Pb2B5O9I: An Iodide Borate with Strong Second Harmonic Generation

Huang, Yi-Zhi; Wu, Li‐Ming; Wu, Xin‐Tao; Li, Long-Hua; Chen, Ling; Zhang, Yongfan

doi:10.1021/ja106066k

Cited by 340 publications

(216 citation statements)

References 19 publications

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“…In order to obtain NLO materials exhibiting strong second-harmonic generation (SHG) effects, a number of methods have been discussed. Combining asymmetric building units, such as distorted octahedra with a d 0 transition metal cation [39][40][41], polyhedra with a d 10 metal cation revealing a polar displacement [42,43], and metal ions with ns 2 lone pair electrons [44] in the frameworks of new materials is a common approach to increase the incidence of many good NLO materials [45,46]. Incorporation of the above mentioned acentric building units into a nitrates system may also enlarge the SHG efficiency of materials.…”

Section: Introductionmentioning

confidence: 99%

Rb2Na(NO3)3: A Congruently Melting UV-NLO Crystal with a Very Strong Second-Harmonic Generation Response

et al. 2016

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Crystals of congruently melting noncentrosymmetric (NCS) mixed alkali metal nitrate, Rb 2 Na(NO 3 ) 3 , have been grown through solid state reactions. The material possesses layers with NaO 8 hexagonal bipyramids and NO 3 triangular units. Rb + cations are residing in the interlayer space. Each NaO 8 hexagonal bipyramid shares its corners and edges with two and three NO 3 units, respectively, in order to fulfill a highly dense stacking in the unit cell. The NaO 8 groups share their six oxygen atoms in equatorial positions with three different NO 3 groups to generate a NaO 6 -NO 3 layer with a parallel alignment. The optimized arrangement of the NO 3 groups and their high density in the structure together produce a strong second-harmonic generation (SHG) response. Powder SHG measurements indicate that Rb 2 Na(NO 3 ) 3 has a strong SHG efficiency of five times that of KH 2 PO 4 (KDP) and is type I phase-matchable. The calculated average nonlinear optical (NLO) susceptibility of Rb 2 Na(NO 3 ) 3 turns out to be the largest value among the NLO materials composed of only [NO 3 ]á nion. In addition, Rb 2 Na(NO 3 ) 3 exhibits a wide transparency region ranging from UV to near IR, which suggests that the compound is a promising NLO material.

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Section: Introductionmentioning

confidence: 99%

Rb2Na(NO3)3: A Congruently Melting UV-NLO Crystal with a Very Strong Second-Harmonic Generation Response

et al. 2016

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“…In inorganic materials, the macroscopic acentricity is often a manifestation of the asymmetric coordination environments of the cations. As for the metal-oxide-based system, there are mainly two types of inorganic asymmetric units which favor SHG activity, including planar (BO 3 ) 3 with a -conjugated system [14][15][16], and cations subject to second-order Jahn-Teller (SOJT) distorted cations such as octahedrally coordinated d 0 transition metal (TM) cations (e.g. Nb 5+ , V 5+ , Mo 6+ ) [17,18], and lone-pair cations (I 5+ , Se 4+ , Te 4+ , Pb 2+ , Bi 3+ , etc) [19][20][21][22][23].…”

Section: Introductionmentioning

confidence: 99%

Structures and properties of functional metal iodates

2011

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Metal iodates with a lone-pair containing I(V) that is in an asymmetric coordination geometry can form a diversity of unusual structures and many of them are promising new second homonic generation (SHG) materials. They exhibit wide transparency wavelength regions, large SHG coefficients and high optical-damage thresholds as well as moderately high thermal stability. In this paper, the structures and properties of the metal iodates are reviewed. The combination of d 0 transition-metal cations with the iodate groups afforded a large number of metal iodates, with cations covering alkali metal, alkaline earth and lanthanide elements. Many of them are noncentrosymmetric (NCS) and display excellent SHG properties due to the additive effects of polarizations from both types of the asymmetric units. Some lanthanide iodates are able to emit strong luminescence in the visible or near-IR regions. The use of transition metal ions with d n (n ≠ 0) electronic configuration into iodate systems can also induce the formation of NCS compounds when the lone pairs of the iodate groups are properly aligned. The d n transition metal cations are normally octahedrally coordinated or in a square-planar coordination geometry. Furthermore, the combination of two different types of lone-pair-containing cations is also an effective strategy to design new SHG materials. second homonic generation (SHG), metal iodates, crystal structures, structure-property relationship

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“…[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.…”

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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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Pb₂B₅O₉I: An Iodide Borate with Strong Second Harmonic Generation

Cited by 340 publications

References 19 publications

Rb2Na(NO3)3: A Congruently Melting UV-NLO Crystal with a Very Strong Second-Harmonic Generation Response

Rb2Na(NO3)3: A Congruently Melting UV-NLO Crystal with a Very Strong Second-Harmonic Generation Response

Structures and properties of functional metal iodates

Cs₂B₄SiO₉: A Deep‐Ultraviolet Nonlinear Optical Crystal

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Pb2B5O9I: An Iodide Borate with Strong Second Harmonic Generation

Cited by 340 publications

References 19 publications

Rb2Na(NO3)3: A Congruently Melting UV-NLO Crystal with a Very Strong Second-Harmonic Generation Response

Rb2Na(NO3)3: A Congruently Melting UV-NLO Crystal with a Very Strong Second-Harmonic Generation Response

Structures and properties of functional metal iodates

Cs2B4SiO9: A Deep‐Ultraviolet Nonlinear Optical Crystal

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Pb₂B₅O₉I: An Iodide Borate with Strong Second Harmonic Generation

Cs₂B₄SiO₉: A Deep‐Ultraviolet Nonlinear Optical Crystal