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Article

Cd4InO(BO3)3: A New Nonlinear Optical Crystal Exhibiting Strong Second Harmonic Generation Effect and Moderate Birefringence

by
Runqing Liu
1,2,
Hongping Wu
1,
Hongwei Yu
1,*,
Zhanggui Hu
1,
Jiyang Wang
1 and
Yicheng Wu
1
1
Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystals, College of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, China
2
College of Material and Chemical Engieering, Tongren University, Tongren 554300, China
*
Author to whom correspondence should be addressed.
Crystals 2022, 12(2), 266; https://doi.org/10.3390/cryst12020266
Submission received: 20 December 2021 / Revised: 28 January 2022 / Accepted: 29 January 2022 / Published: 15 February 2022
(This article belongs to the Special Issue Recent Advances in Nonlinear Optical Crystals)
Browse Figures
Versions Notes

Abstract

:
A new noncentrosymmetric cadmium indium borate, Cd4InO(BO3)3 (CIBO) has been successfully developed via a standard solid-state reaction. Its crystal structure was confirmed by the single crystal X-ray diffraction, which shows that CIBO belongs to the non-centrosymmetric and polar space group Cm. Its structure contains the distorted InO6 and CdOn (n = 6, 8) polyhedra, which link together by sharing an edge or corner to build a three dimensions framework with BO3 triangles accommodated in tunnels. Benefiting from the approximately parallel configuration of BO3 triangles, CIBO exhibited a strong second harmonic generation (SHG) effect (3 × KDP), and moderate birefringence of 0.077@1064 nm. Further optical and thermal characterizations suggest that CIBO possesses a wide transparent window and good thermal stability. Theoretical calculation reveals that the macroscopic SHG coefficients of CIBO results from the synergistic effect of the parallel arrangement of BO3 groups and d10 Cd2+ cation.

1. Introduction

Nonlinear optical (NLO) crystals that can expand the wavelength of a solid-state laser by second-harmonic generation (SHG) have been applied at the forefront of scientific and technological research, such as medicine, scientific research, civil industries, etc. [1,2,3,4]. However, an available NLO crystal must satisfy some structure and performance requirements. Structurally, only non-centrosymmetric (NCS) crystalline materials can exhibit the SHG response [5,6]. As for the properties, NLO crystals also need to possess a large SHG response and moderate birefringence, which are essential to realize phase-matching (PM) in the desired wavelength range and obtain high laser conversion efficiency [7,8,9]. However, it was exceptionally challenging to simultaneously maximize these two optical parameters [10,11]. For example, BPO4 [12], LiGeBO4 [13], and SrB4O7 [14] all exhibited strong SHG responses, originating from the aligned arrangements of tetrahedral BO4 units, but they suffered from a too-small birefringence to achieve a PM condition in transmittance regions. On the contrary, Li2B4O7 and KB5O8·4H2O possessed moderate birefringence and wide transmission range, unfortunately, their weak SHG responses hindered practical applications [15,16]. Therefore, exploring new NLO materials with a large SHG response and moderate birefringence were consequently of enormous current academic and commercial interest.
Traditionally, inorganic planar π-conjugated systems, including borates [17,18,19], cyanurates [20,21], carbonates [22,23], and nitrates [24,25], were excellent candidates for NLO materials because their delocalized π-conjugated groups, such as (BO3)3−, (C3N3O3)3−, (CO3)2−, and (NO3)−. Generally, these units possessed high NCS possibility, strong SHG responses, wide transmittance window, and strong anisotropy [26,27,28]. For instances, KBe2BO3F2 (KBBF) [29], Ca3(C3N3O3)2 [30], and β-Sr3(C3N3O3)2 [31], etc. all exhibited a large birefringence and/or strong SHG coefficients due to the π-conjugated of anionic groups [32,33]. However, it should also be noted that most cyanurates, carbonates, and nitrates were not thermally stable [34]. They often tended to decompose at a high temperature. Therefore, π-conjugated (BO3)3− groups were preferred as the most ideal structural motif for the design of new NLO materials, and a wide range of compounds with the π-conjugated (BO3)3− groups as the basic building units have been synthesized, including KBe2BO3F2 [29], Pb2Ba3(BO3)3Cl [35], Cd4BiO(BO3)3 [18], Li4Sr(BO3)2 [36], Bi3TeBO9 [37], and BaYBO4 [38], etc.
Beyond the π-conjugated systems, introducing some polar distorted polyhedra were also favorable for a large SHG response and birefringence, including the polyhedra with the canter of d10 cations (such as Zn2+, Cd2+, and Hg2+) [11,17,39,40], d0 cations (such as V5+, Mo6+, W6+, Ti4+, etc.) [41,42,43,44], and stereo-chemical active lone pair (SCALP) cations (such as, Bi3+, Te4+, Sn2+ Pb2+, I5+, etc.) [18,35,42,45,46,47]. These cations with second-order Jahn–Teller (SOJT) effects could enhance the birefringence and SHG effect of NLO materials. For example, Sn2B5O9Cl [48] exhibited lager birefringence (0.168@546 nm) than Ba2B5O9Cl [49] (0.010@546 nm) due to the unique [SnO7Cl2] polyhedra with SCALP. Cd4BiO(BO3)3 [18] (6.0 × KDP) and Bi3TeBO9 [37] (20.0 × KDP), displayed extremely strong SHG responses due to the synergistic effects of the BiO6, CdOn (n = 6, 7)/TeO6 polyhedra and the π-conjugated BO3 groups. Thus, the incorporation of the above asymmetric chromophores into borates was a fruitful strategy for designing high-performance NLO crystals.
Inspired by the above ideas, we assembled the π-conjugated BO3 triangles with polar displacement of d10 Cd2+ cations to explore new NLO materials, and successfully synthesized a new NLO crystal, Cd4InO(BO3)3 (CIBO), which exhibited a strong SHG effect (3.0 × KDP), moderate birefringence (0.077@1064), suitable band gap, and wide transparent range. Herein, the synthesis, crystal structure, thermal behavior, spectrum, and NLO properties of CIBO were reported. Theoretical calculations have also been carried to elaborate the relation between its structure and performance. It manifested that CIBO was a promising candidate as new NLO material.

2. Experiment Sections

2.1. Syntheses and Crystal Growth

2.1.1. Reagents

The raw materials of In2O3 (Aladdin Chemistry Co., Ltd., 99.9%), CdO (Tianjin Fu Chen Chemical Co., Ltd., 99%), PbO (Tianjin Fu Chen Chemical Co., Ltd., 99%), and H3BO3 (Aladdin Chemistry Co., Ltd., 99%) were used.

2.1.2. Single Crystal Preparation

Single crystals of CIBO were prepared using the high-temperature solution method. A mixture of In2O3, H3BO3, CdO, and PbO at a molar ratio of 0.25:3.5:4:2 was placed into a Φ 20 × 20 mm platinum (Pt) crucible. Then, the crucible was placed in the center of the furnace, and heated slowly to 300 °C in order to release H2O. Then, the temperature was slowly raised to 960 °C and maintained 24 h to form a homogeneous melt. Subsequently, the homogeneous melt was cooled to 860 °C at a rate of 3 °C/h, and then cooled to room temperature by turning off the furnace. Thus, some colorless and transparent single crystals were obtained for the structure determination.

2.1.3. Polycrystalline Synthesis

The powder sample of CIBO was prepared by conventional solid-state reactions. A mixture of CdO, In2O3, and H3BO3 with a molar ratio of 4:0.5:3 was grounded homogeneously in an agate mortar and transferred into a crucible placed into a programmable furnace. The mixtures were preheated at 350 °C for 10 h to decompose the boron acid, then sintered at 850 °C and maintained for 72 h with several intermediate grindings. The pure phase of CIBO was obtained and characterized by a powder X-ray diffraction method.

2.1.4. Powder X-ray Diffraction

The Smart Lab 9 KW X-ray diffractometer was used to collect the Powder-XRD (PXRD) at room temperature. Data were collected in the 2θ ranging from 10° to 70° using monochromatized Cu-Kα radiation (λ = 1.5418 Å) with a step size of 0.02° and a step time of 2 s. The theoretical XRD patterns were well agreement with experimental PXRD patterns. Mercury software was used for the simulation of the CIBO PXRD pattern.

2.1.5. Single Crystal X-ray Diffraction

A colorless single crystal suitable for the determination of the CIBO compound was mounted on a Bruker D8 Venture APEX II CCD diffractometer with Mo Kα (λ = 0.71073 Å) radiation at 298(2) K. The dates were integrated by the SAINT program [50]. The crystal structure was solved by direct methods SHELXs and refined on F2 by full-matrix least-squares techniques using the program SHELXTL [51]. The structure was checked for missing symmetry elements using PLATON [52]. Details of crystal parameters, data collection, and structure refinement were listed in Table S1. The atom coordinates, the related anisotropic displacement parameters, and bond valance sums (BVSs) are listed in Tables S2 and S3 [53], and the selected bond lengths and angles are presented in Table S4.

2.1.6. Thermal Behaviors

The NETZCH STA 449F3 simultaneous analyzer was used to collect the thermal gravimetric (TG) and differential scanning calorimetry (DSC) data of CIBO. About 10 mg of CIBO samples was placed in the Pt crucibles, and heated at a rate of 5 °C/min in the range of 40–1100 °C under a nitrogen atmosphere.

2.1.7. UV-Vis-NIR Diffuse Reflectance Spectrum

The UV-Vis-NIR diffuse-reflectance data of the sample was obtained on a Hitachi UH4150 UV-vis-NIR spectrophotometer with BaSO4 as the standard of 100% reflectance in the wavelength of 240–2500 nm. The reflectance spectra were converted to absorbance using the Kubelka–Munk function F(R) = (1 − R)2/2R = K/S, where R, K, and S are the reflectance, absorption, and scattering, respectively [54].

2.1.8. Infrared Spectrum

The Fourier transform infrared (FTIR) spectra of CIBO were measured in the range of 4000–400 cm−1 using a Nicolet iS50 Fourier transform infrared spectrometer with a smart orbit attenuated total reflectance (ATR) accessory.

2.1.9. Birefringence Measurement

Birefringence of CIBO was captured on a Nikon Eclipse polarizing microscope E200MV POL with a visible light filter. On the basis of the crystal optics, the birefringence was calculated from the following formula:
R = (|Ne − No|) d = Δn × d
where R, Δn, and d are retardation, birefringence, and thickness, respectively [55].

2.1.10. Powder SHG Measurement

The powder second-harmonic generation (SHG) responses of CIBO were carried out on a Kurtz-NLO system with a 1064 nm Q-switched Nd: YAG laser. According the method of Kurtz and Perry, the SHG intensity was strongly dependent on the particle size of the samples, so the polycrystalline samples of CIBO and KH2PO4 (KDP) were ground and sieved into different particle size ranges (54–75, 76–106, 107–120, 121–150, and 151–180 μm) and KDP served as the reference. The measurements were performed on a 1064 nm Q-switched Nd: YAG laser under the same voltage. [56]

2.1.11. Computational Method

To investigate the relationship between the electronic-structure and optical properties of CIBO. The calculations of the band structure and density of state (DOS) of CIBO were performed by CASTEP based on density functional theory (DFT) [57]. During the calculation, the generalized gradient approximation (GGA) with the Perdew–Burke–Ernzerhof (PBE) function was selected to describe the exchange correlation energy. Under the norm-conserving pseudopotentials (NCP) [58], the valence electrons were set as follows: Cd-4d105s2, In-5s25p1, B-2s22p1, and O-2s22p4. The kinetic energy cutoff of 850 eV and the Monk-horst Pack k-point meshes with a density of (4 × 4 × 7) points in the Brillouin zone were adopted. The cell parameters and atomic positions are optimized using the quasi-Newton method. The linear optical properties of CIBO were calculated by the dielectric function ε(ω) = ε1(ω) + iε2(ω). The ε2(ω) were deduced from the matrix elements that describe the electronic transitions between the occupied and unoccupied states in the CIBO compound. Accordingly, the refractive indices and birefringence (Δn) can be calculated.

3. Results and Discussion

3.1. Crystal Structure of CIBO

CIBO crystallizes in the monoclinic crystal system with an acentric and polar space group of Cm. In the asymmetric unit, CIBO contains one independent In, two Cd, six O, and two B atom(s), respectively. Two different B atoms, B(1) and B(2), coordinated three oxygen atoms to form planar BO3 triangles with B–O bond lengths ranging from 1.330(2) to 1.390(2) Å. The B(1)O3 and B(2)O3 groups were almost oriented parallel to the ab plane, which contributed a large SHG effect and birefringence, as shown in Figure 1. The In(1)3+ cations were six-fold coordinated to form an In(1)O6 octahedra with bond lengths in the range of 2.110(2)–2.226(14) Å. The two types of Cd2+ ions, Cd(1)2+ and Cd(2)2+ cations, were six-fold and eight-fold coordinated to form distorted Cd(1)O6 and Cd(2)O8 polyhedra, respectively. For the Cd−O bonds, their bonds lengths in the range of 2.248(10)–2.801(3) Å. In the structure, Cd(1)O6 and Cd(2)O8 polyhedra interconnect to construct a 1D [Cd2O12] double-chains via edge-sharing and corner-sharing. The In(1)O6 polyhedra also linked with each other via corner-sharing to form the 1D [InO6] single-chain, as shown in Figure 1a. Furthermore, the 1D [Cd2O12] double-chains and [InO6] single-chain connect together by sharing common oxygen atoms to form a 3D framework with the BO3 triangles filled in the tunnels (Figure 1b).
Structurally, CIBO was isostructural with the Cd4ReO(BO3)3 (Re = Y, Gd, Lu), its structure can be considered as the Re3+ cation in Cd4ReO(BO3)3 is replaced by the In3+ cations, and they all presented the classical apatite-like structure [59]. These indicated the feasibility of the substitution of In3+ for rare-earth cations during synthesizing new NLO crystals. Besides, the bond valence sums results [53] were 1.871 to 2.124 for O2−, 2.230 and 1.971 for Cd2+, 3.031 for In3+, and 2.920 and 3.124 for B3+, (Table S2), which were very close to the ideal oxidation, indicating the correctness of the structure.

3.2. UV-Vis-NIR Diffuse Reflectance Spectrum

UV–vis–NIR diffuse reflectance spectrum of the synthesized polycrystalline samples was measured in the range of 240–2500 nm. It reveals that CIBO has a cut-off edge of approximately 313 nm (Figure S1), which is comparable with its isostructural compounds Cd4ReO(BO3)3 (Re = Y, Gd, Lu) whose cut-off edges were approximately 320 nm [59]. Absorption (K/S) data were calculated from the Kubelka–Munk function and manifested that the optical band gap for CIBO was about 3.40 eV (Figure S1).

3.3. Infrared Spectrum

The Infrared Spectrum of CIBO is shown in Figure S2. The peaks at 1174 cm−1 and 933 cm−1 can be assigned to the asymmetric stretching vibrations of the BO3 group [60,61]. The peaks located at 707 cm−1 and 583 cm−1 were assigned as the bending vibrations of BO3 groups. The assignments matched well with those of reported solids containing BO3 groups in the literature [18,35].

3.4. Thermal Analysis

Thermal property of CIBO was performed on a TG−DSC instrument, as shown in Figure 2a. There was one endothermic peak observed at 963 °C on the DSC curve. Meanwhile, the weight loss can also be observed on the TG curve, indicating the CIBO should be an incongruently melting compound. In addition, the powder samples of CIBO were sintered at 1100 °C and cooled down to 900 °C with the rate of 10 °C/h, following a cooled to room temperature by turning off the furnace. The sample was analyzed by the XRD as shown in Figure 2b, which was completely different form the simulated one, further indicating that the compound melts incongruently around 963 °C. Thus, the CIBO single crystals must be grown using the flux growth technique.

3.5. Birefringence Measurements

The birefringence of CIBO was performed on a cross-polarizing microscope. As shown in Figure 3a, the observed interference color in cross-polarized light were the III-order green. According to the Michel–Levy chart, the retardation (R value) for CIBO was 1350 nm and its crystal thickness was measured as 18.1 μm [62,63]. Thus, the birefringence of CIBO in the visible region can be calculated as 0.075 based on Equation (1) [55]. Furthermore, the birefringence of CIBO was also executed based on the theoretical calculation and the calculated result shows that CIBO exhibited a relatively large birefringence of about 0.077@1064 nm (Figure 3b). The experimental value was consistent with the calculated one and greater than that of Cd5(BO3)3Cl (0.054@1064 nm) [64], Ca4YO(BO3)3 (0.043@589 nm) [65], and Ca5(BO3)3F (0.043@589 nm) [65]. The large birefringence of CIBO was beneficial to phase matching in the transparent region.

3.6. Nonlinear Optical Properties

CIBO crystallizes in the NCS space group of Cm, so its NLO properties at 1064 nm fundamental light irradiation were also performed. As shown in Figure 4, the SHG effects become larger with the increasing particles size of the CIBO powders, which suggested that the CIBO is phase-matching according to the rule proposed by Kurtz and Perry [56,66,67]. CIBO has a powder SHG effect about three times of KDP. According to the anionic-group theory [68], the SHG response of NLO materials primary attributes to the anionic group, so the BO3 groups play a key role in the structure [69]. As show in Figure 1b, the arrangement of the BO3 units is approximately parallel to the (001) plane, which contributed to the large SHG effect. Additionally, the number density of BO3 triangles (n/V) was 0.0144 per unit volume for CIBO, which was comparable to those of the reported Cd borates nonlinear optical material, such as CdZn2(BO3)2 (0.0082 per unit volume) [70], and Zn3Cd3(BO3)4 (0.016 per unit volume) [71].
The dipole moment calculation of CIBO was also calculated by the bond valence model [72]. The CdOn (n = 6, 8) polyhedra and BO3 units were performed, respectively. As shown in Table S5, the total net dipole moment of BO3 groups in the unit cell yield 1.025 Debey (D), which is approximately 54.45% of its optimal value. Meanwhile, the Cd−O polyhedra also contributes to the dipole moment of 0.878 D. Therefore, the synergistic effects of the NLO-active BO3 groups and the d10 Cd2+ cations in CIBO endowed the material with a large SHG effect, which is comparable with LiB3O5 [60] and Cd5(BO3)3F [73].

3.7. Electronic Structure

Theoretical calculations of CIBO were carried out by the plane-wave pseudopotential method performed on the CASTEP package based on the density functional theory [57]. CIBO exhibited an indirect band gap of 1.68 eV, as shown in Figure 5a, which was smaller than the experimental values because of the limitation of the GGA−PBE function [74]. Figure 5b shows that the density of states (DOS) and partial DOS of CIBO, which presented that the top of the valence band was mainly made up of the Cd-4d, O-2p orbitals with a mix of B-2p orbitals. The bottom of the conduction band mainly originates from the B-2p and O-2p orbitals. Therefore, the optical properties of CIBO mainly originate from the synergistic effect of BO3 groups and the d10 cation Cd2+.

4. Conclusions

In conclusion, a new NLO material CIBO was reported. The title compound exhibited a 3D framework composed of CdO6, CdO8, and InO6 polyhedra where the B atoms are located in the tunnels. CIBO exhibits a large SHG response about three times that of KDP and a moderate birefringence of 0.077@1064 nm, which mainly originated from the well arrangement and high density of BO3 groups, as well as the d10 Cd2+ cation. The IR and UV−Vis−IR diffuse reflectance spectra indicated that CIBO possess BO3 groups and a wide transparent region, respectively. TG−DSC manifests that the CIBO has good thermal stability up to 963 °C. We hope that these findings will shed valuable information on the development of new NLO materials.

Supplementary Materials

The following are available online at https://www.mdpi.com/article/10.3390/cryst12020266/s1. Figure S1: UV−Vis−NIR diffuse reflectance spectroscopy of CIBO. Figure S2: IR Spectroscopy of CIBO. Table S1: Crystal data and structure refinement for CIBO. Table S2: Atomic coordinates and equivalent isotropic atomic displacement parameters (Å2) for CIBO. Table S3: Bond lengths (Å) for CIBO. Table S4: Bond angles (°) for CIBO. Table S5. Dipole moments of BO3 and CdOn (n = 6, 8) polyhedra in the unit cell. Table S6: The assignments of the Infrared absorption peaks for CIBO.

Author Contributions

R.L.: Writing—Original draft preparation. H.W.: First-principle calculations. H.Y.: Conceptualization, Methodology. Z.H.: Crystal Refinement. J.W. and Y.W.: Revised Manuscript. All authors have read and agreed to the published version of the manuscript.

Funding

We acknowledge financial support from the Natural Science Foundation of Tianjin (19JCZDJC38200), the Science Fund for Distinguished Young Scholars of Tianjin (20JCJQJC00060), the National Natural Science Foundation of China (grant no. 22071179, 51890864, 51802217, 51972230, 61835014, and 51890865), and the National Key R&D Program (grant no. 2016YFB0402103).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Ahmadivand, A.; Gerislioglu, B. Deep- and vacuum-ultraviolet metaphotonic light sources. Mater. Today 2021, 51, 208–221. [Google Scholar] [CrossRef]
  2. Liu, H.; Zhang, B.; Li, L.; Wang, Y. Exploring deep-UV nonlinear optical materials with enhanced second harmonic generation response and birefringence in fluoroaluminoborate crystals. ACS Appl. Mater. Inter. 2021, 13, 30853–30860. [Google Scholar] [CrossRef]
  3. Hu, Y.; Wu, C.; Jiang, X.; Wang, Z.; Huang, Z.; Lin, Z.; Long, X.; Humphrey, M.G.; Zhang, C. Giant second-harmonic generation response and large band gap in the partially fluorinated Mid-Infrared oxide RbTeMo2O8F. J. Am. Chem. Soc. 2021, 143, 12455–12459. [Google Scholar] [CrossRef]
  4. Chen, Q.; Luo, M.; Lin, C. Na4Yb(CO3)3F: A New UV Nonlinear Optical Material with a Large Second Harmonic Generation Response. Crystals 2018, 8, 381. [Google Scholar] [CrossRef] [Green Version]
  5. Cammarata, A.; Zhang, W.; Halasyamani, P.S.; Rondinelli, J.M. Microscopic origins of optical second harmonic generation in noncentrosymmetric-nonpolar materials. Chem. Mater. 2014, 26, 5773–5781. [Google Scholar] [CrossRef]
  6. Li, C.; Wang, X.; Wu, Y.; Liang, F.; Wang, F.; Zhao, X.; Yu, H.; Zhang, H. Three-dimensional nonlinear photonic crystal in naturally grown potassium-tantalate-niobate perovskite ferroelectrics. Light Sci. Appl. 2020, 9, 193–197. [Google Scholar] [CrossRef]
  7. Wang, Y.; Zhang, B.; Yang, Z.; Pan, S. Cation-tuned synthesis of fluorooxoborates: Towards optimal deep-ultraviolet nonlinear optical materials. Angew. Chem. Int. Ed. 2018, 57, 2150–2154. [Google Scholar] [CrossRef]
  8. Shao, M.; Liang, F.; Yu, H.; Zhang, H. Pushing periodic-disorder-induced phase matching into the deep-ultraviolet spectral region: Theory and demonstration. Light Sci. Appl. 2020, 9, 45–49. [Google Scholar] [CrossRef] [Green Version]
  9. Ahmadivand, A.; Semmlinger, M.; Dong, L.; Gerislioglu, B.; Nordlander, P.; Halas, N.J. Toroidal Dipole-Enhanced Third Harmonic Generation of Deep Ultraviolet Light Using Plasmonic Meta-atoms. Nano Lett. 2019, 19, 605–611. [Google Scholar] [CrossRef]
  10. Chen, C.T.; Wang, Y.B.; Wu, B.C.; Wu, K.C.; Zeng, W.L.; Yu, L.H. Design and synthesis of an ultraviolet-transparent nonlinear-optical crystal Sr2Be2B2O7. Nature 1995, 373, 322–324. [Google Scholar] [CrossRef]
  11. Wang, X.; Zhang, F.; Gao, L.; Yang, Z.; Pan, S. Nontoxic KBBF family member Zn2BO3(OH): Balance between beneficial layered structure and layer tendency. Adv. Sci. 2019, 6, 1901679–1901685. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  12. Li, Z.; Lin, Z.; Wu, Y.; Fu, P.; Wang, Z.; Chen, C. Crystal Growth, Optical Properties Measurement, and Theoretical Calculation of BPO4. Chem. Mater. 2004, 16, 2906–2908. [Google Scholar] [CrossRef]
  13. Liu, Q.; Hu, C.; Su, X.; Abudoureheman, M.; Pan, S.; Yang, Z. LiGeBO4: A nonlinear optical material with a balance between deep-ultraviolet cut-off edge and large SHG response induced by hand-in-hand tetrahedra. Inorg. Chem. Front. 2019, 6, 914–919. [Google Scholar] [CrossRef]
  14. Dolzhenkova, E.F.; Baumer, V.N.; Tolmachev, A.V.; Oseledchik, Y.S. On the nature of fracture of SrB4O7 and PbB4O7 single crystals. Crystallogr. Rep. 2007, 52, 889–893. [Google Scholar] [CrossRef]
  15. Tran, T.T.; Yu, H.; Rondinelli, J.M.; Poeppelmeier, K.R.; Halasyamani, P.S. Deep ultraviolet nonlinear optical materials. Chem. Mater. 2016, 28, 5238–5258. [Google Scholar] [CrossRef]
  16. Yang, Y.; Qiu, Y.; Gong, P.; Huang, Q.; Zhao, S.; Luo, S.; Sun, J.; Lin, Z. Synthesis, structure, and properties of the non-centrosymmeteric compound LiNaRbB5O8(OH)2. Cryst. Growth Des. 2018, 18, 5745–5749. [Google Scholar] [CrossRef]
  17. Yang, G.; Gong, P.; Lin, Z.; Ye, N. AZn2BO3X2 (A = K, Rb, NH4; X = Cl, Br): New members of KBBF family exhibiting large SHG response and the enhancement of layer interaction by modified structures. Chem. Mater. 2016, 28, 9122–9131. [Google Scholar] [CrossRef]
  18. Zhang, W.L.; Cheng, W.D.; Zhang, H.; Geng, L.; Lin, C.S.; He, Z.Z. A strong second-harmonic generation material Cd4BiO(BO3)3 originating from 3-chromophore asymmetric structures. J. Am. Chem. Soc. 2010, 132, 1508–1509. [Google Scholar] [CrossRef]
  19. Xie, Z.; Mutailipu, M.; He, G.; Han, G.; Wang, Y.; Yang, Z.; Zhang, M.; Pan, S. A series of rare-earth borates K7MRE2B15O30 (M = Zn, Cd, Pb; RE = Sc, Y, Gd, Lu) with large second harmonic generation responses. Chem. Mater. 2018, 30, 2414–2423. [Google Scholar] [CrossRef]
  20. Xia, M.; Zhou, M.; Liang, F.; Meng, X.; Yao, J.; Lin, Z.; Li, R. Noncentrosymmetric cubic cyanurate K6Cd3(C3N3O3)4 containing isolated planar π-conjugated (C3N3O3)3− Groups. Inorg. Chem. 2018, 57, 32–36. [Google Scholar] [CrossRef]
  21. Lu, J.; Lian, Y.K.; Xiong, L.; Wu, Q.R.; Zhao, M.; Shi, K.X.; Chen, L.; Wu, L.M. How to maximize birefringence and nonlinearity of π-conjugated cyanurates. J. Am. Chem. Soc. 2019, 141, 16151–16159. [Google Scholar] [CrossRef] [PubMed]
  22. Yang, G.; Peng, G.; Ye, N.; Wang, J.; Luo, M.; Yan, T.; Zhou, Y. Structural modulation of anionic group architectures by cations to optimize SHG effects: A facile route to new NLO materials in the ATCO3F (A = K, Rb; T = Zn, Cd) series. Chem. Mater. 2015, 27, 7520–7530. [Google Scholar] [CrossRef]
  23. Peng, G.; Lin, C.; Ye, N. NaZnCO3(OH): A high-performance carbonate ultraviolet nonlinear optical crystal derived from KBe2BO3F2. J. Am. Chem. Soc. 2020, 142, 20542–20546. [Google Scholar] [CrossRef]
  24. Hao, X.; Luo, M.; Lin, C.; Peng, G.; Yan, T.; Lin, D.; Cao, L.; Long, X.; Yang, G.; Ye, N. A(H3C3N3O3)(NO3) (A = K, Rb): Alkali-metal nitrate isocyanurates with strong optical anisotropy. Inorg. Chem. 2020, 59, 10361–10367. [Google Scholar] [CrossRef] [PubMed]
  25. Kim, M.K.; Jo, V.; Ok, K.M. New variant of highly symmetric layered perovskite with coordinated NO3- ligand: Hydrothermal synthesis, structure, and characterization of Cs2PbCl2(NO3)2. Inorg. Chem. 2009, 48, 7368–7372. [Google Scholar] [CrossRef]
  26. Huang, H.; Yao, J.; Lin, Z.; Wang, X.; He, R.; Yao, W.; Zhai, N.; Chen, C. Molecular engineering design to resolve the layering habit and polymorphism problems in deep UV NLO crystals: New structures in MM′Be2B2O6F (M = Na, M′ = Ca; M = K, M′ = Ca, Sr). Chem. Mater. 2011, 23, 5457–5463. [Google Scholar] [CrossRef]
  27. Xue, D.; Zhang, S. Structural analysis of nonlinearities of Ca4ReO(BO3)3 (Re = La, Nd, Sm, Gd, Er, Y). Appl. Phys. A 1999, 68, 57–61. [Google Scholar] [CrossRef]
  28. Li, Z.; Liang, F.; Guo, Y.; Lin, Z.; Yao, J.; Zhang, G.; Yin, W.; Wu, Y.; Chen, C. Ba2M(C3N3O3)2 (M = Mg, Ca): Potential UV birefringent materials with strengthened optical anisotropy originating from the (C3N3O3)3− group. J. Mater. Chem. C 2018, 6, 2879–12887. [Google Scholar] [CrossRef]
  29. Yang, G.; Wu, K. Two-Dimensional Deep-ultraviolet beryllium-free KBe2BO3F2 Family Nonlinear-Optical Monolayer. Inorg. Chem. 2018, 57, 7503–7506. [Google Scholar] [CrossRef]
  30. Kalmutzki, M.; Wang, X.; Meixner, A.J.; Meyer, H.J. Second harmonic generation properties of Ca3(O3C3N3)2− Sr3(O3C3N3)2 solid solutions. Cryst. Res. Technol. 2016, 51, 460–465. [Google Scholar] [CrossRef]
  31. Kalmutzki, M.; Ströbele, M.; Wackenhut, F.; Meixner, A.J.; Meyer, H.J. Synthesis and SHG properties of two new cyanurates: Sr3(O3C3N3)2 (SCY) and Eu3(O3C3N3)2 (ECY). Inorg. Chem. 2014, 53, 12540–12545. [Google Scholar] [CrossRef] [PubMed]
  32. Chen, Y.; Hu, C.; Fang, Z.; Mao, J. K2Pb(H2C3N3O3)4(H2O)4: A potential UV nonlinear optical material with large birefringence. Inorg. Chem. Front. 2021, 8, 3547–3555. [Google Scholar] [CrossRef]
  33. Tang, J.; Liang, F.; Meng, X.; Kang, K.; Zeng, T.; Yin, W.; Xia, M.; Lin, Z.; Kang, B. “Two in one”: An unprecedented mixed anion, Ba2(C3N3O3)(CNO), with the coexistence of isolated sp and sp2 π-conjugated groups. Dalton Trans. 2019, 48, 14246–14250. [Google Scholar] [CrossRef]
  34. Song, J.L.; Hu, C.L.; Xu, X.; Kong, F.; Mao, J.G. A facile synthetic route to a new SHG material with two types of parallel π-conjugated planar triangular units. Angew. Chem. Int. Ed. 2015, 54, 3679–3682. [Google Scholar] [CrossRef] [PubMed]
  35. Dong, X.; Jing, Q.; Shi, Y.; Yang, Z.; Pan, S.; Poeppelmeier, K.R.; Young, J.; Rondinelli, J.M. Pb2Ba3(BO3)3Cl: A material with large SHG enhancement activated by Pb-chelated BO3 groups. J. Am. Chem. Soc. 2015, 137, 9417–9422. [Google Scholar] [CrossRef] [PubMed]
  36. Zhao, S.; Gong, P.; Bai, L.; Xu, X.; Zhang, S.; Sun, Z.; Lin, Z.; Hong, M.; Chen, C.; Luo, J. Beryllium-free Li4Sr(BO3)2 for deep-ultraviolet nonlinear optical applications. Nat. Commun. 2014, 5, 4019–4023. [Google Scholar] [CrossRef] [Green Version]
  37. Xia, M.; Jiang, X.; Lin, Z.; Li, R. “All-Three-in-One”: A new bismuth-tellurium-borate Bi3TeBO9 exhibiting strong second harmonic generation response. J. Am. Chem. Soc. 2016, 138, 14190–14193. [Google Scholar] [CrossRef]
  38. Gao, M.; Wu, H.; Yu, H.; Hu, Z.; Wang, J.; Wu, Y. BaYOBO3: A deep-ultraviolet rare-earth oxy-borate with a large second harmonic generation response. Sci. China Chem. 2021, 64, 1184–1191. [Google Scholar] [CrossRef]
  39. Wu, B.L.; Hu, C.L.; Mao, F.F.; Tang, R.L.; Mao, J.G. Highly polarizable Hg2+ induced a strong second harmonic generation signal and large birefringence in LiHgPO4. J. Am. Chem. Soc. 2019, 141, 10188–10192. [Google Scholar] [CrossRef]
  40. Yu, H.; Wu, H.; Pan, S.; Yang, Z.; Hou, X.; Su, X.; Jing, Q.; Poeppelmeier, K.R.; Rondinelli, J.M. Cs3Zn6B9O21: A chemically benign member of the KBBF family exhibiting the largest second harmonic generation response. J. Am. Chem. Soc. 2014, 136, 1264–1267. [Google Scholar] [CrossRef]
  41. Yu, H.; Nisbet, M.L.; Poeppelmeier, K.R. Assisting the effective design of polar iodates with early transition-metal oxide fluoride anions. J. Am. Chem. Soc. 2018, 140, 8868–8876. [Google Scholar] [CrossRef]
  42. Majchrowski, A.; Sahraoui, B.; Fedorchuk, A.O.; Jaroszewicz, L.R.; Michalski, E.; Migalska-Zalas, A.; Kityk, I.V. β-BaTeMo2O9 microcrystals as promising optically operated materials. J. Mater. Sci. 2013, 48, 5938–5945. [Google Scholar] [CrossRef] [Green Version]
  43. Ra, H.S.; Ok, K.M.; Halasyamani, P.S. Combining second-order Jahn-Teller distorted cations to create highly efficient SHG materials: synthesis, characterization, and NLO properties of BaTeM2O9 (M = Mo6+ or W6+). J. Am. Chem. Soc. 2003, 125, 7764–7765. [Google Scholar] [CrossRef] [PubMed]
  44. Jacco, J.; Loiacono, G.; Jaso, M.; Mizell, G.; Greenberg, B. Flux growth and properties of KTiOPO4. J. Cryst. Growth 1984, 70, 484–488. [Google Scholar] [CrossRef]
  45. Zhang, H.; Zhang, M.; Pan, S.; Dong, X.; Yang, Z.; Hou, X.; Wang, Z.; Chang, K.B.; Poeppelmeier, K.R. Pb17O8Cl18: A promising IR nonlinear optical material with large laser damage threshold synthesized in an open system. J. Am. Chem. Soc. 2015, 137, 8360–8363. [Google Scholar] [CrossRef]
  46. Nguyen, S.D.; Yeon, J.; Kim, S.H.; Halasyamani, P.S. BiO(IO3): A new polar iodate that exhibits an aurivillius-type (Bi2O2)2+ layer and a large SHG response. J. Am. Chem. Soc. 2011, 133, 12422–12425. [Google Scholar] [CrossRef]
  47. Lan, H.; Liang, F.; Jiang, X.; Zhang, C.; Yu, H.; Lin, Z.; Zhang, H.; Wang, J.; Wu, Y. Pushing nonlinear optical oxides into the mid-infrared spectral region beyond 10 μm: Design, synthesis, and characterization of La3SnGa5O14. J. Am. Chem. Soc. 2018, 140, 4684–4690. [Google Scholar] [CrossRef] [PubMed]
  48. Guo, J.; Tudi, A.; Han, S.; Yang, Z.; Pan, S. Sn2B5O9Cl: A material with large birefringence enhancement activated prepared via alkaline-earth-metal substitution by Tin. Angew. Chem. Int. Ed. 2019, 58, 17675–17678. [Google Scholar] [CrossRef]
  49. Fan, X.; Wu, Z.; Wang, L.; Wang, C. Exploring the origin of high dechlorination activity in polar materials M2B5O9Cl (M = Ca, Sr, Ba, Pb) with built-in electric field. Chem. Mater. 2017, 29, 639–647. [Google Scholar] [CrossRef]
  50. SAINT: Program for Area Detector Absorption Correction, Ver, 4.05; Siemens Analytical X-ray Instruments: Madison, WI, USA, 1995.
  51. Sheldrick, G. A short history of shelx. Acta Crystallogr. A 2008, 64, 112–122. [Google Scholar] [CrossRef] [Green Version]
  52. Spek, A.L.J. Single-crystal structure validation with the program PLATON. J. Appl. Crystallogr. 2003, 36, 7–13. [Google Scholar] [CrossRef] [Green Version]
  53. Brown, I.D.; Altermatt, D. Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database. Acta Crystallogr. 2010, 41, 244–247. [Google Scholar] [CrossRef] [Green Version]
  54. Kubelka, P.; Munk, F. An article on optics of paint layers. Z. Tech. Phys. 1931, 12, 259–274. [Google Scholar]
  55. Tauc, J. Absorption Edge and Internal Electric Fields in Amorphous Semiconductors. Mater. Res. Bull. 1970, 5, 721–729. [Google Scholar] [CrossRef]
  56. Kurtz, S.; Perry, T. A powder technique for evaluation of nonlinear optical materials. J. Appl. Phys. 1968, 39, 3798–3813. [Google Scholar] [CrossRef]
  57. Clark, S. First principles methods using CASTEP. Z. Kristall. 2005, 220, 567–570. [Google Scholar] [CrossRef] [Green Version]
  58. Ernzerhof, M.; Scuseria, G. Assessment of the Perdew-Burke-Ernzerhof exchange-correlation functional. J. Chem. Phys. 1999, 110, 5029–5036. [Google Scholar] [CrossRef] [Green Version]
  59. Zou, G.; Ma, Z.; Wu, K.; Ye, N. Cadmium-rare earth oxyborates Cd4ReO(BO3)3 (Re = Y, Gd, Lu): Congruently melting compounds with large SHG responses. J. Mater. Chem. 2012, 22, 19911–19918. [Google Scholar] [CrossRef]
  60. Wang, Q.; Yang, F.; Wang, X.; Zhou, J.; Ju, J.; Huang, L.; Gao, D.; Bi, J.; Zou, G. Deep-ultraviolet mixed-alkali-metal borates with induced enlarged birefringence derived from the structure rearrangement of the LiB3O5. Inorg. Chem. 2019, 58, 5949–5955. [Google Scholar] [CrossRef]
  61. Lv, X.S.; Sun, Y.L.; Han, J.; Gu, G.X.; Wan, S.M.; Cheng, M.J.; Pan, S.L.; Zhang, Q.L. Growth and Raman spectrum of Ba2Mg(B3O6)2 crystal. J. Cryst. Growth 2013, 363, 220–225. [Google Scholar] [CrossRef]
  62. Hou, Y.; Zhang, B.; Wu, H.; Yu, H.; Hu, Z.; Wang, J.; Wu, Y. K3B4PO10 and K2MB4PO10 (M = Rb/Cs): Rare mixed-coordinated borophosphates with large birefringence. Inorg. Chem. Front. 2021, 8, 1468–1475. [Google Scholar] [CrossRef]
  63. Ji, X.; Wu, H.; Zhang, B.; Yu, H.; Hu, Z.; Wang, J.; Wu, Y. Intriguing dimensional transition inducing variable birefringence in K2Na2Sn3S8 and Rb3NaSn3Se8. Inorg. Chem. 2021, 60, 1055–1061. [Google Scholar] [CrossRef] [PubMed]
  64. Song, Y.; Luo, M.; Liang, F.; Lin, C.; Ye, N.; Yan, G.; Lin, Z. Experimental and ab initio studies of Cd5(BO3)3Cl: The first cadmium borate chlorine NLO material with isolated BO3 groups. Dalton Trans. 2017, 46, 15228–15234. [Google Scholar] [CrossRef] [PubMed]
  65. Xu, K.; Loiseau, P.; Aka, G.; Maillard, R.; Maillard, A.; Taira, T. Nonlinear optical properties of Ca5(BO3)3F crystal. Opt. Express 2008, 16, 17735–17744. [Google Scholar] [CrossRef] [PubMed]
  66. Wu, H.; Yu, H.; Pan, S.; Halasyamani, P.S. Deep-ultraviolet nonlinear-optical material K3Sr3Li2Al4B6O20F: Addressing the structural instability problem in KBe2BO3F2. Inorg. Chem. 2017, 56, 8755–8758. [Google Scholar] [CrossRef] [PubMed]
  67. Tran, T.T.; Halasyamani, P.S.; Rondinelli, J.M. Role of acentric displacements on the crystal structure and second- harmonic generating properties of RbPbCO3F and CsPbCO3F. Inorg. Chem. 2014, 53, 6241–6251. [Google Scholar] [CrossRef] [Green Version]
  68. Ye, N.; Chen, Q.; Wu, B.; Chen, C. Searching for new nonlinear optical materials on the basis of the anionic group theory. J. Appl. Phys. 1998, 84, 555–558. [Google Scholar] [CrossRef]
  69. Mutailipu, M.; Poeppelmeier, K.R.; Pan, S. Borates: A rich source for optical materials. Chem. Rev. 2021, 121, 1130–1202. [Google Scholar] [CrossRef]
  70. Zhang, F.; Shen, D.Z.; Shen, G.Q.; Wang, X.Q. Crystal structure of cadmium dizinc diborate CdZn2(BO3)2. Z. Kristallogr. 2008, 223, 3–4. [Google Scholar] [CrossRef]
  71. Sun, T.Q.; Pan, F.; Wang, R.J.; Shen, G.Q.; Wang, X.Q.; Shen, D.Z. A non-linear optical crystal, Cd3Zn3(BO3)4. Acta Cryst. 2003, 59, 107–108. [Google Scholar] [CrossRef] [Green Version]
  72. Brown, I.D. Recent Developments in the Methods and Applications of the Bond Valence Model. Chem. Rev. 2009, 109, 6858–6919. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  73. Yang, Y.; Dong, X.; Pan, S. New fluoroborate Cd8B5O15F with two different isolated borate anions prepared by an open high-temperature solution method. Dalton Trans. 2016, 45, 7008–7013. [Google Scholar] [CrossRef] [PubMed]
  74. Godby, R.W.; Schlüter, M.; Sham, L. Self-energy operators and exchange-correlation potentials in semiconductors. Phys. Rev. B 1988, 37, 10159–10163. [Google Scholar] [CrossRef] [PubMed]
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Figure 1. The structure of the CIBO: (a) The Cd−O double-chains, In−O single-chain, and the BO3 units arrangement viewed along the c axis. (b) The whole 3D framework.
Figure 1. The structure of the CIBO: (a) The Cd−O double-chains, In−O single-chain, and the BO3 units arrangement viewed along the c axis. (b) The whole 3D framework.
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Figure 2. (a) Thermal gravimetric (TG) and differential scanning calorimetry (DSC) curves of CIBO (b) XRD patterns of simulation, experiment, and after melting for CIBO.
Figure 2. (a) Thermal gravimetric (TG) and differential scanning calorimetry (DSC) curves of CIBO (b) XRD patterns of simulation, experiment, and after melting for CIBO.
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Figure 3. (a) The interference color observed for CIBO. (b) Birefringence curve of CIBO.
Figure 3. (a) The interference color observed for CIBO. (b) Birefringence curve of CIBO.
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Figure 4. (a) Phase−matching curves for CIBO at 1064 nm and KDP (KH2PO4) serving as a benchmark sample. (b) The SHG (second harmonic generation) signals at 150–180 μm particle sizes.
Figure 4. (a) Phase−matching curves for CIBO at 1064 nm and KDP (KH2PO4) serving as a benchmark sample. (b) The SHG (second harmonic generation) signals at 150–180 μm particle sizes.
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Figure 5. Electronic properties of CIBO: (a) Band structure; (b) total and partial DOS (density of states).
Figure 5. Electronic properties of CIBO: (a) Band structure; (b) total and partial DOS (density of states).
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Liu, R.; Wu, H.; Yu, H.; Hu, Z.; Wang, J.; Wu, Y. Cd4InO(BO3)3: A New Nonlinear Optical Crystal Exhibiting Strong Second Harmonic Generation Effect and Moderate Birefringence. Crystals 2022, 12, 266. https://doi.org/10.3390/cryst12020266

AMA Style

Liu R, Wu H, Yu H, Hu Z, Wang J, Wu Y. Cd4InO(BO3)3: A New Nonlinear Optical Crystal Exhibiting Strong Second Harmonic Generation Effect and Moderate Birefringence. Crystals. 2022; 12(2):266. https://doi.org/10.3390/cryst12020266

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Liu, Runqing, Hongping Wu, Hongwei Yu, Zhanggui Hu, Jiyang Wang, and Yicheng Wu. 2022. "Cd4InO(BO3)3: A New Nonlinear Optical Crystal Exhibiting Strong Second Harmonic Generation Effect and Moderate Birefringence" Crystals 12, no. 2: 266. https://doi.org/10.3390/cryst12020266

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