The Role of Polar, Lamdba (Λ)-Shaped Building Units in Noncentrosymmetric Inorganic Structures

Donakowski, Martin D.; Gautier, Romain; Yeon, Jeongho; Moore, Donald T.; Nino, Juan C.; Halasyamani, P. Shiv; Poeppelmeier, Kenneth R.

doi:10.1021/ja210984k

Cited by 126 publications

(119 citation statements)

References 68 publications

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“…, Ta 5+ , and Mo 6+ ), [12][13][14] anionic groups with stereochemically active lone pairs (e.g., [IO 3 ] À and [TeO x ] nÀ ), [15,16] [17] which combine with diverse other functional building units to produce materials with large NLO coefficients, for example, Cd 4 BiO-(BO 3 ) 3 (6 KDP), [18] Pb 2 B 5 O 9 I (13.5 KDP), [19] and Ba 23 Ga 8 Sb 2 S 38 (22 AgGaS 2 ). [20] However, the structural units produce an unwanted effect-the UV absorption edge shifts toward the red region, making them less suitable for the deep-UV applications.…”

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confidence: 99%

Cs₂B₄SiO₉: A Deep‐Ultraviolet Nonlinear Optical Crystal

et al. 2013

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The generation of deep-ultraviolet (UV) coherent light from nonlinear optical (NLO) materials [1][2][3][4] as one of the most promising resource, has become a topic of intensive study because of its important applications in a broad range of fields, such as semiconductor photolithography, laser micromachining, photochemical synthesis, and material processing. They are able to shorten the wavelength of light by a factor of two (or doubling the frequency), based on the process of second-harmonic generation (SHG), which occurs only when a centrosymmetric symmetry operation is absent in a crystal. However, for a noncentrosymmetric (NCS) crystal to be used as a nonlinear optical material the essential crystal property requirements are that the crystals possess a large NLO response, wide transparent window, suitable birefringence for phase-matching, good mechanical strength, and chemical stability. [4,5] After continuous efforts over several decades, many NCS compounds were obtained by incorporating functional borate structure units, such as B 3 O 6 and B 3 O 7 . b-BaB 2 O 4 (BBO) [6] and LiB 3 O 5 (LBO) [7] are the most advanced NLO materials, which have widely been used as optoelectronic devices. However, to date, KBe 2 BO 3 F 2 (KBBF) [8,9] is the only material that can generate coherent light wavelengths below 200 nm by direct SHG, which makes KBBF a research hotspot. Unfortunately, the KBBF crystal is very difficult to grow in thickness owing to the growth habit of the layer, which severely limits the coherent light output power. Thus, finding the optimal composition that is facile to synthesize, yields large single crystals, and simultaneously satisfies the NLO requirements has attracted considerable attention. [10,11] The presence of large NLO coefficients in a structure is usually in contradiction with wide band gaps in one compound. For instance, the structural units in the known compounds are second-order Jahn-Teller (SOJT) polar dis- [17] which combine with diverse other functional building units to produce materials with large NLO coefficients, for example, Cd 4 BiO-(BO 3 ) 3 (6 KDP), [18] Pb 2 B 5 O 9 I (13.5 KDP), [19] and Ba 23 Ga 8 Sb 2 S 38 (22 AgGaS 2 ).[20] However, the structural units produce an unwanted effect-the UV absorption edge shifts toward the red region, making them less suitable for the deep-UV applications. It is necessary to create the subtle balance of above-mentioned conflicting factors so as to search for the new deep-UV NLO crystals with excellent comprehensive performances.To circumvent the wide absorption window requirement, basic structural units having excitation energies near the UV region are necessary. Such units are BO 3 , BO 4 , SiO 4 , and PO 4 . [6,7,21] A compound Rb 2 Be 2 Si 2 O 7 [22] was ever expected to be a substitution for KBBF owing to its similar structure characteristics with KBBF and without the layer habit. But, the weak SHG response of Rb 2 Be 2 Si 2 O 7 makes the substitution end in naught. However, the borosilicate may be a potential candidate for a deep-...

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Cs₂B₄SiO₉: A Deep‐Ultraviolet Nonlinear Optical Crystal

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“…However, one must be able to predict the packing of these BBUs into the 3D acentric structure. Two packings are usually described in the literature: (i) the packing of chiral units of one-handedness into chiral materials and (ii) the alignment of polar units into polar materials [1][2][3][4][5][6][7][8]. As a next step towards the engineering of NCS, it is important to explore the general concepts which drive the BBUs to pack in one of these structural arrangements.…”

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Packing of Helices: Is Chirality the Highest Crystallographic Symmetry?

Gautier

Poeppelmeier

2016

Crystals

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Chiral structures resulting from the packing of helices are common in biological and synthetic materials. Herein, we analyze the noncentrosymmetry (NCS) in such systems using crystallographic considerations. A comparison of the chiral structures built from helices shows that the chirality can be expected for specific building units such as 3 1 /3 2 or 6 1 /6 5 helices which, in hexagonal arrangement, will more likely lead to a chiral resolution. In these two systems, we show that the highest crystallographic symmetry (i.e., the symmetry which can describe the crystal structure from the smallest assymetric unit) is chiral. As an illustration, we present the synthesis of two materials ([Zn(2,2'-bpy) 3 ](NbF 6 ) 2 and [Zn(2,2'-bpy) 3 ](TaF 6 ) 2 ) in which the 3 n helices pack into a chiral structure.

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“…[2] Therefore, it is necessary for the material science community to develop new strategies to create these materials.Recently, exotic ABO 3 -type perovskites with unusually small A-site cations have attracted much attention owing to the formation of LiNbO 3 (LN)-type polar structure at high pressure (HP; Supporting Information, Section S1). Their symmetry-dependent properties, such as ferroelectricity/multiferroics, piezoelectricity, pyroelectricity, and second-order harmonic generation (SHG) effect are important for technological applications.…”

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“…[2] Therefore, it is necessary for the material science community to develop new strategies to create these materials. Their symmetry-dependent properties, such as ferroelectricity/multiferroics, piezoelectricity, pyroelectricity, and second-order harmonic generation (SHG) effect are important for technological applications.…”

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“…[1] However, polar crystal design and synthesis is challenging, because multiple effects, such as steric or dipole-dipole interactions, typically combine to form non-polar structures; thus the number of known polar materials, especially polar magnetoelectric materials, is still severely restricted. [2] Therefore, it is necessary for the material science community to develop new strategies to create these materials.Recently, exotic ABO 3 -type perovskites with unusually small A-site cations have attracted much attention owing to the formation of LiNbO 3 (LN)-type polar structure at high pressure (HP; Supporting Information, Section S1). [3] So far, several LN-type ABO 3 oxides have been discovered as metastable quenched phases, including ZnSnO 3 , [4a] CdPbO 3 , [4b] (In 1Àx & x )MO 3Àd (M = Mn/Fe, & = vacancy), [5] ScFeO 3 , [3b] and the high-pressure polymorphs of MnMO 3 (M = Ti, Sn) [6] and FeTiO 3 , [7] which show either SHG [4] or (near) room-temperature (RT) multiferroic behavior.…”

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Polar and Magnetic Mn₂FeMO₆ (M=Nb, Ta) with LiNbO₃‐type Structure: High‐Pressure Synthesis

Walker

Retuerto

et al. 2013

Angew Chem Int Ed

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Polar oxides are of much interest in materials science and engineering. Their symmetry-dependent properties, such as ferroelectricity/multiferroics, piezoelectricity, pyroelectricity, and second-order harmonic generation (SHG) effect are important for technological applications. [1] However, polar crystal design and synthesis is challenging, because multiple effects, such as steric or dipole-dipole interactions, typically combine to form non-polar structures; thus the number of known polar materials, especially polar magnetoelectric materials, is still severely restricted. [2] Therefore, it is necessary for the material science community to develop new strategies to create these materials.Recently, exotic ABO 3 -type perovskites with unusually small A-site cations have attracted much attention owing to the formation of LiNbO 3 (LN)-type polar structure at high pressure (HP; Supporting Information, Section S1). [3] So far, several LN-type ABO 3 oxides have been discovered as metastable quenched phases, including ZnSnO 3 , [4a] [5] ScFeO 3 , [3b] and the high-pressure polymorphs of MnMO 3 (M = Ti, Sn) [6] and FeTiO 3 , [7] which show either SHG [4] or (near) room-temperature (RT) multiferroic behavior. [3,[5][6][7] Compared with the research in HP-stabilized LN-type ABO 3 oxides, there are few studies of systems with multiple B-site cations, such as A 2 BB'O 6 , containing small A-ions.

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The Role of Polar, Lamdba (Λ)-Shaped Building Units in Noncentrosymmetric Inorganic Structures

Cited by 126 publications

References 68 publications

Cs₂B₄SiO₉: A Deep‐Ultraviolet Nonlinear Optical Crystal

Cs₂B₄SiO₉: A Deep‐Ultraviolet Nonlinear Optical Crystal

Packing of Helices: Is Chirality the Highest Crystallographic Symmetry?

Polar and Magnetic Mn₂FeMO₆ (M=Nb, Ta) with LiNbO₃‐type Structure: High‐Pressure Synthesis

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The Role of Polar, Lamdba (Λ)-Shaped Building Units in Noncentrosymmetric Inorganic Structures

Cited by 126 publications

References 68 publications

Cs2B4SiO9: A Deep‐Ultraviolet Nonlinear Optical Crystal

Cs2B4SiO9: A Deep‐Ultraviolet Nonlinear Optical Crystal

Packing of Helices: Is Chirality the Highest Crystallographic Symmetry?

Polar and Magnetic Mn2FeMO6 (M=Nb, Ta) with LiNbO3‐type Structure: High‐Pressure Synthesis

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Cs₂B₄SiO₉: A Deep‐Ultraviolet Nonlinear Optical Crystal

Cs₂B₄SiO₉: A Deep‐Ultraviolet Nonlinear Optical Crystal

Polar and Magnetic Mn₂FeMO₆ (M=Nb, Ta) with LiNbO₃‐type Structure: High‐Pressure Synthesis