Pb2BO3I: A Borate Iodide with the Largest Second‐Harmonic Generation (SHG) Response in the KBe2BO3F2 (KBBF) Family of Nonlinear Optical (NLO) Materials

Yu, Hongwei; Koocher, Nathan Z.; Rondinelli, James M.; Halasyamani, P. Shiv

doi:10.1002/anie.201802079

Cited by 195 publications

(53 citation statements)

References 47 publications

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“…The IR spectra of three compounds have been measured and shown in Figure S6. The strong vibrations at 1239–1248 cm −1 and 687–748 cm −1 can be assigned to stretching and bending vibrations of BO 3 groups, respectively, indicating the existence of isolated BO 3 triangles in the structures . Further, their UV‐vis‐NIR diffusion spectra were also measured, which indicates all these compounds have the deep‐UV transmission with the UV cut‐off edges lower than 190 nm (Figure S7).…”

Section: Figurementioning

confidence: 92%

CsZn₂BO₃X₂ (X₂=F₂, Cl₂, and FCl): A Series of Beryllium‐Free Deep‐Ultraviolet Nonlinear‐Optical Crystals with Excellent Properties

et al. 2020

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Designing deep-ultraviolet (DUV) nonlinear-optical (NLO) crystals is one of the major current research interests, but it faces a great challenge. In order to overcome the problem of crystal growth and the toxicity of BeO raw materials in KBe 2 BO 3 F 2 (KBBF), the only applicable DUV NLO crystal so far, we substitute Be 2+ cations with Zn 2+ in the KBBF structure and modify the halogen anions, by which three new Zncontaining KBBF-like compounds, CsZn 2 BO 3 X 2 (X 2 = F 2 , Cl 2 , and FCl), have been successfully synthesized. They all exhibit excellent NLO properties, including improved SHG responses (2.8-3.5 KDP) and short UV cutoff edges (< 190 nm). In comparison with KBBF, CsZn 2 BO 3 X 2 (X 2 = F 2 , Cl 2 , and FCl) are all chemically benign and have better growth habits, so they are all promising as DUV NLO crystals. Further study on structure-property relationships indicates that the mixing of halogen anions is a feasible strategy to enhance the SHG responses of the KBBF family.

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Section: Figurementioning

confidence: 92%

CsZn₂BO₃X₂ (X₂=F₂, Cl₂, and FCl): A Series of Beryllium‐Free Deep‐Ultraviolet Nonlinear‐Optical Crystals with Excellent Properties

et al. 2020

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“…Perhaps the most cited examples are -BaB 2 O 4 (Chen et al, 1985) and -BiB 3 O 6 (Hellwig et al, 1999). The subsequent discovery of outstanding activity (an order of magnitude above KDP) in Pb 2 B 5 O 9 I (Huang et al, 2010) and Pb 2 BO 3 I (Yu et al, 2018) has resulted in borate iodides attracting increasing interest. Their crystal chemistry remains mostly unexplored, not in the least due to synthetic difficulties, with many iodides being volatile and prone to hydrolysis and/or oxidation at elevated temperatures in air.…”

Section: Introductionmentioning

confidence: 99%

The first bismuth borate oxyiodide, Bi₄BO₇I: commensurate or incommensurate?

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et al. 2020

Acta Crystallogr Sect B

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The first bismuth borate oxyiodide, Bi4BO7I, has been prepared by solid-state reaction in evacuated silica ampoules. Its crystal structure [space group Immm(00γ)000] comprises litharge-related layers of edge-sharing OBi4 tetrahedra; the interlayer space is filled by I− and [BO3]3− anions. The wavevector, q = 0.242 (3)c*, is very close to the rational value of c*/4, yet refinement based on commensurate modulation faces serious problems indicating the incommensurate nature of the modulation. The I-/[BO3]3− anions are ordered in a complex sequence along [001], i.e. –<–BO3–BO3–I–I–> n = 28–I–I–I–<–BO3–BO3–I–I–> n = 28–BO3–BO3–BO3–, leading to a structural modulation. The principal feature of the latter is the presence of –I–I–I– and –BO3–BO3–BO3– sequences that cannot be accounted for in the a × b × 4c supercell. The thermal expansion of Bi4BO7I is weakly anisotropic (αa = 8, αb = 15 and αc = 17 × 10−6 K−1 at 500 K) which is caused by preferential orientation of the borate groups.

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“…Structurally, the perfectly coplanar [BO 3 ] 3− anionic groups in the 2 ∞ [Be 2 BO 3 F 2 ] layers of KBBF provide a relatively large SHG coefficient ( d 11 = 0.47 pm/V) and a moderate birefringence (Δ n = 0.07 @1064 nm), which endow KBBF with unprecedented performances [88,89]. The excellence for the KBBF family crystals used as the DUV NLO crystals inspirits researchers to explore beryllium-free borates with benign KBBF-type layered structures [90,91,92,93].…”

Section: Structural Chemistry Of Zincoboratesmentioning

confidence: 99%

Research and Development of Zincoborates: Crystal Growth, Structural Chemistry and Physicochemical Properties

et al. 2019

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Borates have been regarded as a rich source of functional materials due to their diverse structures and wide applications. Therein, zincobrates have aroused intensive interest owing to the effective structural and functional regulation effects of the strong-bonded zinc cations. In recent decades, numerous zincoborates with special crystal structures were obtained, such as Cs3Zn6B9O21 and AZn2BO3X2 (A = Na, K, Rb, NH4; X = Cl, Br) series with KBe2BO3F2-type layered structures were designed via substituting Be with Zn atoms, providing a feasible strategy to design promising non-linear optical materials; KZnB3O6 and Ba4Na2Zn4(B3O6)2(B12O24) with novel edge-sharing [BO4]5− tetrahedra were obtained under atmospheric pressure conditions, indicating that extreme conditions such as high pressure are not essential to obtain edge-sharing [BO4]5−-containing borates; Ba4K2Zn5(B3O6)3(B9O19) and Ba2KZn3(B3O6)(B6O13) comprise two kinds of isolated polyborate anionic groups in one borate structure, which is rarely found in borates. Besides, many zincoborates emerged with particular physicochemical properties; for instance, Bi2ZnOB2O6 and BaZnBO3F are promising non-linear optical (NLO) materials; Zn4B6O13 and KZnB3O6 possess anomalous thermal expansion properties, etc. In this review, the synthesis, crystal structure features and properties of representative zincoborates are summarized, which could provide significant guidance for the exploration and design of new zincoborates with special structures and excellent performance.

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Pb₂BO₃I: A Borate Iodide with the Largest Second‐Harmonic Generation (SHG) Response in the KBe₂BO₃F₂ (KBBF) Family of Nonlinear Optical (NLO) Materials

Cited by 195 publications

References 47 publications

CsZn₂BO₃X₂ (X₂=F₂, Cl₂, and FCl): A Series of Beryllium‐Free Deep‐Ultraviolet Nonlinear‐Optical Crystals with Excellent Properties

CsZn₂BO₃X₂ (X₂=F₂, Cl₂, and FCl): A Series of Beryllium‐Free Deep‐Ultraviolet Nonlinear‐Optical Crystals with Excellent Properties

The first bismuth borate oxyiodide, Bi₄BO₇I: commensurate or incommensurate?

Research and Development of Zincoborates: Crystal Growth, Structural Chemistry and Physicochemical Properties

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Pb2BO3I: A Borate Iodide with the Largest Second‐Harmonic Generation (SHG) Response in the KBe2BO3F2 (KBBF) Family of Nonlinear Optical (NLO) Materials

Cited by 195 publications

References 47 publications

CsZn2BO3X2 (X2=F2, Cl2, and FCl): A Series of Beryllium‐Free Deep‐Ultraviolet Nonlinear‐Optical Crystals with Excellent Properties

CsZn2BO3X2 (X2=F2, Cl2, and FCl): A Series of Beryllium‐Free Deep‐Ultraviolet Nonlinear‐Optical Crystals with Excellent Properties

The first bismuth borate oxyiodide, Bi4BO7I: commensurate or incommensurate?

Research and Development of Zincoborates: Crystal Growth, Structural Chemistry and Physicochemical Properties

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Pb₂BO₃I: A Borate Iodide with the Largest Second‐Harmonic Generation (SHG) Response in the KBe₂BO₃F₂ (KBBF) Family of Nonlinear Optical (NLO) Materials

CsZn₂BO₃X₂ (X₂=F₂, Cl₂, and FCl): A Series of Beryllium‐Free Deep‐Ultraviolet Nonlinear‐Optical Crystals with Excellent Properties

CsZn₂BO₃X₂ (X₂=F₂, Cl₂, and FCl): A Series of Beryllium‐Free Deep‐Ultraviolet Nonlinear‐Optical Crystals with Excellent Properties

The first bismuth borate oxyiodide, Bi₄BO₇I: commensurate or incommensurate?