nm (550–587 nm). Additionally, the FWHM of the laser under such experimental setup was less than 0.1 nm even without the resonant cavity, and the threshold of the laser was about 26 μJ, which was very low as we known.     

Tunable ultraviolet laser source based on solid-state dye laser technology and CsLiB(6)O(10) harmonic generation

Tunable UV radiation centered at 289nm was obtained from a 532-nm Nd:YAG pumped high-brightness solid-state dye laser, frequency doubled in CsLiB(6)O(10). Frequency doubling to 284-294 nm was demonstrated from a singly doped, rotating pyrromethene dye plastic disk with damage threshold >3 J/cm(2) . UV energies up to 44 mJ at 10 Hz were obtained with a 15% absolute conversion efficiency from 532 nm.     

Laser Performance of Some Oxazole Laser Dyes in Restricted Matrices

This article reports the optical properties such as absorption profile, molar absorptivity, fluorescence profile and photo-physical parameters such as dipole moment, oscillator strength, fluorescence quantum yields, fluorescence lifetimes, laser performance and finally photostability of 2,5-Bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BBOT),1,4-Bis(5-phenyl-2-oxazolyl)benzene (POPOB), 5-diphenyel-oxazole (PPO) laser dyes in different restricted hosts. (BBOT), (POPOB) and (PPO) are embedded in transparent silica-based nanoporous sol-gel glass and copolymer matrix of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA). The absorption and fluorescence properties of these laser dyes in sol-gel glass matrices are compared with their respective properties in copolymer host. In case of sol-gel matrix, all dyes had higher quantum yields as well as lasing wavelength maxima. The laser performances as well as the photostability of these laser dyes in sol-gel glass displayed senior behavior compared with (MMA/ HEMA) copolymer samples upon using nitrogen laser (337.1 nm) as pumping energy.     

New photopolymer with trifunctional monomer for holographic applications

New holographic recording materials based on photopolymerizable systems have contributed significantly to the recent growth of holographic applications. Previously, we reported that in photopolymerizable systems with a difunctional monomer, Ethylene Glycol DiMethAcrylate (EGDMA) improves the behaviour of the system and explains the role played by an eosin ester that has an oxo-oxime group in the production of amine initiator radicals. This comparative study was carried out in our laboratory using differential scanning photo-calorimetry and holography. The results of the new photosensitive recording materials for holography indicate that this system can be used for the formulation of very promising photopolymers that have a better performance. The aim of this study was to change the crosslinking monomer in order to increase the energetic sensitivity and discover the rest of the behavior. The new photo-polymerizable mixture contains PentaErythritol TriAcrylate (PETA) in a 1:1 ratio of volume and a 2-Hydroxy-Ethylene MethAcrylate monomer (HEMA). A diffraction efficiency of 80% is achieved with an energetic sensitivity of 3 J/cm² at 514 nm, and the spatial resolution is up to 2000 lines/mm.Part of this paper was presented at the IS&T/SPIE Symposium in Electronic Imaging, Science and Technology (Holographic Materials), February 5–10, San Jose, CA, USA     

Accumulation morphology on the surface of stainless steel irradiated by a nanosecond Nd:YAG pulsed laser

In this study, results in the irradiation of stainless steel AISI 304 in air with nanosecond laser pulses at laser irradiation power density 4×10⁷ W/cm² are reported. Laser processing parameters, such as wavelengths 532 and 1064 nm, pulse duration 20 ns and repetition rate 10 Hz were used. It is shown that the surface morphology of the stainless steel is related to the number of pulses applied to the same spot. The following surface morphological changes were observed: (i) occurrence of the micro-grains microstructures at wavelengths 532 and 1064 nm after 10 000 pulses irradiation and (ii) occurrence of vermiform-like microstructures at wavelength 1064 nm after 1000 pulses irradiation. Generally, it is concluded that irradiation due to several consecutive pulses caused significant damage and enhanced the stainless steel surface roughness.     

多脉冲激光对碳纳米管悬浮液光限幅特性影响

利用实验的方法研究了碳纳米管悬浮液对脉宽8 ns,波长532 nm多脉冲激光的光限幅效应.分析了直径分布为10~20 nm的多壁碳纳米管悬浮液对重复频率分别为1 Hz、 3 Hz、 5 Hz、 10 Hz情况下532 nm激光的光限幅效应,分析计算了不同重复频率下碳纳米管悬浮液的限幅阈值,比较了不同焦距的透镜会聚入射光束情况下对碳纳米管悬浮液光限幅效果的影响.实验结果表明：碳纳米管悬浮液对不同重复频率的532 nm 激光都具有较强的光限幅特性;碳纳米管悬浮液对激光在不同重复频率入射情况下的光限幅阈值变化很大,当入射激光的重复频率为5 Hz时,碳纳米管悬浮液的光限幅阈值比单脉冲激光入射时的限幅阈值低了2倍,重复频率为10 Hz时的限幅阈值比单脉冲时的限幅阈值低了近3倍;碳纳米管在紧焦系统中的光限幅效果更好.     

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

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

车载式1 064 nm和532 nm双波长米散射激光雷达

 新近研制的车载式双波长米散射激光雷达可用于1 064 nm 和532 nm两个波长对白天与夜晚对流层气溶胶消光系数垂直分布进行的探测。该激光雷达由激光发射单元、接收光学和后继光学单元、信号探测和采集单元以及系统运行控制单元组成,后继光路之间采用光纤导光、高低层分层探测等关键技术。该激光雷达使用1 064 nm和532 nm的两个波长,其单发脉冲能量分别为400和300 mJ,重复频率都为20 Hz,光束发散角小于0.5 mrad ;望远镜接收视场为1～3 mrad,滤光片的中心波长为1 064 nm和532 nm,带宽1 nm。分别使用R3236及H7680的PMT和VT120及Phillips777的放大器对两个波长的信号进行探测;对532 nm波长用3 A/D采集卡、1 064 nm波长用了光子计数卡。给出了双波长测量对流层气溶胶消光系数垂直分布的结果,该激光雷达可以探测10 ^-5～1之间的消光系数,探测高度可达10 km以上。     

An efficient lasing action from pyrromethene 556 dye-doped organically modified silicates

Organically modified solid-state silicates (ORMOSILS) doped with a new laser dye 1,3,5,7,8-pentamethylpyrromethene-2,6-disulfonate-BF₂ complex (pyrromethene 556) have been synthesized by a sol-gel method and the compositional effects on pore characteristics, fluorescence and lasing properties have been investigated. It is found that the use of dimethylsulfoxide and γ-glycidoxypropyltrimethoxysilane could greatly change the structure properties of sol-gel derived ORMOSILS cage, and thus the fluorescence and lasing properties of the materials could improve significantly. A successful laser oscillation from this dye-doped ORMOSILS sample has been achieved upon pumping with a Q-switched frequency-doubled Nd:YAG laser at 532 nm. A slope efficiency of 54% with a useful lifetime greater than 10,000 shots has been demonstrated at a pump repetition rate of 1 Hz and a pump intensity of 1 J/cm² by using the new ORMOSILS cage on our newly designed laser system. Our results have shown that it is possible to obtain a high-efficiency with a long-lifetime for a compact new laser device by low cost dye-doped solid-state ORMOSILS.     

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     

Laser performance and photostability of Rhodamin B in solid host matrices

Laser dye Rhodamine B was incorporated at different concentrations in GMA polymer, sol–gel glass and organic–inorganic hybrid material synthesized using the sol–gel process. The amplified spontaneous emission (ASE) was studied using Nd-YAG laser of 532 nm. The effect of laser excitation in transfer pumping configuration and the influence of dye concentration on the ASE were studied. Also, the gain and the energy conversion efficiencies were investigated. Relatively high efficiencies (to ～48%) were obtained with good photostabilities where a decrease to ～30% of the initial amplified spontaneous emission output energy were observed after pumping by 35000 shots at relatively high repetition rate (10 Hz) and energy (15 mJ). The composition and the properties of the matrix were found that optimize the laser performance and photostability of an investigated dye.     

High-power, continuous-wave, singly resonant optical parametric oscillator based on MgO:sPPLT

We report a high-power, widely tunable, cw singly resonant optical parametric oscillator (OPO) based on MgO:sPPLT. The OPO is pumped in the green by a cw diode-pumped Nd:YVO(4) laser at 532 nm and can provide continuously tunable output across 848-1430 nm. Using a 30 mm crystal and double-pass pumping, an oscillation threshold of 2.88 W has been obtained, and single-pass idler powers in excess of 1.51 W have been generated over 1104-1430 nm for 6W of pump power at an extraction efficiency of 25.2% and photon conversion efficiency of 56.7%.     

Laser and absorption saturation measurements of Cr crystals, pumped by broadband pulsed 940 nm radiation

The characteristics of a 940 nm pumped Cr⁴⁺:forsterite laser have been investigated using a pulsed colour centre laser as the excitation source. Laser threshold, slope efficiency and temporal behaviour have been determined for high and low Cr⁴⁺ doped material. 940 nm pumping is found to be more efficient than 532 and 730–770 nm excitation. Discrepancies with 1064 nm pumping are attributed to excited state absorption. Absorption saturation measurements have been used to assess the potential applications of Cr⁴⁺:forsterite, Cr⁴⁺:YAG and Cr⁴⁺: Lu₃A1₅O₁₂ (LuAG) as passive Q-switches for Nd lasers in the 940 nm region.     

PM567-Doped solid dye lasers based on PMMA

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