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Mar 9, 2018 - Beryllium-Free Nonlinear-Optical Crystals A3Ba3Li2Ga4B6O20F(A=K and Rb): Members of the Sr2Be2(BO3)2O Family with a Strong. Covalent ...
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Article Cite This: Inorg. Chem. 2018, 57, 5669−5676

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Beryllium-Free Nonlinear-Optical Crystals A3Ba3Li2Ga4B6O20F (A = K and Rb): Members of the Sr2Be2(BO3)2O Family with a Strong Covalent Connection between the 2∞[Li2Ga4B6O20F]9− Double Layers Xianghe Meng,†,‡ Fei Liang,†,‡ Mingjun Xia,*,† and Zheshuai Lin†,‡ †

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Beijing Center for Crystal Research and Development, Key Laboratory of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China ‡ University of Chinese Academy of Sciences, Beijing 100190, China S Supporting Information *

ABSTRACT: Two gallium-based borates, K3Ba3Li2Ga4B6O20F (I) and Rb3Ba3Li2Ga4B6O20F (II), have been successfully grown in the M2O (M = K, Rb)−LiF−B2O3 flux. They can be recognized as the element cosubstitutions of Sr for K/Rb and Ba and of Be for Li and Ga from Sr2Be2(BO3)2O (SBBO), which uses poisonous beryllium oxide during the synthesis and crystal growth process and also exhibits the problem of structural instability. The isostructural borates crystallize into the noncentrosymmetric space group P6̅2c, with a = 8.6398(12) Å and c = 16.827(3) Å for I and a = 8.7214(12) Å and c = 17.180(3) Å for II. In the structures, the basic anionic units are the BO3 triangles and GaO4 and LiO3F tetrahydra. These anionic units bond together through O atoms, forming the infinitely extended 2∞[LiGa2B3O12]8− single layer at the ab plane. The adjacent layers are further coupled to the 2∞[Li2Ga4B6O20F]9− double layers by means of bridged O and F atoms. Then the adjacent double layers are strongly joined together via O atoms of the GaO4 tetrahedra to form a three-dimensional skeleton, with K/Rb and Ba atoms occupying the network for charge balance. I and II have considerable second-harmonic-generation responses of about 0.7 and 0.5 as large as that of KH2PO4, respectively. In addition, the first-principles calculations were conducted to confirm that they address the structural instability issues in SBBO.

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INTRODUCTION

In order to solve the above problem of highly toxic beryllium oxide as the synthetic material in SBBO, K2Al2B2O7 (KABO) was found by replacing Be for Al according to the diagonal rule, proposed as a fourth-harmonic-generation material with an application wavelength at 266 nm.33,34 Nevertheless, Fe3+ impurity substitution for Al3+ in the original structure in the growth process causes nonintrinsic absorption and seriously lowers the conversion efficiency.35−37 Then, the task of exploring the SBBO family NLO materials is still ongoing. In 2016, a new SBBO-type NLO material, K3Ba3Li2Al4B6O20F, without structural instability was found by Luo’s group.13 After that, Rb3Ba3Li2Al4B6O20F and K3Sr3Li2Al4B6O20F were successively synthesized with different topological structures and moderate second-harmonic-generation (SHG) responses.13,37−40 In this work, we synthesized two novel borates without toxic elements, K3Ba3Li2Ga4B6O20F (I) and Rb3Ba3Li2Ga4B6O20F (II), for the first time by a chemical replacement strategy of the Li−F and Ga−O bonds for the Be−O strong bonds in SBBO. I and II possess double layers that are strongly interconnected via Ga−O bonds, compared with the relatively weak bonding

Nonlinear-optical (NLO) crystals, as the basis for the development of modern laser technology, have aroused great attention.1−5 Lasers having different frequencies have widespread applications, i.e., optics communication, laser photolithograph, micromanufacturing, and so forth.6−11 NLO crystals can be employed to expand the laser wavelengths in the range from IR to deep-ultraviolet (UV), e.g., chalcogenide AgGaS2, phosphates including KTiOPO4 and KH2PO4 (KDP), borates containing LiB 3 O 5 , KBe 2 BO 3 F 2 , β-BaB 2 O 4 , Sr 2 Be 2 B 2 O 7 (SBBO), etc.12−18 Noncentrosymmetric (NCS) construction of a basic structural block is an essential prerequisite of NLO crystals, and many researchers try to introduce NCS building blocks to design new NLO materials with intrigued properties.19−28 In 1995, Chen et al. successfully developed the new compound SBBO, which features 2∞[Be2B2O7]4− double layers interconnected by Sr−O bonds rather than a single-layer 2 [Be2BO3F2]− interconnected by a relatively structure ∞ impotent bonding interaction in KBBF.17,29 However, in addition to containing highly toxic beryllium oxide as the synthetic material, SBBO experienced a structural instability problem. The existence of these problems hinder its practical application.9,30−32 © 2018 American Chemical Society

Received: March 9, 2018 Published: April 20, 2018 5669

DOI: 10.1021/acs.inorgchem.8b00632 Inorg. Chem. 2018, 57, 5669−5676

Article

Inorganic Chemistry

Powder X-ray Diffraction (PXRD). The PXRD data of two samples were collected on a Bruker D8 Focus diffractometer equipped with Cu Kα radiation (λ = 1.5418 Å) in the 2θ range of 10−70° at room temperature (Figures S1 and S2). Thermal Analysis. The differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were performed on a Labsys TG-DTA16 (SETARAM) thermal analyzer under N2 flow with a sample heating rate of 20 °C/min from room temperature to 1100 °C. UV−Vis−Near-IR (NIR) Diffuse-Reflectance Spectrum. The reflectance spectra were measured in the range of 200−2000 nm by a PerkinElmer Lambda 900 UV−vis−NIR spectrometer equipped with an integrating sphere. BaSO4 was employed as the 100% reflectance standard. SHG Measurement. Powder SHG experiments of I and II were carried out on a Q-switched Nd:YAG laser at a wavelength of 1064 nm, which was used to irradiate the samples by the Kurtz−Perry method. The polycrystalline powders of I and II were finely ground and sieved into six particle size ranges: 20−50, 50−74, 74−100, 100− 150, 150−180, and 180−212 μm. For comparison, KDP powders with the same particle sizes were utilized as standard samples. First-Principles Computational Method. The first-principles simulations for the title compounds (I and II) were performed by the CASTEP package42 on the basis of density functional theory methods, as has been applied on many borate NLO materials.43−47 The lattice constants and unit cell volumes are fixed at experimental results in first-principles calculations. The generalized gradient approximation Perdew−Burke−Ernzerhof (GGA-PBE) exchange-correlation functionals are used, and norm-conserving pseudopotentials are adopted for all elements to describe the ion−electron interactions.48,49 In this model, K 3s23p64s1, Rb 4s24p65s1, Li 1s2, Ba 5s25p66s2, B 2s22p1, Ga 3d104s24p1, O 2s22p4, and F 2s22p5 valence electrons are used. A cutoff energy of 940 eV and Monkhorst−Pack k-point meshes (6 × 6 × 2) in the first Brillouin zone are adopted.50 The scissors operator,51 which is set as the energy difference between the experimental and calculated band gaps, is adopted to calculate the NLO coefficients. Meanwhile, the phonon vibrational properties of I and II are obtained by the linear response function.52 The LO−TO phonon frequency splitting at the Γ point is also included in the phonon calculations. The dispersion separation of 0.01/Å3 is adopted to ensure good convergence.

interaction between the A cations (A = Ba and Sr) and O anions in the compounds K3A3Li2Al4B6O20F. These two UV NLO crystals show moderate NLO effects. Herein, we report the syntheses, single-crystal structures, and thermal and optical properties of the two compounds, and theoretical calculations are also conducted to unravel their structural stabilities and optical properties.

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EXPERIMENTAL SECTION

Synthesis of Polycrystalline I and II. Polycrystalline I and II were successfully prepared by the high-temperature ceramic reaction technique. The analytically pure reagents of K2CO3 (0.622 g, 0.0045 mol) or Rb2CO3 (1.039 g, 0.0045 mol), BaCO3 (1.776 g, 0.009 mol), Li2CO3 (0.111 g, 0.0015 mol), Ga2O3 (1.125 g, 0.006 mol), LiF (0.078 g, 0.003 mol), and H3BO3 (1.113 g, 0.018 mol) were mixed and thoroughly ground quickly. Then, the mixture was gradually heated from room temperature to 500 °C at a rate of 20 °C/h and held there for 24 h to adequately decompose the reactants. Finally, the powders were further heated to 650 °C for 48 h. Crystal Growth. Small colorless single crystals of I and II were obtained by the spontaneous crystallization method using the M2O (M = K and Rb)−LiF−B2O3 flux system at a molar ratio of I/II:M2CO3 (M = K and Rb):LiF:B2O3 = 1:1.5:2.5:3. A mixture of I/II polycrystalline powders and the flux K2CO3 or Rb2CO3−LiF−B2O3 was put into a platinum crucible after being fully ground. Then, the mixture was slowly heated to 820 °C and held there for 24 h for complete homogenization of the melt. Afterward, the melt was cooled to 650 °C at a cooling rate of 1 °C/h. Then the furnace was switched off (to reach room temperature) after the crystal growth process was completed. The millimeter-level regular-shaped crystals were grown on the melt surface. Single-Crystal Structure Determination. Small crystals were picked for structure analysis using the single-crystal X-ray diffraction method. The diffraction data were collected on a Rigaku AFC10 single-crystal diffractometer equipped with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at 153 K. The crystal structures were solved by direct methods with the program SHELXS-97 and refined by full-matrix least squares on F2 by SHELXL-97 programs.41 The structures were verified using the ADDSYM algorithm from the program PLATON, and no higher symmetry was found. The relevant crystallographic data are listed in Table 1. Additional crystallographic information is given in Tables S1−S4.

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RESULT AND DISCUSSION Crystal Structure. The two compounds crystallize in the NCS space group P6̅2c (No. 190). Because of their isotypic structures, structure II is discussed in detail. II exhibits a threedimensional framework stacked from the 2∞[Li2Ga4B6O20F]9− double layers via Ga−O covalent connections (Figure 1a). The cations of Ba2+ and Rb+ occupy the anionic skeleton of the network to keep an electroneutral balance. The double layers are built through the long Ga−O and Li−F bond interconnections of the two adjacent 2∞[LiGa2B3O12]8− single layers (Figure 1b). As shown in Figure 1c, three BO3, two GaO4, and one LiO3F anionic groups bond together through O atoms, forming the 2∞[LiGa2B3O12]8− single layer at the ab plane. Notably, the 2∞[LiGa2B3O12]8− single layer can be viewed as an infinitely edge-sharing linkage of the 12-membered rings (12-MRs) composed of three BO3, two GaO4, and one LiO3F. The B atoms coordinate to three O atoms to build typical BO3 planar triangles with B−O bond distances of 1.36(3)−1.42(3) Å. Also, there are two types of GaO4 and one type of LiO3F tetrahedra, and the bond distances of Ga−O, Li−O, and Li−F are 1.670(3)−1.820(13), 2.01(2), and 1.86(5) Å, respectively. It is worth mentioning that our group reported a similar compound, K2Ba4Ga4Li2B6O21, with the incorrect formula of K3Ba3Li2Ga4B6O20F in 2014, probably because of the similar atomic radius between O and F. Structural Evolution. Structures I and II can be viewed as variants from the SBBO family. As shown in Figure 2, the

Table 1. Crystallographic Data for I and II empirical formula fw (g/mol) cryst color cryst syst space group a/Å c/Å V/Å3 Z μ/mm−1 F(000) R(int) GOF(F2) Flack parameter final R indicesa final R indices (all data)a

K3Ba3Li2Ga4B6O20F 1325.94 colorless hexagonal P6̅2c (No. 190) 8.6398(12) 16.827(3) 1087.8(3) 2 10.893 1108 0.0509 1.082 0.02(6) R1 = 0.0464, wR2 = 0.1170 R1 = 0.0464, wR2 = 0.1172

Rb3Ba3Li2Ga4B6O20F 1365.05 colorless hexagonal P6̅2c (No. 190) 8.7214(12) 17.180(3) 1131.7(3) 2 16.329 1216 0.0522 1.133 0.10(7) R1 = 0.0529, wR2 = 0.1201 R1 = 0.0530, wR2 = 0.1202

R1 = ∑||Fo| − |Fc||/∑|Fo| and wR2 = [∑[w(Fo2 − Fc2)2]/ ∑[w(Fo2)2]]1/2 for Fo2 > 2σ(Fc2). a

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DOI: 10.1021/acs.inorgchem.8b00632 Inorg. Chem. 2018, 57, 5669−5676

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Figure 1. (a) Crystal structure of II, (b) the 2∞[Li2Ga4B6O20F]9− double layer, and (c) the 2∞[LiGa2B3O12]8− single layer composed of three BO3, two GaO4, and one LiO3F groups at the ab plane. Color code: Rb, gray; Ba, blue; Ga, gold, Li, violet, F, yellow; B, green; O, red.

Figure 2. Structural comparison of the SBBO family NLO crystals including (a) SBBO, (b) KABO, (c) K3Ba3Li2Al4B6O20F, and (d) I. 5671

DOI: 10.1021/acs.inorgchem.8b00632 Inorg. Chem. 2018, 57, 5669−5676

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Inorganic Chemistry

Figure 3. (a) Reflectance spectra of I and II. (b) Powder SHG data for I and II at 1064 nm.

Figure 4. Arrangement of the BO3 groups in (a) K3Ba3Li2Al4B6O20F and (b) II along the c axis.

Figure 5. (a) Electronic band structure of I. (b) DOS and partial DOS plots of I. (c) Electronic band structure of II. (d) DOS and partial DOS plots of II.

plane and further connected through the apical O atoms of the XO4 (X = Be, Al, and Ga) or LiO3F groups to form the double layers. The main difference of the SBBO family structure is the stacking patterns between the double layers along the c direction, except for the element types. In the structures of I and II, the double layers are stacked from the strongly covalent

SBBO family NLO materials include SBBO, KABO, K3Ba3Li2Al4B6O20F, I, and II by the element substitutions. All of these borates consist of the fundamental building groups BO3 and XO4 (X = Be, Al, and Ga). Then similar single layers are built from the 12-MRs composed of the fundamental building groups BO3 and XO4 (X = Be, Al, and Ga) at the ab 5672

DOI: 10.1021/acs.inorgchem.8b00632 Inorg. Chem. 2018, 57, 5669−5676

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Inorganic Chemistry

Figure 6. Calculated refractive indices and PM SHG limits for (a) I and (b) II in the wavelength range of 250−1200 nm.

Figure 7. Phonon dispersion of (a) I and (b) II.

compound is superposed from all BO3 groups. If all of the BO3 groups are well aligned along the identical direction, the contribution to the SHG effect will reach a maximum, especially when the twisting angle between the BO3 groups is close to zero. The twisting angles of the BO3 groups in I are about 29.3°, while that of the K3Ba3Li2Al4B6O20F crystal is 13.1° (Figure 4), giving the main reason for the smaller nonlinear effect of I than that of K3Ba3Li2Al4B6O20F. Second, the number of BO3 groups in the whole structure becomes smaller from I to K3Ba3Li2Al4B6O20F because of the larger radius of the Ga atom. First-Principles Calculations. To elucidate the relationship between the structures and properties of the title compounds, first-principles calculations were performed. Here, compound II was described as a representative. The electronic structure of II shows that II is a direct-gap material and the forbidden gap at Γ point is 3.42 eV (Figure 5b), which is smaller than the experimental value (5.90 eV) because of the intrinsic insufficiency of GGA-PBE functionals.53 Figure 5d presents the partial density of states (DOS) analysis on II. Clearly, the upper region of the valence band (−8 to 0 eV) consists of B 2p, Ga 3p, and O 2p electrons, in which there is high orbital hybridization on the O and B/Ga orbitals; therefore, there is strong covalent bonding between the B/Ga and O atoms. Rb and Ba also make nonignorable contributions to the electronic states because of the contribution from the orbitals of all atoms on the conduction-band bottom. Notably,

Ga−O bonding, which are different from the previously reported double-layer structure of K3Ba3Li2Al4B6O20F, whose interactions are between double layers via Ba−O bonds. It is very interesting that the connection between the double layers changed markedly from K3Ba3Li2Al4B6O20F and I, although Al3+ and Ga3+ belong to the same main family element. The connection radius of Ga3+ is about 1.2 times that of Al3+, and this may be the reason. Thermal Properties. Both I and II started to lose weight and exhibited small endothermal peaks at the heating temperatures above 720 °C in the TGA and DSC curves (Figures S2 and S3). Compounds I and II, after melting, decompose to BaGa2O4, further confirming their incongruent melt properties (Figures S4 and S5). Optical Properties. As shown in Figure 3a, I and II possess high transmission in the range of 200−2000 nm, indicating potential applications as UV NLO crystals. Owing to the NCS structure and belonging to the SBBO family, I and II are expected to pursue NLO effects with similar SHG responses. The SHG signal intensities of I and II are about 0.7 and 0.5 as large as that of the reference KDP, respectively (Figure 3b), which are obviously smaller than that of K3Ba3Li2Al4B6O20F (1.5KDP). This may be due to the following two reasons. First, the planar BO3 groups are the main contributor to nonlinear effects in borates according to the anionic group approximation. The nonlinear effect of the 5673

DOI: 10.1021/acs.inorgchem.8b00632 Inorg. Chem. 2018, 57, 5669−5676

Inorganic Chemistry

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the Mullkien populations between the Ga−O bonds (∼0.40− 0.45) are smaller than those of the Al−O bonds (∼0.47−0.64), thus indicating the weaker covalancy of the Ga−O bonds. As a result, the terminal O nonbonding states of the BO3 units are not totally saturated; hence, there is a smaller band gap in Gabased compounds. Because of the point group of 6̅m2, both of them have only one nonzero independent NLO coefficient d22. The calculated d22 results are 0.15 and 0.08 pm/V for I and II, respectively. As shown in Figure 6, the optical birefringences were calculated as 0.0416 and 0.0434 (at 800 nm) for the K and Rb analogues, respectively, which is close to that of CsLiB6O10 (0.049).54 Accordingly, it is confirmed that they are type I phase-matching (PM) materials examined by the experimental tests. Moreover, the shortest SHG wavelengths of I and II were obtained as 282 and 290 nm. Therefore, NLO crystals of I and II can be utilized as the third harmonic generation at 355 nm of Nd-based lasers. To gain further insight on their structural stability and interatomic interaction, the phonon vibrational dispersion spectra were defined by first-principles calculations. In previous work, the SBBO structure kinetically destabilizes (imaginary phonon eigenvalues) because of the large Sr atoms locating in the interlayer space, thereby producing negative BO3 twisting vibrational modes. It can be seen from Figure 7 that all phonon mode eigenvalues are positive, theoretically indicating that the structures of I and II are stable. Moreover, this is also in agreement with the small structural residue factors for I and II (0.031 and 0.023) compared with SBBO (0.043). The higher structural stability can be attributed to larger Ga−O−Ga bridge bonds. Thus, the interlayer space is bigger than that of SBBO, which provide a more flexible coordination environment for Rb/K and Ba atoms. I and II can be recognized as SBBO family materials, but they get over the structural problem of SBBO.

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Fei Liang: 0000-0002-4932-1329 Mingjun Xia: 0000-0001-8092-6150 Zheshuai Lin: 0000-0002-9829-9893 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work is financially supported by the National Natural Science Foundation of China (Grants 51502307, 51772304, 51702329, 91622118, and 11474292), the Youth Innovation Promotion Association of the Chinese Academy of Sciences (2018035), and the Foundation of the Director of Technical Institute of Physics and Chemistry, CAS. We thank Dr. Sangen Zhao for help with the powder SHG test and Dr. Xin Gao for useful discussion.

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REFERENCES

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CONCLUSION Inheriting all of the merits of SBBO, two new beryllium-free borates, I and II, were successfully grown via the hightemperature solution method. They feature 2∞[Li2Ga4B6O20F]9− double layers with a strong covalent interconnection by the Ga−O bonds. As shown by powder SHG measurements, their NLO signals are comparable to that of KDP. These findings reveal that I and II are two new UV NLO materials for application at 355 nm.

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Article

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b00632. PXRD patterns, DSC and TGA curves, and atom coordinates, equivalent isotropic displacement parameters, bond valence sums, and selected bond distances and angles for I and II (PDF) Accession Codes

CCDC 1821881 and 1821900 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. 5674

DOI: 10.1021/acs.inorgchem.8b00632 Inorg. Chem. 2018, 57, 5669−5676

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DOI: 10.1021/acs.inorgchem.8b00632 Inorg. Chem. 2018, 57, 5669−5676