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Wen-Dan Cheng, Chen-Sheng Lin, Wei-Long Uhang, Hao Zhang: Structural Designs and Property Characterizations for Second-Harmonic Generation Materials.- Fang Kong, Chuan-Fu Sun, Bing-Ping Yang, Jiang-Gao Mao: Second-order Non-linear Optical Materials based on Metal Iodates, Selenites and Tellurites.- Guo-Fu Wang: Structure, growth, nonlinear optics and laser properties of RX3(BO3)4 (R=Y, Gd, La; X=Al, Sc).-

Chaoyang Tu, Zhaojie Zhu, Zhenyu You, Jianfu Li, Yan Wang, Alain Brenier: The Recent Development of Borate SF-conversion Laser Crystal.- Ning Ye: Structure design and crystal growth of UV nonlinear borate materials.- Yi-Zhi Huang, Li-Ming Wu, Mao-Chun Hong: Cation Effect in Doped BBO and Halogen Anion Effect in Pb2B5O9X (X– = I–, Br–, Cl–).



Structural Designs and Property Characterizations for Second-Harmonic Generation Materials

Second-harmonic generation (SHG) materials only exist in solids that have no inversion center space groups, and they are constructed by the building blocks or chromophores of noncentrosymmetricity (NCS). In this chapter, we employed one or multiple chromophores that result from the coordination structure distortions of a d0 cation, polar displacement of d10 cation center, a stereochemically active lone pair (SCALP) of cations, and asymmetrical delocalization π-charge systems, as building blocks to obtain some new compounds with NCS space group. The single-crystal structures were characterized, and physical properties, in particular SHG responses, were measured for these compounds. The electronic structures and density of states were calculated by DFT method, and the SHG properties are simulated to gain an insight into the relations between structure and NLO properties for the materials. The electronic origination of large SHG responses was assigned in terms of the calculated results.
Wen-Dan Cheng, Chen-Sheng Lin, Wei-Long Zhang, Hao Zhang

Second-Order Nonlinear Optical Materials Based on Metal Iodates, Selenites, and Tellurites

In this chapter, the syntheses, structures, and Second Harmonic Generation (SHG) properties of metal iodates, selenites, and tellurites all of which contain a lone pair cation in an asymmetric coordination geometry were reviewed. A second asymmetric building unit such as distorted octahedra of the d0 transition-metal (TM) cations such as V5+, Mo6+, other cations with a stereochemically active lone pair such as Pb2+ and Bi3+, and tetrahedral groups such as BO 4 5− and PO 4 3− , can be introduced into metal iodates, selenites, and tellurites. The combination of d0 transition-metal cations with the iodate groups afforded a large number of new metal iodates, a number of which display excellent SHG properties due to the additive effects of polarizations from both types of the asymmetric units. Introducing other lone-pair cations such as Pb2+ and Bi3+ into the metal iodates is also an effective strategy to design new SHG materials. With respect to the metal selenite or tellurite systems, many compounds in the alkali or alkaline earth-d0 TM–Se(IV)/Te(IV)–O systems can also exhibit excellent SHG properties due to the additive effects of polarizations from both types of asymmetric units. Lanthanide or posttransition metal main group element-d0 TM–Se(IV)/Te(IV)–O compounds are usually structurally centrosymmetric and not SHG active, but they can also display abundant structural diversities and interesting magnetic or luminescent properties. Metal tellurites and selenites containing tetrahedral groups of the main group elements such as BO4 and PO4 may also form NCS structures with excellent SHG properties.
Fang Kong, Chuan-Fu Sun, Bing-Ping Yang, Jiang-Gao Mao

Structure, Growth, Nonlinear Optics, and Laser Properties of RX3(BO3)4 (R = Y, Gd, La; X = Al, Sc)

As well known, the borate crystals are an important laser host material and nonlinear optical crystal. After an examination on the crystal structure and growth technology of RX3(BO3)4 (R = Y, Gd, La; X = Al, Sc), this chapter reviews research progress of Nd3+-, Cr3+- and Ti3+-doped RX3(BO3)4 (R = Y, Gd, La; X = Al, Sc) including the nonlinear optical crystal materials.
Guo-Fu Wang

The Recent Development of Borate SF-Conversion Laser Crystal

As a laser host, Borates possess favorable chemical and physical characteristics as well as higher damnification threshold. Especially, Borates usually have higher nonlinear optical efficiency resulted from its B–O structure. When doped with active ions, Borates can serve as a self-frequency conversion multifunction laser medium. For example, rare-earth ions and Cr3+-doped RX3(BO3)4, especially GdAl3(BO3)4 and TmAl3(BO3)4, are typical self-frequency conversion multifunction laser crystals. After wide surveys of known research on the growth, crystal structure, and properties including thermal, optical, and spectral characteristics and laser property, this chapter reviews the recent advances in the development of these crystals. Self-frequency conversion laser technology including the self-frequency doubling, self-difference-frequency mixing and self-sum-frequency mixing methods were dealt with. As a result, the laser outputs with high efficiency at various wavelengths ranged from UV to IR have been achieved.
Chaoyang Tu, Zhaojie Zhu, Zhenyu You, Jianfu Li, Yan Wang, Alain Brenier

Structure Design and Crystal Growth of UV Nonlinear Borate Materials

Crystal design and growth of huntite-type and alkaline beryllium borates used for UV and deep-UV frequency conversion are summarized. A series borates crystallizing in the trigonal-huntite structure, ReM3(BO3)4 (Re = La, Ga, Y, Lu; M = Y, Lu, Sc, Ga, Al), has been discovered through structural design with respect to the size tuning on trigonal prism or/and octahedral site in the structure. The structural, optical, and chemical–physical properties are detailed. They all have large NLO coefficients, moderate birefringence for UV phase matching, and robust chemical and physical properties. The NLO coefficients of those containing Bi are larger due to the contribution from the lone-pair electron of Bi, while the UV cutoff of these crystals is redshift for about 100 nm. The systematical synthesis of a series of new alkaline beryllium borates with the stoichiometry NaBeB3O6, ABe2B3O7 (A = K, Rb), and Na2CsBe6B5O15 in order to obtain deep-UV NLO crystals containing new beryllium borate anionic groups or framework was presented. A new beryllium borate anionic group [Be2B3O11]9− was found in the structure of NaBeB3O6 and α-KBe2B3O7. β-KBe2B3O7, γ-KBe2B3O7, RbBe2B3O7, and Na2CsBe6B5O15 consist of 2D alveolate beryllium borate network [Be2BO5]. Furthermore, the adjacent [Be2BO5] layers in these compounds were connected by covalent bonds.
Ning Ye

Cation Effect in Doped BBO and Halogen Anion Effect in Pb2B5O9X (X− = I−, Br−, Cl−)

This chapter is intended to be a small research progress report on borate nonlinear optical (NLO) materials focusing on the cation and anion effects in two selected systems. The cation-doped BBO, Ba1−x B2−yz O4-Si x Al y Ga z (x = 0–0.15, y = 0–0.1, z = 0–0.04), has improved NLO-related performance relative to the undoped one, and the origins of the second harmonic generation (SHG) improvement on the basis of the whole electron structures are discussed. And halide borates, Pb2B5O9X (X = I , Br , Cl ), are presented to emphasize the discrepancy in optical properties, crystallographic and electronic structures, and origin of SHG response. Importantly, the cation and anion effects are both crucial to improve the SHG performance and to design NLO materials.
Yi-Zhi Huang, Li-Ming Wu, Mao-Chun Hong


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