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.

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.

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.

Optical and defect properties of S-doped and Al-doped GaSe crystals

S-doped and Al-doped GaSe crystals are promising materials for their applications in nonlinear frequency conversion devices. The optical and defect properties of pure, S-doped, and Al-doped GaSe crystals were studied by using photoluminescence（PL） and Fourier transform infrared spectroscopy（FT-IR）. The micro-topography of（0001） face of these samples was observed by using scanning electron microscope（SEM） to investigate the influence of the doped defects on the intralayer and interlayer chemical bondings. The doped S or Al atoms form the SSe^0 or AlGa^＋1） substitutional defects in the layer GaSe structure, and the positive center of AlGa-^＋1 could induce defect complexes. The incorporations of S and Al atoms can change the optical and mechanical properties of the GaSe crystal by influencing the chemical bonding of the layer structure. The study results may provide guidance for the crystal growth and further applications of S-doped and Al-doped GaSe 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.

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.

Research progress of cholesteric liquid crystals with broadband reflection characteristics in application of intelligent optical modulation materials

Cholesteric liquid crystals（CLCs） have recently sparked an enormous amount of interest in the development of soft matter materials due to their unique ability to self-organize into a helical supra-molecular architecture and their excellent selective reflection of light based on the Bragg relationship.Nowadays,by the virtue of building the self-organized nanostructures with pitch gradient or non-uniform pitch distribution,extensive work has already been performed to obtain CLC films with a broad reflection band.Based on authors＇ many years＇ research experience,this critical review systematically summarizes the physical and optical background of the CLCs with broadband reflection characteristics,methods to obtain broadband reflection of CLCs,as well as the application in the field of intelligent optical modulation materials.Combined with the research status and the advantages in the field,the important basic and applied scientific problems in the research direction are also introduced.

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.

Tunable Optical Filters Based on Different Configurations with Cholesteric Liquid Crystals

Optical filters with different configurations based on cholesteric liquid crystals （CLCs） are designed. The central wavelength from CLCs can be tuned by the electric field or temperature. For the electric field tuning, the ITO is designed with circular patterns, which can make the tunable range 18 nm. For the temperature tuning, two-layer- CLC configurations are used. The experimental results indicate that a deepened or broadened bandgap from the CLC can be achieved by different handedness or concentrations of chiral dopants. The spectrum study is carried out.

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.

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.

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.

Determining the imaging plane of a retinal capillary layer in adaptive optical imaging

Even in the early stage,endocrine metabolism disease may lead to micro aneurysms in retinal capillaries whose diameters are less than 10 μm.However,the fundus cameras used in clinic diagnosis can only obtain images of vessels larger than 20 μm in diameter.The human retina is a thin and multiple layer tissue,and the layer of capillaries less than10 μm in diameter only exists in the inner nuclear layer.The layer thickness of capillaries less than 10 μm in diameter is about 40 μm and the distance range to rod＆cone cell surface is tens of micrometers,which varies from person to person.Therefore,determining reasonable capillary layer（CL） position in different human eyes is very difficult.In this paper,we propose a method to determine the position of retinal CL based on the rod＆cone cell layer.The public positions of CL are recognized with 15 subjects from 40 to 59 years old,and the imaging planes of CL are calculated by the effective focal length of the human eye.High resolution retinal capillary imaging results obtained from 17 subjects with a liquid crystal adaptive optics system（LCAOS） validate our method.All of the subjects＇ CLs have public positions from 127 μm to 147 μm from the rod＆cone cell layer,which is influenced by the depth of focus.

Synthesis,Crystal Structure,and Optical Property of Zero-dimensional Quaternary Thioborate：Ba9B3GaS15

A new zero-dimensional（0D） thioborate Ba_9B_3GaS_（15） has been discovered by conventional high-temperature solid-state reaction. The compound crystallizes in orthorhombic space group Pbca with a = 8.4759（8）,b = 22.266（2）,c = 31.426（3） ？,V = 5931（2） ？~3,Z = 8,Mr = 1819.11,Dc = 4.075 g/cm3,μ = 13.684 mm^（-1）,F（000） = 6320,S = 1.034,（Δρ）max = 5.039,（Δρ）min = –5.409 e/？~3,the final R = 0.0362 and w R = 0.1053 for 19243 observed reflections with I 〉 2σ（I）. The structure is constructed by discrete [BS_3]^（3–） trigonal planes and isolated [GaS_4]^（5–） tetrahedra with Ba^（2＋） and isolated S^（2–） filled among them. The UV-Vis-near-IR spectrum reveals a wide band gap of 3.15 eV that agrees with the electronic structure calculation.

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.

Helioal Structure and Optical Activity of Two New Derivatives of R(+)-1,1'-Binaphthyl-2,2'-diol

Correlation between the belieal structure and optical activity of two derivatives of R(+)- 1, 1'-binaphthyl-2,2'-diol was derived from a study of their optical rotations, CD curves and Xray crystal structures.

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.

Ferroelectric Liquid Crystal Optical Switches

The dynamic response of molecular orientation, and the temperature and pulse shape dependences of the switching behavior in ferroelectric liquid crystal are described. The switching speed and the surface energy of ferroelectric liquid crystal are given.

Physical and Chemical Properties of GdN: A Critical Comparison between Single Crystals and Thin Films, Theory and Experiment

Since about 10 years, there is a controversy about physics and chemistry of GdN between stoichiometric (tested) large single crystals and off-stoichiometric thin films. GdN single crystals are anti-ferromagnetic for applied magnetic fields of only 10 Oe, become ferromagnetic for excess electrons and larger magnetic fields. They are semimetallic. Thin films are ferromagnetic and semiconductors. Over the time, many experiments have been performed on both systems and the physics in each system is consistent. Band structure computations either yield ferromagnetic semimetals or ferromagnetic semiconducting thin films. There seems to be two incompatible worlds, those of single crystals and those of thin films. In the present work, the author compares directly the various measurements and calculations and gives reasons for their different results.