Ba4B8TeO19: A UV Nonlinear Optical Material - ACS Publications

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Ba4B8TeO19: A UV Nonlinear Optical Material Lili Liu,† Joshua Young,‡ Manuel Smeu,‡ and P. Shiv Halasyamani*,† †

Department of Chemistry, University of Houston, 112 Fleming Building, Houston, Texas 77204, United States Department of Physics, Binghamton University − SUNY, 25 Murray Hill Road, Binghamton, New York 13902, United States

‡

S Supporting Information *

ABSTRACT: We report a new noncentrosymmetric barium tellurium borate, Ba4B8TeO19 that has potential ultraviolet (UV) nonlinear optical (NLO) applications. Ba4B8TeO19 was synthesized by a flux method and crystallizes in the noncentrosymmetric space group Cc. The material exhibits a framework structure of [B8O17]∞ double layers connected to distorted TeO6 octahedra. Second harmonic generation (SHG) measurements at 1064 and 532 nm on polycrystalline Ba4B8TeO19 indicate that the title compound is phasematchable (type I) with a moderate SHG response (1 × KH2PO4 at 1064 nm and 0.2 × β-BaB2O4 at 532 nm). In addition, a short absorption edge (210 nm) was measured. Using density functional theory calculations, we show that the SHG response originates from contributions from O 2p and Te 5s states at the valence and conduction band edges. Finally, by computing the linear optical properties, we find that this compound displays a moderate birefringence of 0.055 at 1064 nm and 0.059 at 532 nm, necessary conditions for phase-matching in UV NLO materials.

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alkaline earth cation (Ba2+) resulted in the discovery of Ba4B8TeO19. This new noncentrosymmetric material exhibits a moderate SHG effect (1 × KH2PO4 at 1064 nm and 0.2 × βBaB2O4 at 532 nm), as well as a short absorption edge (210 nm). Herein we report on the synthesis, characterization, and structure−property relationships in Ba4B8TeO19.

INTRODUCTION Over the past half-century, inorganic materials capable of SHG have been used to generate coherent radiation.1,2 This is especially true in the UV region, i.e., λ < 300 nm. Generation of 266 nm radiation starting with a 1064 nm (Nd:YAG) laser can be achieved through cascaded frequency conversion: fourth harmonic generation (FOHG), i.e., 1064 nm/4 = 266 nm. Four materials have been shown to generate coherent radiation at 266 nm. These are YAl3(BO3)3 (YAB),3 Li2B4O7 (LB4),4,5 CsLiB6O10 (CLBO),6−8 and β-BaB2O4 (β-BBO).9,10 Each material has its drawbacks. YAB has a large SHG coefficient, but its low transmittance in the 200−320 nm range precludes its practical application.11,12 With LB4, high-quality crystals have been grown, but the reported SHG coefficient is very small.13 Thus, CLBO and β-BBO are often used to generate coherent 266 nm radiation. However, CLBO and β-BBO also have their drawbacks. CLBO is hygroscopic and β-BBO exhibits a large birefringence that results in walk-off issues leading to a reduction in the SHG conversion efficiency.14,15 Thus, the challenge remains: how to design and synthesize a new UV NLO material? Often the discovery of new NLO materials occurs through trial and error. However, the structural framework of known NLO materials can be exploited in the discovery of new NLO materials. Recently many NLO borates have been reported,16−20 especially a series of fluorooxoborates, i.e., AB4O6F (A = NH4, Rb, or Cs).16−18 These materials exhibit excellent NLO properties and feature two-dimensional [B4O6F]∞ layers composed of BO3F and BO3 groups. Analogous to the [B4O6F]∞ layers, we used [B4O9]∞ layers that in combination with tellurate octahedra (TeO6) and an © XXXX American Chemical Society

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EXPERIMENTAL SECTION

Reagents. BaCO3 (Fisher Scientific Company, 99%), TeO2 (Alfa Aesar, 99%), B2O3 (Alfa Aesar, 99%), and K2CO3 (Sigma-Aldrich, 99.9%) were used as received. Synthesis. Polycrystalline sample of the title compound was synthesized by conventional solid-state methods. Stoichiometric amounts of the reactants were ground thoroughly, packed tightly in a platinum crucible, and preheated at 400 °C for 10 h. Then, the temperature was increased to 700 °C and held for 3 days with several intermittent grindings. The purity of the polycrystalline samples was confirmed by powder X-ray diffraction (XRD) measurements (see Figure S1a). Powder X-ray Diffraction. Powder XRD measurements were carried out at room temperature on a PANalytical X’Pert PRO diffractometer equipped with Cu Kα radiation (λ = 1.5418 Å). Data were collected in the two-theta range of 10−70° with a step scan width of 0.008° and a scan time of 0.5 s. The powder XRD patterns for the powder sample of Ba4B8TeO19 are shown in Figure S1a that indicates the experimental and calculated patterns are in excellent agreement. Crystal Growth. Single crystals of Ba4B8TeO19 were grown by spontaneous crystallization method using K2CO3 and TeO2 as flux. This solution was prepared in a platinum crucible by melting a mixture of K2CO3, BaCO3, TeO2, and B2O3 at a molar ratio of 3:1:3:2. The Received: February 26, 2018

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DOI: 10.1021/acs.inorgchem.8b00510 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry mixture was heated in a programmable furnace to 800 °C and held at this temperature for 10 h. The melt was cooled slowly (2 °C/h) to 500 °C and then cooled to room temperature over 12 h. Using this cooling profile, submillimeter-sized Ba4B8TeO19 crystals were obtained and mixed with known phases of BaTeO3 and BaTeO4 (Figure S1b). As the main phase of product, the yield of Ba4B8TeO19 crystals is around 80% based on B2O3. Structural Characterization. The crystal structure of the title compound was determined by single crystal X-ray diffraction. Data were collected on a Bruker SMART APEX2 diffractometer equipped with a 4K CCD area detector using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) and were integrated with the SAINT program.21 A multiscan technique was applied for the absorption corrections. The structure was solved by direct methods using SHELXS-97.22 All atoms in the structure were refined using full matrix least-squares techniques, and final least-squares refinement was on F02 with data having F02 ≥ 2σ (F02). The structure was checked with PLATON and no higher symmetry was found.23 Crystal data and structure refinement information for Ba4B8TeO19 are listed in Table 1. The final refined atomic positions, isotropic thermal parameters and bond valence are given in Table S1, and selected bond lengths and angles are listed in Table S2.

Calculations. Density functional theory25 calculations were performed with the Vienna ab initio Simulation Package (VASP)26,27 using projector augmented wave (PAW) pseudopotentials28 and the PBEsol29 functional. The noncentrosymmetric Ba4B8TeO19 crystal structure was fixed to the experimental lattice constants and the internal atomic positions were relaxed until the forces on the atoms were converged to within 10−4 eV/Å. A 900 eV plane wave cutoff and a Γ-centered 6 × 8 × 4 k-point mesh were used. To obtain the refractive index and birefringence, the real and imaginary parts of the frequency dependent dielectric constant were computed; 2000 empty bands were included in this calculation.

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RESULTS AND DISCUSSION Crystal Structure. Single crystal data indicated that Ba4B8TeO19 crystallizes in the noncentrosymmetric space group Cc (No. 9). The unit cell of Ba4B8TeO19 is shown in Figure S2. Ba4B8TeO19 exhibits a three-dimensional structure consisting of B4O11 units and TeVIO6 octahedra (Figure 1). In the structure, there are eight different boron atoms of which six are coordinated to four oxygen atoms, and two are bonded to three oxygen atoms. As such, BO4 tetrahedra and BO3 triangles are formed. One BO3 and three BO4 groups corner-share to create a [B4O11] group. As shown in Figure 1a, there are two kinds of [B4O11] groups in the structure of Ba4B8TeO19. The first [B4O11] group is composed of B(1)O4, B(2)O4, B(8)O4, and B(5)O3, and these [B4O11] groups connect to form a [B4O9]∞ layer (layer I) in the ab-plane via B(8)O4 sharing corners with B(1)O4 and B(5)O3 groups (Figures 1b and S3a). The second [B4O11] group consists of B(3)O4, B(4)O4, B(6)O4 and B(7)O3, and these [B4O11] groups connect to form another [B4O9]∞ layer (layer II) in the ab plane via B(4)O4 sharing corners with B(3)O4 and B(7)O3 groups (Figures 1b and S3b). Subsequently, B(1)O4 and B(6)O4 corner-share to link layer I and layer II together to further create the [B8O17]∞ double layers (Figures 1c and S3c). The [B8O17]∞ double layers are stacked along the c axis and are connected by distorted TeO6 octahedra to create the threedimensional [B8TeO19]∞ framework (Figure 1c). Ba2+ cations reside in the cavities of the framework (Figure 1c). In connectivity terms, the structure of Ba4B8TeO19 may be described as {[TeO4/2O2]2−6[BO4/2]−2[BO3/2]}8− with the charge balanced by the four Ba2+ cations. Large 18-membered rings (MRs) are observed on each [B4O9]∞ layer with the B···B distances ranging from 4.50(1) to 7.39(1) Å (Figures 1b and S4), with Ba2+ cations located in the center of the 18-MR (Figure S4). The large 18-MR suggests that Ba2+ may be replaced by other alkaline earth cations. In Ba4B8TeO19, the Ba2+ cations are bonded to 9 and 11 oxygen atoms (Figure 1d), with Ba−O bond distances ranging from 2.636(5) to 3.212(6) Å (Table S2). The Te−O and B−O bond distances range between 1.871(5)−1.965(5) Å and 1.355(10)−1.536(9) Å, respectively. Bond valence calculations32,33 on Ba, Te, B, and O resulted in values of 2.10−2.36, 5.91, 2.88−3.02, and 1.89−2.18, respectively (Table S1). These values are consistent with the reported oxidation states. In inorganic borotellurates system, two series of compounds have been reported: noncentrosymmetric Bi3TeBO9 and centrosymmetric Na2Ln2TeB2O10 (Ln = Y, Dy−Lu).30,31 The structure of Bi3TeBO9 is formed through the connection of BiO6 polyhedra, BO3 triangles and distorted TeO6 octahedra (Figure S5a). Na2Ln2TeB2O10 is composed of TeO4(BO3)2 anions connected to Y3+ and Na+ cations (Figure S5b). In the title compound Ba4B8TeO19, boron atoms exhibit two types of coordination environments: BO3 triangles and BO4 tetrahedra.

Table 1. Crystal Data and Structure Refinement for Ba4B8TeO19 chemical formula formula weight temperature wavelength crystal system, space group unit cell dimensions

Z volume (Å3) calculated density (mg/m3) absorption coefficient (mm−1) reflections collected/unique completeness to theta = 28.29° goodness-of-fit on F2 final R indices [I > 2sigma(I)]a R indices (all data) Flack parameter extinction coefficient largest diff. peak and hole (e·Å−3)

Ba4B8TeO19 1067.44 296(2) K 0.71073 Å monoclinic, Cc (No. 9) a = 11.512(2) Å b = 6.667(1) Å β = 105.734(2)° c = 19.700(3) Å 4 1455.3(4) 4.872 12.761 10178/3313 [R(int) = 0.0226] 99.9% 1.160 R1 = 0.0214, wR2 = 0.0537 R1 = 0.0214, wR2 = 0.0537 0.04(2) 0.00131(5) 1.886 and −0.926 e·A−3

R1 = Σ||F0| − |Fc||/Σ|F0| and wR2 = [Σw(F02-Fc2)2/ΣwF04]1/2 for F02 > 2σ(F02)

a

Infrared Spectroscopy. The infrared spectrum (IR) in the 400− 4000 cm−1 range was recorded by using a Thermo Scientific Nicolet iS10 FT-IR Spectrometer at room temperature. UV−Vis−NIR Diffuse Reflectance Spectrum. The UV−vis− NIR diffuse reflectance spectrum of Ba4B8TeO19 was measured at room temperature with a Cary 5000 UV−vis−NIR spectrophotometer in the 200−2500 nm wavelength range. Thermal Analysis. The thermal properties were carried out on an EXSTAR TG/DTA 6300 at a temperature range 40−1000 °C with a heating rate of 5 °C min−1 in flowing N2. SHG Measurements. The powder SHG intensity was measured by using the Kurtz-Perry method at 1064 and 532 nm.24 Polycrystalline Ba4B8TeO19, KH2PO4 and β-BBO were ground and sieved into distinct particle size ranges (125 μm). Sieved KH2PO4 and β-BBO powders were used as the references. The samples were placed in 1 mm thick fused silica tubes. The intensity of the frequency doubled radiation from the samples was measured using a photomultiplier tube. B

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Figure 1. Ball-and-stick representation of Ba4B8TeO19 is shown. (a) Two different B4O11 groups formed by differen boron atoms, (b) [B4O9]∞ layer I and [B4O9]∞ layer II formed by different B4O11 groups, (c) [B8O17]∞ double layers connected by distorted TeO6 octahedra to form the threedimensional [B8TeO19]∞ framework with Ba2+ cations residing in the cavities, and (d) coordination environments of cations.

The fundamental building block (FBB) of Ba4B8TeO19 is an infinite B4O11 group composed of one BO3 and three BO4 groups. The ratio between BO3 and BO4 in Ba4B8TeO19 is 1:3 that does not enhance its SHG response. In Bi3TeBO9 and Na2Ln2TeB2O10, boron atoms only form planar BO3 triangles. As is known, Bi3TeBO9 exhibits a strong SHG response of 20 × KH2PO4 that is much larger than that of the title compound.30 This is because Bi3TeBO9 incorporates three NLO-active units: π-orbital planar BO3 groups, a stereochemically active lone pair cation Bi 3+ , and distorted TeO 6 octahedra. However, Ba4B8TeO19 only contains π-orbital planar BO3 groups, and as such has a weaker SHG response. As mentioned above, Ba4B8TeO19 was synthesized based on the structure of AB4O6F (A = NH4, Rb, and Cs). The FBB of AB4O6F is the B4O8F group that is made of three BO3 triangles and one BO3F tetrahedron (Figure 2a). In the B4O8F group, when three BO4 tetrahedra replace the three BO3 triangles and a BO3 triangle replaces the BO3F tetrahedron, we obtain the B4O11 group, a FBB of Ba4B8TeO19 (Figure 2b). In NH4B4O6F and Ba 4 B 8 TeO 19 , each FBB (B 4 O 8 F or B 4 O 11 group respectively) shares corners with four additional FBBs (B4O8F or B4O11 groups, respectively). This results in the formation of a [B4O6F]∞ layer in NH4B4O6F, and a [B4O9]∞ layer in Ba4B8TeO19. As seen in Figure 2, these layers are structurally very similar. It is well-known that BO3 groups with π-conjugated electron systems have enhanced second-order susceptibility compared with BO4 groups that do not exhibit πconjugation.34,35 In Ba4B8TeO19, 75% of boron atoms form BO4 tetrahedra, which may lead to a smaller SHG effect compared with NH4B4O6F in which 75% of boron atoms form BO3 triangles. Infrared Measurement. The IR spectrum of Ba4B8TeO19 is shown in Figure S6. The bands near 1346 cm−1 can be

Figure 2. (a) [B4O6F]∞ layer in NH4B4O6F composed of B4O8F groups, (b) [B4O9]∞ layer in Ba4B8TeO19 composed of B4O11 groups.

assigned to the asymmetric stretches of the BO3 groups. The absorption band around 966 cm−1 is caused by the asymmetric stretching vibration of the BO4 tetrahedra, and the band around 829 cm−1 belongs to the symmetric stretching vibration of the BO4 tetrahedra. Then, peaks around 629 cm−1 can be assigned to the bending vibrations of the BO3 or BO4 groups. These assignments are consistent with those previously reported.36,37 UV−Vis−NIR Diffuse Reflectance Spectrum. The UV− vis−NIR diffuse reflectance spectrum is shown in Figure S7. Ba4B8TeO19 has an absorption edge of about 210 nm, indicating that a crystal of this compound may have potential use in UV NLO applications, i.e., FOHG generation of 266 nm radiation. C

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Figure 3. Powder SHG measurements for Ba4B8TeO19 at 1064 nm (a) and 532 nm (b).

Thermal Behavior. The TG/DTA curves of Ba4B8TeO19 are shown in Figure S8a. The TG curve indicates that Ba4B8TeO19 is stable until 800 °C. DTA measurements show that Ba4B8TeO19 exhibits an endothermic peak around 826 °C during the heating cycle and no exothermic peak during the cooling cycle. The main remnants after TG/DTA are α-BBO and β-BBO that was confirmed by powder XRD patterns (Figure S8b). Therefore, Ba4B8TeO19 is an incongruent compound. Second Harmonic Generation. The noncentrosymmetric structure of Ba4B8TeO19 prompted us to measure its SHG properties. The SHG measurements were carried out at 1064 and 532 nm with KH2PO4 and β-BBO used as the references, respectively. The results revealed that the SHG intensity of Ba4B8TeO19 is approximately equal to KH2PO4 at 1064 nm and 0.2 times that of β-BBO at 532 nm in the same particle size range of 90−125 μm (Figure 3). In addition, from Figure 3, it is clear that Ba4B8TeO19 is phase-matchable.24 According to anionic group theory,2,34 planar BO3 groups provide a greater contribution to the SHG intensity compared to BO4 tetrahedra. As Ba4B8TeO19 has more BO4 tetrahedra and fewer BO3 groups compared to NH4B4O6F and CsB4O6F, the SHG intensity is smaller, i.e., 1 × KH2PO4 versus 3 × KH2PO4 and 2 × KH2PO4 respectively. Electronic Structure and Optical Properties. We next investigated this material using density functional theory (DFT) calculations to better understand the origin of its NLO properties. By computing the electronic band structure, we find a direct band gap of 3.42 eV at the Γ-point (Figure 4). Although this is smaller than the experimentally determined 5.90 eV, standard exchange-correlation functionals in DFT are well-known to underestimate the magnitude of the band gap.38 Because the NLO properties of a material depend strongly on the atomic character of the band edges, we next computed the atom-resolved density of states (DOS, Figure 4b). We find that the top of the valence band consists primarily of O 2p states, as is typical of oxygen-containing NLO materials. Interestingly, the bottom of the conduction band is a narrow band consisting of only Te 5s and O 2p states. The presence of such states is in agreement with our previous DFT studies, which demonstrated that the presence of Te 5s states can help enhance the SHG response of Pb-based NLO materials.39 However, the lack of additional states at the conduction band minimum in this material is likely the reason for it displaying only a moderate SHG response. A combination of Ba 4d states and small

Figure 4. (a) Electronic band structure and (b) atomically resolved density of states for Ba4B8TeO19 computed using density functional theory.

amounts of O 2p states make up a band approximately 2.5 eV higher than these Te 5s states. Finally, we computed the linear optical properties and found a moderate birefringence (Δn) of 0.055 at 1064 nm (Figure S9), which is close to ideal for UV NLO materials.14

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CONCLUSION A new UV NLO material, Ba4B8TeO19, was reported as the first NLO alkali-earth metal tellurate borate. Ba4B8TeO19 exhibits a short UV absorption edge at about 210 nm. Ba4B8TeO19 is phase-matchable and can achieve 532 and 266 nm light generation by direct SHG. The SHG responses of Ba4B8TeO19 are approximately 1 × KH2PO4 at 1064 nm and approximately 0.2 × β-BBO at 532 nm. Using ab initio calculations, we showed that the SHG response originates from the O 2p and Te 5s states making up the band edges. We also computed a birefringence of 0.055 at 1064 nm and 0.059 at 532 nm. The moderate SHG response, as well as the short UV absorption edge and moderate birefringence, suggests Ba4B8TeO19 is a promising UV NLO material.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b00510. D

DOI: 10.1021/acs.inorgchem.8b00510 Inorg. Chem. XXXX, XXX, XXX−XXX

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Atomic coordinates and equivalent isotropic displacement parameters; selected bond lengths and angles; bond valence analysis; powder XRD patterns; crystal structure of Ba4B8TeO19; IR spectrum and UV−vis−NIR diffuse reflectance spectrum of Ba4B8TeO19; TG/DTA curves of Ba4B8TeO19; computed birefringence of Ba4B8TeO19. (PDF) Accession Codes

CCDC 1584831 contains 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 data_ [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Manuel Smeu: 0000-0001-9548-4623 P. Shiv Halasyamani: 0000-0003-1787-1040 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS L.L. and P.S.H. thank the Welch Foundation (Grant E-1457) and the National Science Foundation (DMR-1503573) for support. J.Y. and M.S. thank Binghamton University for support and providing the computational resources.

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DOI: 10.1021/acs.inorgchem.8b00510 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.8b00510 Inorg. Chem. XXXX, XXX, XXX−XXX