Laser induced surface damage, thermal transport and microhardness studies on certain organic and semiorganic nonlinear optical crystals

N-alkyl-2,6-dimethyl-4(1H)-pyridinones, salts of 4-dimethylaminopyridine and 2-amino-5-nitropyridine are considered to be potential candidates for nonlinear optical (NLO) applications, in particular for the generation of blue-green laser radiation. Single crystals were grown following the slow evaporation technique at constant temperature. Single-shot laserinduced surface damage thresholds in the range 3–10 GW/cm2 were measured using a 18 ns Q-switched Nd:YAG laser. The surface morphologies of the damaged crystals were examined under an optical microscope and the nature of damage identified. The Vicker’s microhardness was determined at a load of 98.07 mN. The thermal transport properties, thermal diffusivity (α), thermal effusivity (e), thermal conductivity (K) and heat capacity (Cp), of the grown crystals were measured by an improved photopyroelectric technique at room temperature. All the results are presented and discussed.

Lithium D-Isoascorbate Monohydrate, a New Nonlinear Optical Material

Single crystals of lithium D-isoascorbate monohydrate (LDAM), (C6H7O6Li center dot H2O), are grown by a solution growth method. The crystal structure of LDAM is solved using single crystal X-ray diffraction. The space group is orthorhombic P2(1)2(1)2(1) with four formula units per unit cell and lattice parameters a = 7.7836(3) angstrom, b = 8.7456(3) angstrom, and c = 11.0368(4) angstrom. Solubility of the material in water is determined thermogravimetrically and found to have a positive temperature coefficient of solubility. Large optical quality single crystals are subsequently grown from aqueous solution by a slow cooling method. The crystal has a bulky prismatic habit and among the prominent faces the c face appears as the only principal morphological face. The crystal exhibits a (010) cleavage. Dielectric spectroscopy reveals a nearly Debye type Cole-Cole behavior with anisotropy in relaxation. Optical transmission range is found to be from 300 to 1400 nm. The principal refractive indices of this biaxial crystal, measured using Brewster's angle method, at wavelengths 405, 543, and 632.8 nm, show high dispersion. The crystal is negative biaxial with 2V(z) = 107.8 degrees (405 nm) and belongs to the Hobden class 3. Theoretically generated type 1 and type 2 second order phase matching curves match very well with the experimental results. The second-order nonlinear coefficient d(14) was determined to be 7 x 10(-13) m/V. For the optimum phase matching direction (type 2), the second-order effective nonlinear coefficient and the walk off angle are determined to be 0.84 times d(14) and 3.5 degrees respectively. The crystal possesses high multiple surface damage thresholds of 18 GW/cm(2) and 8 GW/cm(2) at laser wavelengths 1064 and 532 nm, respectively.

Studies on lithium L-ascorbate dihydrate: An interesting chiral nonlinear optical crystal

Lithium L-Ascorbate dihydrate (LLA) is a new metal organic nonlinear optical crystal belonging to the saccharide family. Single crystals of LLA were grown from aqueous solution. Solubility of the crystal has a positive temperature coefficient facilitating growth by slow cooling. Rietveld refinement was used to confirm the phase formation. The crystal has prismatic habit with (010), (001) and (10-1) prominent faces. Thermal analysis shows that the crystal is stable up to 102 degrees C. Transmission spectrum of the crystal extends from 302 nm to 1600 nm. Dielectric spectroscopic analysis revealed Cole Cole behaviour and prominent piezoelectric resonance peaks were observed in the range of 100-200 kHz. Second harmonic generation (SHG) conversion efficiency of up to 2.56 times that of a phase matched KDP crystal was achieved when the (010) plate of LLA single crystal was rotated about the +ve c axis, by 9.4 degrees in the clockwise direction. We also observed SHG conical sections which were attributed to noncollinear phase matching. The observation of the third conical section suggests very high birefringence and large nonlinear coefficients. A detailed study of surface laser damage showed that the crystal has high multiple damage thresholds of 9.7 GW cm(-2) and 42 GW cm(-2) at 1064 nm and 532 nm radiation respectively. (C) 2012 Elsevier B.V. All rights reserved.

Crystal growth and nonlinear optical properties of sodium D-isoascorbate monohydrate

Optical quality single crystals of sodium D-isoascorbate monohydrate were grown by a slow cooling technique. The crystal possesses a bulky prismatic morphology. Thermal analyses indicate that the crystals are stable up to 125 degrees C. The optical transmission window ranges from 307 nm to 1450 nm. The principal refractive indices have been measured employing Brewster's angle method. The crystallographic and the principal dielectric axes coincide with each other such that a lies along Z, b along X and c along Y. The optic axis is oriented 58 degrees (at 532 nm) to the crystallographic a axis in the XZ plane and the crystal is negative biaxial. Type 1 and type 2 phase matching curves are generated and experimentally verified. No polarization dependence of the light absorption was observed confirming the validity of Kleinman's symmetry conjecture, leading to a single nonvanishing nonlinear tensor component. According to Hobden's classification the crystal belongs to class 3. The crystal also exhibits second order noncollinear conic sections. The single shot and multiple shot surface laser damage thresholds are determined to be 32.7 GW cm(-2) and 6.5 GW cm(-2) respectively for 1064 nm radiation.

Wideband two-port beam splitter of a binary fused-silica phase grating

The usual beam splitter of multilayer-coated film with a wideband spectrum is not easy to achieve. We describe the realization of a wideband transmission two-port beam splitter based on a binary fused-silica phase grating. To achieve high efficiency and equality in the diffracted 0th and -1st orders, the grating profile parameters are optimized using rigorous coupled-wave analysis at a wavelength of 1550 nm. Holographic recording and the inductively coupled plasma dry etching technique are used to fabricate the fused-silica beam splitter grating. The measured efficiency of (45% x 2) = 90% diffracted into the both orders can be obtained with the fabricated grating under Littrow mounting. The physical mechanism of such a wideband two-port beam splitter grating can be well explained by the modal method based on two-beam interference of the modes excited by the incident wave. With the high damage threshold, low coefficient of thermal expansion, and wideband high efficiency, the presented beam splitter etched in fused silica should be a useful optical element for a variety of practical applications. (C) 2008 Optical Society of America.

高激光损伤阈值溶胶-凝胶ZrO2薄膜

采用醇热法水解氧氯化锆（ZrOCl2·8H2O）制备ZrO2溶胶，提拉法涂膜。采用粘度、粒度分布、折射率、IR、DSC、AFM等测试手段对溶胶和薄膜性能进行表征。结果表明，ZrO2溶胶颗粒的平均粒径为18．9nm，薄膜经300℃热处理后折射率可高达1．95，膜层表面均匀平整，表面平均粗糙度仅为0．561nm，膜层的激光损伤阈值为14J／cm^2（1064nm，1ns）。

Optimization of near-field optical field of multi-layer dielectric gratings for pulse compressor

Multi-layer dielectric (MLD) gratings for pulse compressors in high-energy laser systems should provide high diffraction efficiency as well as high laser induced damage thresholds (LIDT). Nonuniform optical near-field distribution is one of the important factors to limit their damage resistant capabilities. Electric field distributions in the gratings and multi-layer film region are analyzed by using Fourier modal method. Optimization of peak electric field in the gratings ridge is performed with a merit function, including both diffraction efficiency and electric field enhancement when the top layer material is HfO2 and SiO2, respectively. A set of optimized gratings parameters is obtained for each structure, which reduce the peak electric field within the gratings ridge to being respective 1.39 and 1.84 times the value of incident light respectively. Finally, we also discuss the effects of gratings refractive index, gratings sidewall angle and incident angle on peak electric field in the gratings ridge. (c) 2006 Elsevier B.V. All rights reserved.

多层介质膜光栅和介质膜反射镜抗激光损伤阈值研究

对多层介质膜光栅以及介质膜反射镜的激光损伤阈值进行了系统的研究。测试方法采用国际测试标准。测试结果表明，介质光栅的损伤阈值远低于未刻蚀的多层介质膜。对样品损伤形貌的扫描电镜照片分析发现，相比于未刻蚀的多层介质膜，介质膜光栅的初始损伤主要发生在光栅槽形的侧壁，且损伤主要是由驻波场的空间分布引起的本征吸收、制备过程中引入的杂质污染以及刻蚀过程中HfO2的化学计量机失衡引起的。

Ta2O5膜在532, 800 和 1064 nm波长的n-on-1体系下的激光损伤阈值研究

Ta2O5膜采用传统的电子束蒸发方法制备，并在氧气中673 K的条件下进行了退火12 h处理。首先在1-on-1体系下对Ta2O5膜进行了532和1064 nm波长下的激光损伤阈值（LIDT） 研究，然后在n-on-1体系下分别对532，800和1064 nm三种波长下的激光损伤阈值进行了研究。结果表明在n-on-1体系下Ta2O5膜在532和1064 nm波长下的阈值均高于1-on-1体系下的阈值。此外，在n-on-1体系下，薄膜的阈值随波长增加而增大。同时发现，在氧气中进行退火对Ta2O5膜的光学性能

1064nm与532nm激光对电子束蒸发制备的HfO2／SiO2高反膜损伤比较

研究了电子束蒸发制备的HfO2／SiO2高反膜在1064nm与532nm激光辐照下的损伤行为。基频激光辐照时损伤形貌主要为节瘤缺陷喷溅留下的锥形坑。当能量密度较大时出现分层剥落；二倍频激光损伤主要是由电子缺陷引起的平底坑，辐照脉冲能量密度稍高时也会产生吸收性缺陷引起的锥形坑，但电子缺陷的损伤阈值更低；随着辐照脉冲能量密度的增大分层剥落逐渐成为主要的损伤形貌。分析认为，辐照激光波长的变化。引起吸收机制的变化从而导致了损伤阈值及损伤机制的差异。

引入过渡层提高介质减反膜的抗激光损伤阈值

提出了一种用于提高介质减反膜的损伤阈值的新的方法，在H2.5L (H:HfO2, L:SiO2)的膜层与基底之间引入4个1/4光学厚度的SiO2薄膜，发现抗激光损伤阈值提高了50%，并且保持1064nm处的反射率低于0.09%。本文分析了造成这一提高的机制，一定厚度的氧化硅过渡层的引入是一种提高介质减反膜的损伤阈值的灵活有效的方法。

三种不同后处理方式对ZrO_2薄膜性能的影响

采用有氧热处理、激光预处理和离子后处理三种方式对电子束蒸发(EBE)制备的单层ZrO_2薄膜进行了后处理,并分别对样品的光学性能和抗激光损伤阈值(LIDT)特性进行了研究。实验结果表明,热处理方式可以有效排除膜层内吸附的水气,弥补薄膜制备过程中的氧损失,使得光谱短移、吸收减小、损伤阈值增高;激光预处理过程可以在一定程度上减少缺陷、提高损伤阈值,但对膜层的光谱和吸收情况没有明显的改善作用;而离子后处理能够提高膜层的堆积密度、减少缺陷、降低吸收从而提高损伤阈值。由于三种方式处理机制不同,在实际应用中应根据膜层的性能选择合适的处理方式。

不同方法制备的Ta_2O_5薄膜光学性能和激光损伤阈值的对比分析

采用电子束蒸发(EBE)和离子束溅射(IBS)制备了不同的Ta_2O_5薄膜,同时对电子束蒸发制备的薄膜进行了退火处理。研究了制备的Ta_2O_5薄膜的光学性能、激光损伤阈值(LIDT)、吸收、散射、粗糙度、微缺陷密度和杂质含量。结果表明,退火可使电子束蒸发制备的薄膜的光学性能得到改善,接近离子束溅射的薄膜的光学性能。电子束蒸发制备的薄膜的损伤阈值较低的主要原因在于吸收大,微缺陷密度和杂质含量高,而与薄膜的散射和粗糙度关系不大。退火后薄膜的吸收和微缺陷密度都明显降低,损伤阈值得到提高。退火后的薄膜损伤阈值仍然低于溅射得到的薄膜损伤阈值是因为退火并不能降低膜内的杂质含量,因此选用高纯度的蒸发膜料和减少电子束蒸发过程中的污染有可能进一步提高薄膜的损伤阈值。

X-ray laser-induced ablation of lead compounds

The recent commissioning of a X-ray free-electron laser triggered an extensive research in the area of X-ray ablation of high-Z, high-density materials. Such compounds should be used to shorten an effective attenuation length for obtaining clean ablation imprints required for the focused beam analysis. Compounds of lead (Z=82) represent the materials of first choice. In this contribution, single-shot ablation thresholds are reported for PbWO4 and PbI2 exposed to ultra-short pulses of extreme ultraviolet radiation and X-rays at FLASH and LCLS facilities, respectively. Interestingly, the threshold reaches only 0.11 J/cm(2) at 1.55 nm in lead tungstate although a value of 0.4 J/cm(2) is expected according to the wavelength dependence of an attenuation length and the threshold value determined in the XUV spectral region, i.e., 79 mJ/cm(2) at a FEL wavelength of 13.5 nm. Mechanisms of ablation processes are discussed to explain this discrepancy. Lead iodide shows at 1.55 nm significantly lower ablation threshold than tungstate although an attenuation length of the radiation is in both materials quite the same. Lower thermal and radiation stability of PbI2 is responsible for this finding.

Optical-limiting response of rare-earth metallo-phthalocyanine-doped copolymer matrix

The nanosecond optical-limiting characteristics (at 532 nm) of some rare-earth metallo-phthalocyanines (Sm(Pc)2, Eu(Pc)2, and LaPc) doped in a copolymer matrix of poly(methyl methacrylate) and methyl-2-cyanoacrylate have been studied for the first time to our knowledge. The optical-limiting response is attributed to reverse saturable absorption due to excited-state absorption. The performance of LaPc in a copolymer host is studied at different linear transmissions. The laser damage thresholds of all the samples are also reported.