BaB2S4: An Efficient and Air-stable Thioborate as Infrared Nonlinear

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BaB2S4: An Efficient and Air-stable Thioborate as Infrared Nonlinear Optical Material with High Laser Damage Threshold Hao Li, Guangmao Li, Kui Wu, Bingbing Zhang, Zhihua Yang, and Shilie Pan Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.8b03642 • Publication Date (Web): 16 Oct 2018 Downloaded from http://pubs.acs.org on October 16, 2018

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Chemistry of Materials

BaB2S4: An Efficient and Air-stable Thioborate as Infrared Nonlinear Optical Material with High Laser Damage Threshold Hao Li,†‡# Guangmao Li,†# Kui Wu,† Bingbing Zhang,† Zhihua Yang,*† Shilie Pan*† †CAS

Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, CAS; Xinjiang Key Laboratory of Electronic Information Materials and Devices, 40-1 South Beijing Road, Urumqi 830011, China ‡University of Chinese Academy of Sciences, Beijing 100049, China ABSTRACT: The development of infrared (IR) laser still lacks the efficient IR frequency-conversion materials. Borates as critical nonlinear optical (NLO) materials have been achieved the deep UV to visible laser output, but they cannot satisfy the demand of IR laser limited by their low IR absorption edges. With this in mind, thioborates are focused by the optimization-based anionic group design through the replacement of B-O with the B-S units, which could extend the IR transmission range and simultaneously maintain the large bandgaps as well as strong NLO effects. Herein, the millimeter-level crystals of thioborate BaB2S4 compound (1.5 × 1.5 × 0.5 mm3) as a new breakthrough of IR NLO material with the suitable balance among wide bandgap (3.55 eV) and large second harmonic generation (SHG) effect (0.7 × AgGaS2), as well as high laser damage threshold (8 × benchmark AgGaS2) were successfully synthesized and exhibit good air stability, which breaks the prejudice of thioborates in air-sensitivity. These high laser damage threshold and unexpected air stability suggest the potential of thioborates applied as IR NLO materials. Remarkably, the theoretical calculation also analyzes the specific contribution for performances on the thioborates basic building units ([BS3]3and [BS4]5-), the result indicates that the [BS3]3- group can be expected as the excellent gene to design new promising IR NLO candidates.

Nonlinear optical (NLO) crystals are of great importance in producing coherent ultraviolet-visible (UV-vis), deep-UV (DUV) or infrared (IR) light sources for civil and military applications by frequency-conversion technology.1-23 Borates are widely applied as short-wave NLO materials because of their large bandgaps and high laser damage threshold that originate from strongly covalent B-O bonds in [BO3]3- and [BO4]5- anionic groups, such as β-BaB2O41, LiB3O52, and KBe2BO3F23, etc., unfortunately, they cannot be used in IR region because of absorption resulting from their B-O vibration modes which limits the infrared transmission. Meanwhile, chalcogenides6, owing to its wide optical transmission range and strong NLO response, are wildly researched for IR NLO materials. Recently, in view of the performance drawbacks (low laser damage threshold (LDT) and harmful two photon absorption) of commercial IR NLO materials,24-26 it is urgent to explore new excellent IR NLO materials27-33 with suitable balance between wide bandgap (Eg ≥ 3.0 eV) and large second harmonic generation (SHG) effect (NLO coefficient dij ≥ 0.5 × benchmark AgGaS2).34 Considering the advantages of borates and chalcogenides, we propose a feasible strategy by the optimization-based anionic group design from the B-O units to the B-S units taking borates as the template, for designing new IR NLO materials, namely, thioborates could own wide IR transmission range and simultaneously maintain the large bandgap as well as strong NLO effect. Interestingly, the B atoms exhibit the similar coordination environment ([BXn]: X = S, O; n = 3, 4) with the S or O atoms in the thioborates and borates (shown in Figure 1a). As we all know, the physicochemical properties of one material depend on its microstructural performances, especially on anionic groups.

Thus, we have focused on the diverse effect degrees between the anionic groups [BXn] and macroscopic performances of thioborates including vibration frequencies vs IR transmission range, HOMO-LUMO gap vs optical bandgap and hyperpolarizability vs SHG effect, respectively. Gaussian 09 package35 was performed to calculate these microstructural performances of [BX3] and [BX4] groups that are modeled as regular triangles and tetrahedra (See SI for more calculated details). As a result, the vibrational frequencies of [BSn] show obvious shift to low absorption energies (maximum 911 cm-1) in comparison with those of [BOn] (maximum 1452 cm-1), which shows that thioborates have the long IR absorption edge (911 cm-1, > 10 μm) that covers two atmospheric transparent windows (3–5 and 8–10 μm). In addition, the [BSn] groups still exhibit the large HOMO-LUMO gaps that benefit for enlarging the bandgap of thioborates. Note that the difference (1.3 eV) between [BS4]5- and [BS3]3- for HOMO-LUMO gaps is much smaller than that (2.6 eV) between [BO4]5- and [BO3]3, because of weak covalent bond. This smaller difference enables thioborates containing the [BS3]3- group to gain large bandgap. Moreover, calculated maximal hyperpolarizability values of the [BXn] groups show that |βmax| of [BSn] is obviously larger than that of [BOn], especially for [BS3]3displaying dozens of times that of typical [BO3]3- groups. The higher hyperpolarizability value suggests the ability of thioborates obtaining large second harmonic generation (SHG) effect.

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Table 1. Calculated optical properties (Eg and dij) of selected three thioborates (BaB2S4, LiSrB3S6 and LiBaB3S6).

Figure 1. Calculated properties of [BXn] (X = S, O; n = 3, 4) groups, including a) vibrational data, b) HOMO–LUMO gap, and c) hyperpolarizability (|βmax|).

To sum up, taking the above factors into consideration, thioborates can be expected as the optimal research system to explore new IR NLO materials. Herein, we have focused our attentions on the exploration of IR NLO materials in the thioborate system. Considering the demand of noncentrosymmety (the requirement for SHG effect), wide band gap and high LDT, the alkali and/or alkaline earth thioborates are focused on. Then, there are only three known compounds BaB2S436, LiSrB3S637 and LiBaB3S638 without atomic disorder.. The first-principles method was performed to predict their optical properties (shown in Table 1). Among these compounds, BaB2S4 shows a satisfactory balance between wide bandgap (calculated Eg = 3.63 eV > 3.5 eV) and large SHG effect (calculated d12 = 7.84 pm/V > 6.95 pm/V (0.5 × AgGaS2)), which is expected to be synthesized as a proming IR NLO material. Unfortunately, thioborates have been rarely investigated as IR NLO materials due to the highly hydroscopic prejudice for a long time. In this work, by optimizing synthesizing process, pure phase and millimeterlevel single crystals (colorless) of BaB2S4 were successfully synthesized by spontaneous crystallization. They are stable in air over half a year without any surface changes, which breaks the prejudice of air-sensitivity. Remarkably, the experimental results (Figure 3e) show that BaB2S4 exhibits the excellent performances including the wide Eg (3.55 eV), good SHG effect (0.7 × AgGaS2) with phase-matching ability, and high LDT (8 × AgGaS2), which indicates that these performances achieve the suitable balance between wide Eg and good dij that satisfy the performance demand as one excellent IR NLO material. The structure-performance relationship has also been studied systematically by the first-principle method and the result is consistent with that of our original propose that the [BSn] groups produce the main contribution for NLO effect, which also further proves the potential of thioborates as IR NLO candidates. Thioborates, just like borates, have a rich structural chemistry. The coordination numbers of the B atoms in thioborates can be either three (the [BS3]3- groups) or four (the [BS4]5- tetrahedra) forming 0D-cluster, 1D-chain, 2D-layer and 3D-network.39-41 Additionally, similar bond length between SS (1.890 Å) and B-S (2.078 Å)40 in perthioborates can make the connection modes of the B-S units more various structure types with unusual S-S bonds, including [B 2 S 5 ] 2- cluster 42 ,

Compounds

Space group

Eg(eV)

Calculated dij (pm/V)

BaB2S4

Cc

3.63

d11= 0.69; d12 = 7.84; d13= -6.88; d15= -0.64; d24= -3.18; d33= 1.11

LiSrB3S6

Cc

3.98

d11= -2.35; d12 = 2.69; d13= -0.69; d15= 2.06; d24= -2.88; d33= 0.82

LiBaB3S6

Cc

3.92

d11= -3.49; d12 = 3.22; d13= -0.62; d15= 1.99; d24= -3.16; d33= 0.57

[BS3]- chain43, [B3S10]3- chain43, and [B2S7]2- chain44. Trigonalplanar [BS3]3- units can tend to form isolated clusters, including [BS3]3-, [B2S4]2-, [B2S5]2- and [B3S6]3- etc.,45 and tetrahedral [BS4]5- units are always connected to form Tnsupertetrahedra cluster46,47, such as (B4S10)8- (T2)48 and (B10S20)10- (T3)48. However, the isolated (BS4)5– has not been observed so far. Based on our detailed literature survey, BaB2S4 is the only one containing the coexistence of trigonalplanar [BS3]3- and tetrahedral [BS4]5- units in the known alkali and/or alkaline earth thioborates so far. Note that the NLO properties of BaB2S4 have not been experimentally studied because of the difficulty of synthesis process caused by the SiB exchange over 650 oC.

Figure 2. Crystal structure of BaB2S4 formed by zigzag 1[B2S4 ]2chains ([BS3]3- and [BS4]5- arranged alternately) with Ba2+ filled in the inter-chains along c axis.

In this work, BaB2S4 was successfully synthesized and its structure and optical properties were characterized systematically. The optimal synthesis process includes two main tips: (1) the inner surface of silica tubes should be coated with a tight layer of carbon; (2) excess amorphous B powder should be added into the reaction. In this way, not only the polycrystalline, but also millimeter-level crystals were harvested. Crystallographic data are shown in Table S1. BaB2S4 crystallizes in the polar space group Cc (no. 9), its [BS3]3- and [BS4]5- units connect together by sharing corners to form the infinite zigzag 1[B2S4 ]2- chains along the c-axis, where the Ba2+ cations with eight-fold coordination number are located in the interchain (Figure2). The millimeter-level crystals of BaB2S4 are colorless and transparent (the largest one is 1.5 × 1.5 × 0.5 mm3 shown in Figure 3b). Powder X-ray diffraction analysis was performed with the microcrystals of BaB2S4 and the experimental and theoretical XRD patterns (derived from the CIF data) match well (shown in Figure 3a), which demonstrates the purity of the compound. Both the powder and crystals can stably exist


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Chemistry of Materials

Figure 3. The experimental and calculated results of BaB2S4. a) Powder XRD patterns of BaB2S4, theoretical and experimental results before and after half a year; b) The photograph of the BaB2S4 crystals; c) Optical spectra of BaB2S4. The inserted diagram is the experimental bandgap; d) SHG intensities of BaB2S4 and AgGaS2 at 2.09 μm radiation; e) Properties comparison between BaB2S4 and AgGaS2; f) SHG density of BaB2S4 at the occupied and unoccupied state of VE process.

in air (humidity < 20%), which could be revealed by the XRD pattern of BaB2S4 remeasured after half a year. The two patterns show no change with each other, which means that BaB2S4 is resistant to the oxygen in air and further proves the air-stability of BaB2S4. As shown in Figure 3c, the experimental Eg of BaB2S4 is 3.55 eV, which is much larger than that of commercial crystal AgGaS2 (2.64 eV49). General knowledge indicates a positive correlation between large Eg and high LDT.50,51 Thus, the powder LDT of BaB2S4 (ground AgGaS2 single crystals as the reference) was measured using a Q-switched pulse laser52 (1064 nm, 10 ns, 10 Hz). The results show that BaB2S4 has a high LDT of 265 MW/cm2, about 8 times that of benchmark AgGaS2 (33 MW/cm2). The SHG response as another important parameter was also studied with a 2.09 µm Q-switch laser using different particle sizes (shown in Figure 3d). The results show that it is type-І phase-matchable and exhibits the good SHG response about 0.7 times that of AgGaS2 at the maximum particle size. The dispersions of the linear refractive indices for BaB2S4 were calculated using the CASTEP package53 and a so-called length-gauge formalism54,55 was adopted to estimate its SHG coefficients, which has the capability to obtain the accurate results in metal chalcogenides. The calculated birefringence ([email protected] µm) of BaB2S4 confirms its type-І phase-matchability. BaB2S4 belongs to Cc point symmetry and has six independent SHG coefficients (Revised results based on the experimental bandgap shown in Table S3), and the maximum value (d12 = 8.22 pm/V) is about 0.66 times that of AgGaS2 (12.5 pm/V)49, which is consistent with the result obtained by Kurtz powder measurement technique52. All above results demonstrate that BaB2S4 has a high LDT that optimizes the drawback of AgGaS2, satisfies the good balance between wide Eg (≥3.0 eV) and large dij (≥0.5 × AgGaS2) and BaB2S4 could be regarded as a promising IR NLO candidate.

To deeply study the relationship between the structure and property, SHG density diagram56,57 of BaB2S4 was also calculated to quantify the SHG contribution. The SHG process is denoted by two virtual transition processes, namely virtual electron (VE) and virtual hole (VH) processes. The obvious contribution of VE process (~ 65.5%) for the largest SHG tensors (d12) indicates that its SHG effect mainly comes from the VE process. Figure 3f shows the SHG densities of BaB2S4 at the occupied state and unoccupied state in VE processes. It could be seen that the [BSn] groups make the main contribution to the SHG coefficient. Moreover, a real-space atom-cutting technique58 was adopted to further determine the proportion of [BS3]3- and [BS4]5- in detail, respectively. As shown in Table S4, the contribution of [BS3]3- is 6.1 times that of [BS4]5-, which is corresponding to the previous hyperpolarizability ratio (5.9) and has further verified that [BS3]3- has larger contribution to SHG response compared with [BS4]5-. As another important feature, the preferred bandgap of a promising IR NLO material should be larger than 3.0 eV. To further check whether the bandgaps of thioborates with the [BSn] groups are suitable, HSE06 hybrid functional59 was adopted to simulate the bandgaps of alkali/alkaline-earth metal thioborates, and the results are shown in Table S2. The calculated values of BaB2S4 and AgGaS2 are 3.63 and 2.40 eV, respectively, which are in accordance with the experimental ones of 3.55 and 2.64 eV, respectively, illustrating the reliability of the HSE06 hybrid function. From Table S2, it is clear that all the bandgaps of the selected thioborates are larger than 3.0 eV, accordingly larger than that of AgGaS2. Because of the positive correlation between large Eg and high LDT, the LDTs of alkali/alkaline-earth metal thioborates could be larger than that of AgGaS2, which benefit for searching promising IR NLO materials in this system. In the process, it can be found that Li2CsBS3 has a large bandgap of 4.10 eV and its anionic group is only [BS3]3-, which means that the [BS3]3- group



could lead to a large bandgap. Together with the large susceptibility, parallel alignment of [BS3]3- in the structure of one material may produce high SHG effect, spontaneously keep a large bandgap. In summary, we proposed an optimization-based anionic group design strategy: changing the [BOn] groups to the [BSn] groups, the microscopic groups and corresponding macroscopic property are studied by the theoretical and experimental methods. The results show that thioborates can broaden IR absorption edge and reserve the large band gap, as well as strong SHG effect. Based on the above strategy, an excellent IR NLO material BaB2S4 with the good balance between bandgap (3.55 eV) and SHG effect (about 0.7 times of AgGaS2), additionally a high LDT about 8 times that of AgGaS2 was discovered. Moreover, air-stable millimeter-level single crystals of BaB2S4 were obtained, which breaks the prejudice of air-sensitivity for thioborates. Meanwhile, the [BS3]3- group is also proven as an excellent NLO active unit, which not only holds the large bandgap, but also exhibits the high SHG effect. It suggests that thioborates with proper arrangement of trigonal planar [BS3]3- units might exhibit the greatly integrated performances as promising IR NLO materials.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website. Synthetic methods, experimental details, structural refinement and crystal data, details for anionic group model building, computational details. IR spectrum, thermal gravimetric and differential scanning calorimetry curves additional tables, as well as additional tables. (PDF). CIF file (cif)

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] *E-mail: [email protected].

Author Contributions Hao Li: 0000-0002-3388-0740 Bingbing Zhang: 0000-0002-1334-5812 Zhihua Yang: 0000-0001-9214-3612 Shilie Pan: 0000-0003-4521-4507

Author Contributions #H.L.

proposed the main idea and performed predictions. G.L. performed all experimental work. S.P., Z.Y., K.W. and B.Z. conceived and designed the experiments. H.L., G.L. and K.W. wrote the draft paper. All the authors discussed the results and commented on the manuscript.

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT This work was supported by National Natural Science Foundation of China (Grant Nos. 51872324, 91622107, 51425206,11774414, 11474353), National Basic Research Program of China (Grant No. 2014CB648400), the Western Light Foundation of CAS (Grant Nos. 2016-YJRC-2, 2016-QNXZ-B-9), National Key Research Project (Grant Nos. 2016YFB1102302, 2016YFB0402104) and Foundation of Director of XTIPC, CAS (Grant No. 2016PY004).

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BaB2S4: An Efficient and Air-stable Thioborate as Infrared Nonlinear

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