ORGANIC NONLINEAR OPTICAL CRYSTAL:N-(4-NITROPHENYL)-(s)-(+)-2-PYRROLIDINEMETHYLENE TOSYLATE(NPP-OTs)

Large crystal NPP-OTs has been obtained by growth from solution,its powder SHG efficiency is 1/3 of urea.It shows it is a new convenient approach to obtain organic second-order NLO crystal:the dipole-dipole interaction is oppos- ed by introducing a large side group.

New Complex Nonlinear optical Crystal-Bis(4-methoxybenzaldehyde thiosemicarbazone) Zinc Chloride(ZnL_2Cl_2)

The structure of ZnL2Cl2 (L=4-methoxybenzaldehyde thiosemicarbazone) has beenobtained by x-ray diffraction. The compound crystallized in space group Cc with Z=4, in a unit cellof dimensions, a=9.08909(10), b=22. l420(10), c=11 .7890(l0)A,β=90.050(10)°, v=2374.6(12)A3,Dc=1 .552gcm-3. H=1 .463mm-1. R=0.0338. and Rw=0.0418. The structure contains individualZnL2Cl2 distorted tetrahedral units in which L molecules are S-bonded as monodentate to the metalions; chloride ions are also coordinated. The nonlinear optical properties of the zinc complex arealso presented in this letter.

Evaluating refractive index and birefringence of nonlinear optical crystals:Classical methods and new developments

Nonlinear optical(NLO)materials play an increasingly important role in laser technology.Birefringence is one of the most important parameters for NLO materials to realize angle phase-matching conditions.In comparison with other desirable optical properties,the availability of birefringence and refractive index dispersion is especially problematic owing to the strict requirements for single crystals.In this review,we described how to obtain the refractive index and birefringence of NLO materials from crystals sub-millimeters to centimeters in size.Espe-cially,recently developed methods including the minimum deflection angle method,auto-collimation method,prism coupling method,oil immersion technique,interference color method,and theoretical calculation(DFT)for rapid assessment of birefringence are summarized,the contents of which are mainly focused on the principles and typical applications,together with the advantages and drawbacks.In addition,representative examples of bire-fringent measurements were presented.The purpose of this work is to provide a useful perspective on the characterization of birefringence for NLO materials.It is hoped that this review can give a clear description of the birefringence measurements and accelerate the discovery of new NLO crystals.

Crystal Growth and Structure of Novel Tolane Nonlinear Optical Materials

A novel tolane 4-methoxy-4'-nitro-diphenyl-acetylene (MONA) has been prepared quantitatively by reacting cuprous p-methoxy phenyl-acetylene with p-iodonitrobenzene. A single crystal of the Moan was grown by solution growth method. The crystal was then characterized by X-ray diffraction structure analysis and second-harmonic generation(SHG)investigation. Polymorphous crystal forms of the MONA were grown from different solvents having different nonlinear optical properties depending on their different crystal structures. The relationship between the crystal growth and crystal structure is discusse.

Deep-ultraviolet nonlinear optical crystals by design:A computer-aided modeling blueprint from first principles

Deep-ultraviolet(DUV)nonlinear optical(NLO)crystal is indispensable in current DUV all-solid-state laser technology,which is the key device to generate DUV light by frequency conversion.Due to stringent criteria,DUV NLO crystals are scarce and their discovery faces a big challenge.Although KBe2BO3F2(KBBF)is already excellent for current uses,the development of DUV science requires the materials with shorter output wavelengths and larger NLO effects,so as to meet the needs of DUV lasers with higher precision and higher power.Therefore,how to efficiently design DUV NLO materials has always been the core issue in NLO materials science.Looking back on the development of NLO materials,it turns out that theoretical modeling and simulation is an effective and efficient method,not only for mechanism understandings,but also for experimental exploration.In this article,in order to accelerate the process of DUV materials discovery,we summarize and propose a powerful computeraided modeling system and design blueprint that can be used to evaluate the DUV NLO performance in a faster way than pure experiments.With this in hand,we enrich the understanding of NLO structure-property correlation,and systematically prospect the DUV NLO properties on the basis of many existing and designed structures according to different structural types and chemical compositions.Seven novel structures are predicted for the first time to exhibit potential DUV NLO capabilities.All the results enable us to believe that the computer-aided modeling blueprint will play an important role in the exploration of new DUV NLO crystals.

Thermal and Transmission Properties of UV Nonlinear Optical Material——ZnCd(SCN)_4 Crystal

zinc cadmium thiocyanate (ZCTC), ZnCd(SCN)_4, has been discoveredas a UV second-order nonlinear optical coordination crystal. Titsthermal and transmission Properties are reported. The thermaldecomposition is characterized by using the X-ray Powder diffraction(XRPD) and infrared (IR) spectroscopy at room temperature. TheAbsorptions of intrinsic ions and ZCTC in a solution state arediscussed as well as Transmission properties of the ZCTC crystal. Aneffective method of reducing the surface Reflection loss of ZCTCcrystal is introduced.

Ultraviolet Nonlinear Optical Crystals inπ-Conjugated System

UV nonlinear optical(NLO)crystals are essential materials for UV solid state laser output.To date,frequency conversion in UV region is mainly dependent on borates with planar BO3 or B3O6 units.Since the practical applications require more and more high comprehensive properties of crystals,it is urgent to develop new UV NLO crystals.However,it is more and more difficult to find new borate NLO crystals because borate NLO crystals have been studied for several decades.Therefore,it is important to search new systems for the exploration of UV NLO crystals.Based on the relationship between the microstructure and properties of the groups,we proposed that inorganic(CO3)2-and(NO3)-groups can be as new NLO active units for UV NLO crystals because they haveπ-conjugated configuration.Accordingly,our group have performed related work in carbonate and nitrate systems in recent years,which resulted in finding some excellent carbonates and nitrates NLO crystals.In addition,we have recently expanded the research field from inorganic to organicπ-conjugated systems,such as isocyanurates.This mini review will introduce the research results of our team in the field of UV NLO crystals including carbonates,nitrates and cyanurates in recent years.

Properties of second harmonic generation in nonlinear optical crystals CsLiB_6O_(10) and K_2Al_2B_2O_7

The phase-matching for nonlinear optical crystal, the nonlinear phase matching angle, effective nonlinear coefficient, walk-off angles, permitted angle, and permitted wavelength are obtained in type-I and type-II phase matching in ultraviolet （UV） nonlinear optical crystals CsLiB6O10 （CLBO） and K2Al2B2O7 （KABO） by detailed theoretical simulation. Through analysis and comparison, the phase matching characteristics of the second harmonic generation in the crystals are discussed when the wavelengths of the basic frequency lights turn continually.

Research progress on mid-IR nonlinear optical crystals with high laser damage threshold in China

Nonlinear optical(NLO)crystals have been playing an increasingly important role in laser science and technology.The NLO crystals used in the middle infrared(mid-IR)region,compared with the NLO crystals in the other wavelength regions,are still not good enough for the application of high-energy laser.The main defect is that their laser damage thresholds(LDT)are low.Chinese scientists have made a lot of important contributions to the UV and visible NLO crystals.In the last decade,they also did a lot of work on the mid-IR NLO materials.The main purpose of these researches is to increase the LDT and simultaneously balance the other properties.This paper presents a brief summary of their research progress in this topic on three types of materials:chalcogenides,oxides,and halides.The emphasis is put on the design strategy and quality control of the crystals.

Influence of Metallic Substitutions on the Optical and Mechanical Properties of NLO Benzoyl Glycine Crystals

Benzoyl glycine （BG） is a promising organic nonlinear optical （NLO） crystal, whose second harmonic generation （SHG） efficiency is much higher than that of KDP （potassium dihydrogen phosphate）. Single crystals of pure, Cu2＋ and Cd2＋ doped BG were grown by slow evaporation technique. Optically transparent and defect free single crystals of size up to 10 mm×15 mm×10 mm were harvested in a period of 40-60 days. The growth conditions of pure and doped crystals of BG were optimized and the grown crystals were confirmed by single crystal XRD （X-ray diffraction）. The grown crystals were characterized by FTIR （Fourier transform infrared spectroscopy）, optical absorption and microhardness studies. The microhardness studies confirm that BG has a moderate VHN （Vickers hardness number） value in comparison to the.other organic NLO crystals. The efficiency of frequency doubling was measured for the using Nd：YAG laser and the results were discussed.

High-Energy Tunable 6.5-12 μm Picosecond Mid-Infrared Radiation Generated from Optical Parametric Amplifier Based on LiInSe_(2) Crystal

We report high-energy tunable 6.5-12 μm ps mid-infrared radiation generation based on OPA pumped using 1064 nm laser in LISe crystal.We simulated the relationship between the idler energy and crystal length.An optimum LISe length of 4 mm was used to enhance the idler energy experimentally.At a pump energy of ~9.4 mJ, energy levels of ~146 and of ~27 μJ are generated at 6.5 μm and 12 μm, respectively.The highest energy of ~205 μJ is achieved at 8.1 μm at a pump energy of ~19 mJ.Finally, the angular and spectral width acceptance are measured.

Ba(SO_(3)CH_(3))-(2):A Deep-Ultraviolet Transparent Crystal with Excellent Optical Nonlinearity Based on a New Polar Non-π-Conjugated NLO Building Unit SO_(3)CH_(3)^(−)

In this study,the first methyl sulfonate deepultraviolet(DUV)nonlinear optical(NLO)crystal,Ba(SO_(3)CH_(3))_(2),was successfully synthesized with the polar non-π-conjugated tetrahedron,SO_(3)CH_(3)^(−),as a novel DUV NLO building unit.Results showed that Ba(SO_(3)CH_(3))_(2)not only had a very short absorption edge of 159 nm,which is the shortest among reported phase-matchable sulfates or sulfonates,but also exhibited excellent optical properties.(Powder X-ray diffractionwas ca.1.5×KH_(2)PO_(4)and birefringence was 0.04 at 589.3 nm.)It also exhibited high thermal stability and remarkable stability against air and moisture.Additionally,bulk Ba(SO_(3)CH_(3))_(2)crystal could be obtained conveniently from a simple solution evaporation process.Therefore,Ba(SO_(3)CH_(3))_(2)should have great potential as a DUV NLO crystal in the near future.

Recent Developments in Functional Crystals in China

Functional crystals are the basic materials for the development of modern science and technology and are playing key roles in the modern information era. In this paper, we review functional crystals in China, including research history, significant achievements, and important applications by highlighting the most recent progress in research. Challenges for the development of functional materials are discussed and possible directions for development are proposed by focusing on potential strengths of these materials.

Generation of femtosecond laser pulses at 263 nm by K_3B_6O_(10)Cl crystal

The third harmonic generation（THG） of a linear cavity Ti：sapphire regenerative amplifier by use of a K3B6O（10）Cl（KBOC） crystal is studied for the first time. Output power up to 5.9 mW is obtained at a central wavelength of 263 nm,corresponding to a conversion efficiency of 4.5% to the second harmonic power. Our results show a tremendous potential for nonlinear frequency conversion into the deep ultraviolet range with the new crystal and the output laser power can be further improved.

Generation of femtosecond laser pulses at 396 nm in K_3B_6O_(10)Cl crystal

K3B6O10Cl （KBOC）, a new nonlinear optical crystal, shows potential advantages for the generation of deep ultraviolet （UV） light compared with other borate crystals. In this paper we study for the first time the second harmonic generation （SHG） of a femtosecond Ti：sapphire amplifier with this crystal. Laser power is obtained to be as high as 220 mW at the central wavelength of 396 nm with a 1-mm-long crystal, and the maximum SHG conversion efficiency reaches 39.3%. The typical pulse duration is 83 fs, The results show that second harmonic （SH） conversion efficiency has the room to be further improved and that the new nonlinear crystal is very suited to generate the high efficiency deep ultraviolet laser radiation below 266 nm.

β-BaB_(2)O_(4) with special cut-angle applied to single crystal cascaded third-harmonic generation

High-efficiency single crystal cascaded third-harmonic generation(THG)was realized inβ-BaB_(2)O_(4)(BBO)material with special cut-angle.By analyzing effective nonlinear optical coefficient(d_(eff))of the cascaded THG process,which was composed by type-II frequency doubling and type-I sum-frequency,the optimum phase matching(PM)direction in BBO crystal was determined to be(θ=32.1°,φ=11°).With an optimized 9-mm long sample which was processed along this direction,the highest cascaded THG conversion efficiency reached 42.3%,which is much superior to the similar components reported previously,including ADP,KDP,and Gd_(x)Y_(1-x)COB crystals.

Raman Spectra and Crystallographic Properties of a New NLO Material,ZnCd(SCN)_4 Crystal

The crystallographic properties and R aman spectra of the title compound ZnCd(SCN) 4, which is a new nonlinear optica l crystal(NLO), are reported for the first time. This crystal is orthorhombic and its space group is I - 4 with unit cell parameters a =1.113 5(0.2) nm, c =0.437 60(1) nm. There are two formulas per unit cell. Raman spectra of zinc cadmium thiocyanatec (ZCTC) are given and the electron activities in the crystal are shown.

Fluorooxoborates:A precious treasure of deep-ultraviolet nonlinear optical materials

As the key components of all-solid-state deep-ultraviolet(DUV,λ<200 nm)laser sources,exploring DUV nonlinear optical(NLO)materials has been a research hotspot for a long time.However,as the only material that has been practically used to generate DUV coherent light through the direct second harmonic generation(SHG)process,KBe_(2)BO_(3)F_(2)(KBBF)still meets bottlenecks,namely,severe layered crystal growth tendency,for extensive application.In the search for the next generation of DUV NLO materials,fluorooxoborates are highly expected due to their excellent NLO performances,flexible structures,and rich structural chemistry.So far,a large number of materials with prominent properties have emerged in the fluorooxoborate system.By investigating the differences in structures and properties among fluorooxoborates and borates and borate fluorides,the excellent NLO per-formances of fluorooxoborates are attributed to functionalized B-O/F chromophores.In this review,by analyzing the published fluorooxoborates,the fluorooxoborate system is a precious treasure for exploring DUV NLO ma-terials.The synthesis,structures,and properties of some representative fluorooxoborates in the research history are introduced and summarized.Finally,we put forward the opportunities and challenges of future research in fluorooxoborate DUV NLO crystals.

掺锶的偏硼酸钡(Sr_xBa_(1-x)B_2O_4)大块单晶的生长和表征

Barium metaborate (BaB 2O 4) exists in two forms the high temperature for m α phase and the low temperature form β phase,with the phase transition poi nt at around 925℃.The low temperature phase (β BBO) is an excellent NLO cryst al for UV region,while the high temperature one (α BBO) is known as a good bir efringent material.α BBO crystal possesses better transparency in the ultravio let region compared with commonly used YVO 4 and CaCO 3 crystals.However,due t o phase transition problem,it is difficult to grow single α BBO crystals by D CZ method,which restricts its wider application.α BBO crystal usually cracks upon cooling resulted from phase transition to β phase.Therefore,it is difficult to grow β BBO single crystals directly from pure BaB 2O 4 mel t;however,to grow single crystals of α BBO is not easy,either. Our recent experiments showed that one could avoid cracking of α BBO cryst als by Sr 2+ doping.This minute amount of Sr 2+ plays the role of structure stabilizer,which inhibits structural reconstruction. In this way,Sr 2+ d op ed BBO single crystals do not subject to phase transition from 925℃ down to roo m temperature. We have mow successfully grown out α BBO single crystals 30mm in diameter by D CZ method from Sr x Ba 1- x BO 4 melt with Sr concentration 0.3 0 .5%.The ratation rate is 10 15r/min,pulling speed is 1 2mm/h.Preliminary tests revealed that its structure and physic chemical properties were almost identic al to those grown from pure melts.These Sr 2+ doped α BBO crystals are no w being widely used in optical isolators.

功能晶体材料CMTD生长动力学和结晶习性的研究

Process of crystal growth can be controlled by both surface kinetics and by volume transport as well.Although the complicated relation between the surface kinetics and volume transport exsits,generally,they are studied seprately.Due to the mathematical complexity of heat and mass transport equations,the in depth studies of heat and mass transport process become difficult.Most of the studies on the transport were performed for the growth from melt.Most of the work on Surface kinetics has been done for crystal growth from aqueous solution because the in situ observation of crystal growth is easily carried out.In recent years,the surface kinetics studies on the nanometer scale,even atomic scale,are demonstrated by using AFM.