Li3VO4: A Promising Mid-Infrared Nonlinear Optical Material with

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Li3VO4 : A Promising Mid-IR Nonlinear Optical Material with Large Laser Damage Threshold Zhaohui Chen, Zhizhong Zhang, Xiaoyu Dong, Yunjing Shi, Yaqin Liu, and Qun Jing Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00250 • Publication Date (Web): 30 Mar 2017 Downloaded from http://pubs.acs.org on March 31, 2017

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Crystal Growth & Design

Li3VO4 : A Promising Mid-IR Nonlinear Optical Material with Large Laser Damage Threshold Zhaohui Chena*, Zhizhong Zhanga, Xiaoyu Dongc, Yunjing Shic, Yaqin Liua, Qun Jinga,b* a

Physical and Chemical Detecting Center, Xinjiang University, 666 Shengli Road, Urumqi 830046, China;

b

Department of Physics, College of Sciences, Shihezi University, Shihezi, 832000, China; c

Engineering Department of Chemistry and Environment, Xinjiang Institute of Engineering, 236 Nanchang Road, Urumqi 830091, China

*To whom correspondence should be addressed. E-mail: [email protected] (Z. Chen), [email protected] (Q. Jing). Phone: (86)-991-8582966. Fax: (86)-9918582966. Abstract: Laser damage threshold (LDT) and second harmonic generation (SHG) effect have been considered as key parameters of infrared (IR) nonlinear optical (NLO) materials. The IR NLO crystals with both large LDT and strong SHG efficiency are very scarce. The combination of the V5+ cations with d0 electrons and alkali metal Li+ cations generates an IR NLO material, low temperature phase Li3VO4. The single crystal of Li3VO4 with sizes up to 25 mm × 14 mm × 3 mm has been grown by the top-seeded solution growth (TSSG) method using the V2O5 flux in an open system in this work. The material exhibits a large LDT value of 125.5 MW/cm2, which is about 25 times that of AgGaS2. The inclusion-free Li3VO4 crystal is very favorable for 1

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improving the LDT. It also exhibits an excellent SHG response: 1.6 times that of AgGaS2, the benchmark IR NLO crystal at 2090 nm, and 9.5 times that of KDP, the benchmark UV NLO crystal at 1064 nm. Electronic structure and optical properties studies elucidate that the large NLO responses originate mainly from the polarities of the VO4 tetrahedra and partly from the LiO4 tetrahedra. Additionally, superior crystal growth method, comparatively simple chemical composition and wide transmission range enable Li3VO4 possess much better comprehensive performances for the practical mid-infrared (Mid-IR) NLO applications. Keywords: Mid-IR nonlinear optical crystal, Crystal growth, Large SHG, High LDT, Numerical calculation Introduction Nonlinear optical (NLO) materials have attracted more attentions recently1-8. In the ultraviolet and visible regions, many excellent materials have been invented by scientists9-19. Generation of coherent mid-infrared (Mid-IR) radiation is also important in diverse applications in molecular spectroscopy20-23, telecommunications24-27, sensing of atmospheric gases28,29 and optical biomarkers30-33. However, up to now, only a few high-performance IR NLO crystals (e.g., the chalcopyrite-type compounds AgGaS2, AgGaSe2 and ZnGeP234-38) have been commercially used in the IR region3940

. Generally speaking, these crystals suffer from two main obstacles, including low

laser damage thresholds (LDT) and the difficulty for growing crystals with highquality41, which seriously hinder their applications. It is known to all that a large energy band gap may lead to a high LDT, while it can also reduce the SHG coefficients42,43. Thus, designing and synthesizing an efficient Mid-IR NLO material with a balance between LDT and the SHG coefficient is still a huge challenge. 2


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It is reported that the combination with low electronegativity element, for instance, alkali metal or alkaline earth metal, into structure can broaden the band gap of the compound and a higher LDT can be generated44,45. Recently, extensive research has been focused on alkali- or alkaline earth metals containing chalcogenides with large band gap, such as, LiGaS246, LiInS247, Li2Ga2GeS648, Li2CdGeS449, Li2In2SiS650, Li2In2GeS650, BaGa4S751, BaGa2SiS652, BaGa2GeS652, NaBa4Ge3S10Cl53, Li2MnGeS454, Na2Hg3M2S8 (M = Si, Ge, and Sn)55, Na2BaMQ4 (M = Ge, Sn; Q = S, Se)56, Na2ZnGe2S657, and RbPbPS58. Since the vanadium atom has different coordination environments, such as the VO4, VO5 and VO6 polyhedra, it may form many new structures, and has many interesting properties. Our interest in vanadium is based on its ability to form distorted tetrahedra, pentahedra, triangular pyramids, octahedral and this type of distortion d0 transition metal may produce a high SHG response. In the past few decades, a series of vanadates with excellent properties have been synthesized successively, such as α‑ and β‑Ag3VO459 by the Poeppelmeier group; A4(VO2)2(SeO3)4(Se2O5) (A = Sr2+ or Pb2+)60, CuVOF4(H2O)761, A2[(VO)2(C4H4O6)(C4H2O6)(H2O)2](H2O)2 (A = Cs, Rb)62 and Cs2V3O863 by the Halasyamani group; K(VO)2O2(IO3)364, NaVO2(IO3)2(H2O)65 and Zn2(VO4)(IO3)66 by the Mao group; Na3VO2B6O1167 and K2SrVB5O1268 by the Pan group. The large SHG responses of these vanadate compounds are mainly derived from the different structures of vanadium atoms. For a good Mid-IR NLO crystal, the band gap should be more than 3.0 eV while NLO effects and LDT should be stronger than that of AgGaS2. In addition to the above conditions, the good chemical stability and mechanical property are very beneficial to the practical applications of a NLO crystal. In order to discover or design NLO 3



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materials having the above advantages, we combine alkali metal lithium, vanadium and oxygen into one compound, Li3VO4, which has been found successfully by us with very interesting properties. Its structure was first reported by R. D. Shannon and C. Calvo69. Some researchers studied its SHG response, crystal growth methods and electron band structure etc.

70-72

. In this work, the linear and nonlinear properties of

the compound are studied by experiments and theoretical calculations. We have grown large crystals by the top-seeded solution growth (TSSG) method in the open system and this crystal exhibits large band gap (4.27eV), large LDT (25 times that of AgGaS2), strong SHG properties (1.6 times that of AgGaS2 at 2090 nm and 9.5 times that of KDP at 1064 nm) and easy to grow. Additionally, the compound has a wide transmission range (0.29 to 6.05 µm). The theoretical studies reveal that the VO4 tetrahedra play more important role in its NLO response. Experimental Section Solid State Synthesis. Polycrystalline samples of Li3VO4 were synthesized by traditional solid-state reaction. Stoichiometric amounts of Li2CO3 (98.0%, Tianjin Yaohua Chemical Reagent Co., Ltd), V2O5 (99.5%, Shanghai Shanpu Chemical Co., Ltd) were ground together and then packed into a porcelain crucible. The temperature was raised to 450 °C at a rate of 2 °C/min in order to avoid ejection of starting materials from the crucible owing to vigorous evolution of CO2. After preheating at 450 °C for 10 h, the sample was cooled to room temperature and ground up again. Then the reaction mixture was heated at 680 °C for 48 h with adequate grinding. The furnace was turned off and the samples cooled down to room temperature. Powder X-ray Diffraction. The powder X-ray diffraction (PXRD) data were recorded on an automated Bruker D2 X-ray diffractometer with Cu Kα radiation (λ = 4


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1.5418 Å) at room temperature in the angular range of 2θ = 10−70° with a scan step width of 0.02 and a fixed counting time of 1 s/step. Both the experimental and simulated PXRD of Li3VO4 are shown in Figure S1 in the Supporting Information. No impurity peaks were observed on the two profiles, which indicates a high purity of the as-synthesized compound. Single Crystal Growth. Currently, most Mid-IR materials are grown in a closed system in sealed silica tubes by the conventional Bridgman-Sockbarger technique. Growth of the Li3VO4 crystals in an open system is more flexible to regulate crystal growth conditions and more likely to grow large-sized and high-quality crystals. The Li3VO4 crystals were grown by the TSSG method using V2O5 as the flux. Firstly, Li2CO3 and V2O5 with a molar ratio of 57:43 (21.06g, 39.13g) were ground and mixed thoroughly in an agate mortar. The concoction was packed into a Pt crucible and gradually heated to 700 °C at 20 °C/h in an electric furnace, and then held it for 24 h to ensure a homogeneous solution. Subsequently, a Pt wire was dipped into the obtained solution and the temperature was cooled at a rate of 3 °C/h until suitable size crystal was obtained. Then the crystal was pulled out from the liquid surface and quickly cooled it at 15 °C/h, ended up to room temperature. High-quality Li3VO4 seed crystals were obtained by spontaneous nucleation attach to the Pt wire during the slow cooling process.

In the following stage of crystal growth, the original reactants were heated to 700 °C and held at this temperature for 24 h, and then cooled it to 675 °C at 5 °C/h. A seed crystal was strapped on a Pt wire and slowly dipped into the surface of solution. The temperature was held for 15 min to dissolve the rough surfaces of the seed crystal and 5



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was decreased to 672 °C in 60 min. Then the crystal was grown with a rotation rate of 15 rpm and the temperature was reduced at a rate of 1 °C/d. After 15 days, the crystal was slowly pulled out of the solution and cooled to room temperature at a rate of 15°C/h. As shown in Figure 1, the as-grown Li3VO4 crystal is as large as 25 mm × 14 mm× 3 mm. Structure Determination. A single crystal of Li3VO4 with dimensions 0.18 mm × 0.15 mm × 0.10 mm was selected under microscope, and then glued on an end of a glass fiber for single crystal X-ray determination study. The diffraction data were collected at room temperature on a Bruker Smart APEX II single crystal diffractometer equipped with a 4K CCD-detector (graphite Mo Kα radiation, λ = 0.71073 Å). The reduction of data was carried out with the Bruker Suite software package73. A multi-scan absorption correction was performed with the SADABS program74. The structures were solved by direct methods in SHELXS-97 system. The structures were refined by the full-matrix least-squares method in SHELXL-97 system with anisotropic displacement parameters75. The structures were checked for missing symmetry elements with PLATON76. Details of crystal parameters, data collection, and structure refinement are listed in Table S1. The final refined atomic positions and isotropic thermal parameters, as well as bond valence sums (BVS) of each atom are summarized in Table S2. Selected bond distances and angles are given in Table S3. TG/DSC Analysis. Thermal analysis was conducted on a HITACHI STA 7300 thermal analyzer instrument. The crystal samples (5−10 mg) were enclosed in Al2O3 crucibles and heated from 30 to 1000 °C at a rate of 10 °C/min under argon 6


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atmosphere. Transmittance Spectra. Transmittance Spectra were measured on a 1 mm thick Li3VO4 single-crystal at room temperature using a UV-Vis-NIR spectrophotometer (SolidSpec-3700DUV) for the range of 190−2600 nm (0.19−2.6 µm) and by a Mid spectrophotometer (VERTEX 70) for the range of 4000−400 cm-1 (2.5−25 µm). Second-Order Nonlinear Optical Measurements. The SHG responses of Li3VO4 were measured on a modified Kurtz–Perry system77 using a 1064 nm light output from a Q-switched Nd:YAG laser (1064 nm) and an EO-Q-switched Cr:Tm:Ho:YAG laser (2090 nm). A detailed description of the equipment and methodology has been published67,78. Since the SHG efficiency has been shown to depend strongly on particle size, Li3VO4 was ground and sieved into distinct particle size ranges 20–38, 38–55, 55–88, 88–105, 105–150, 150–200 and 200-250 µm. To make relevant comparison with known SHG materials, crystalline KDP and AgGaS2 samples were also ground and served as references and sieved into the same particle size ranges. Structure–Property Relationships. To better understand the structure−property relationship of Li3VO4, we calculated the local dipole moment in the individual asymmetric tetrahedron by using a bond-valence method. The well-known Debye equation, µ = neR79 (µ is the net dipole moment in Debye, n the total number of electrons, e the charge on an electron, R the difference), was used to calculate the local dipole moment of individual Li–O and V–O bonds. LDT Measurements. The single pulse powder LDT measurement method was introduced to evaluate the powder LDT of Li3VO4 using AgGaS2 as the reference80. 7



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The same particle size samples of Li3VO4 and AgGaS2 were selected and pressed into disks with diameter of 8 mm with a pulsed YAG laser (1.06 µm, 10 ns, 10 Hz). The judgment criterion is as follows: with increasing laser energy, the color change of the powder sample is constantly observed by optical microscope to determine the damage threshold. To adjust different laser beams, an optical concave lens is added into the laser path. The damage spot is measured by the scale of optical microscope. Numerical Calculation Details. The electronic structure and optical property were calculated using the DFT method implemented in the CASTEP package81,82. During the calculation, the generalized gradient approximation (GGA) with Perdew-BurkeErnzerhof

(PBE)

functional

was

adopted83.

Under

the

norm-conserving

pseudopotential (NCP)84,85, the following orbital electrons were treated as valence electrons: Li:2s1, O:2s22p4, V:3d34s2. The kinetic energy cutoffs of 830 eV was chosen, and the numerical integration of the Brillouin zone was performed using a 4 × 5 × 5 Monkhorst-Pack k-point sampling. In present investigation, the geometry optimization was firstly performed, and then the electronic structures and the optical properties were obtained based on the optimized geometry. During the geometry optimization, the cell parameters and the atomic coordinates of all the atoms were optimized. The geometry optimization was converged when the residual forces on the atoms were less than 0.01 eV/Å, the displacements of atoms were less than 5×10-4 Å, and the energy change was less than 5.0 ×10-6 eV per atom. Furthermore, in order to get reliable linear and second-order NLO susceptibilities, about three times that of valence bands was chosen as the empty bands during the optical calculations. The other calculation parameters and convergent criteria were the default values of the CASTEP code. 8


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After the electronic structures obtained, the imaginary part of the dielectric constant ε2(ω) can be obtained by

=

Ω

∑ ,,|< | ∙ | >| ( − − )

In which Ω is the volume of the elemental cell, v, and c represent the valence and conduction bands, respectively, and u is the vector defining the polarization of the electric field of the incident light. Since the dielectric constant describes a causal response, the real and imaginary parts are linked by a Kramers-Kronig transform. This transform is used to obtain the real part of the dielectric function, ε1 (ω), and then the refractive index n. The SHG coefficients can be estimated using the length-gauge formalism at a zero frequency limit86,87. The static second-order coefficients can be written as, χ αβγ ( 2 ) = χ αβγ ( 2 ) (VE)+ χ αβγ ( 2 ) (VH)+ χ αβγ ( 2 )( two-bands )

In this formalism, the total SHG coefficient χ(2)is divided into the contribution from three different processes which are virtual-electron (VE), virtual-hole (VH) and twoband processes. After carefully checked, the contribution from two-band process was found so small that can be neglected, so in this paper we would just pay close attention to the contribution from the virtual-electron and virtual-hole processes. The formulas for calculating the contribution from VE, and VH are as follows, χαβγ ( 2) (VE ) =

e3 d 3k 1 2 P(αβγ ) Im  Pvvα′ Pcvβ′ Pcvγ  ( 3 2 + 4 ) 3 ∑∫ 3 2hm vv′c 4π ωcvωv′c ωvcωcv′

χαβγ ( 2) (VH ) =

e3 d 3k 1 2 P (αβγ ) Im  Pcvα Pccβ′ Pcγ′v  ( 3 2 + 4 ) 3 ∑∫ 3 2hm vcc′ 4π ωcvωvc′ ωvcωc′v 9



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Here, α, β, γ are Cartesian components, v and v′ denote valence bands, c and c′ refer to conduction bands, and P (αβγ) denotes full permutation. The band energy difference and momentum matrix elements are denoted as ℏω. Results and Discussion Crystal Structure Description. Li3VO4 crystallizes in Pmn21 space group and is isostructural to Li3PS4. So it belongs to diamond-like materials and can be classified into the I3-V-VI4 group88. In the asymmetric unit (Figure 2), there are two crystallographically independent Li atoms and one crystallographically independent V atom, which are all coordinated with four oxygen atoms to form tetrahedral units. The Li–O and V–O bond distances range from 1.952(7) to 2.03(2) Å and from 1.700(2) to 1.7178(14) Å, respectively. The LiO4 tetrahedra building units connect with each other via sharing the O vertices to form

1 ∞ [LiO4]

chains, while the

1

∞[LiVO7]

chains

are alternately built by the LiO4 and VO4 building blocks via sharing the O vertices along the a-axis. The∞1[LiO4] and

1 ∞[LiVO7]

chains arrange alternately and densely

connect by the Li–O and V–O bonds, forming

1

∞[Li2VO9]

layers. The

1

∞[Li2VO9]

layers are further connected by the V–O bonds and Li–O bonds forming a compact 3D network. The bond valences of all atoms in Li3VO4 were calculated89,90 and listed in Table S2. The valences of each atom agree well with expected oxidation states. Thermal Analysis. TG and DSC were measured to investigate the thermal property of Li3VO4 shown in Figure S2. The TG curve indicates that Li3VO4 has not weight loss from 30 to 1000 °C. It is clear that the compound has a high thermal stability within 1000 °C. The endothermic peaks at 741 and 773 °C in the heating curve and the exothermic peaks at 601 and 691 °C in the cooling curve of DSC diagram are assigned as four phase transitions of the Li3VO4 crystal, which correspond reasonably 10


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well with those found by Reisman and Mineo91. Because of the easy reversibility of the high-low temperature phase transitions, there is mainly low temperature Li3VO4 after cooling to room temperature, which is also confirmed by PXRD measurement of before and after melting compound Li3VO4 (see Figure S3 ). Transmittance Spectra. The UV−Vis−NIR transmittance spectrum was measured on a 1 mm thick Li3VO4 single-crystal (see Figure S4). The UV−Vis−NIR (0.19−2.6 µm) and Mid (2.5−25 µm) transmittance spectra are shown in Figure 3. No optical absorption peaks are observed in Mid-IR transmittance spectrum from 2.5 to 6.05 µm, meanwhile, little absorptions occur in UV-Vis-NIR transparent spectrum (0.29−2.5 µm). Hence, Li3VO4 is transparent in the range of 0.29−6.05 µm. The results indicate that the cutoff edge of the crystal is about 290 nm and the experimental band gap value of the crystal is about 4.27 eV, which is much higher than that of available IR NLO crystals such as AgGaS2 (2.64 eV), AgGaSe2 (1.83 eV), ZnGeP2 (2.10 eV), Pb17O8Cl18 (3.44 eV). The result implies that Li3VO4 may exhibit a surprise large LDT as a Mid-IR NLO material. SHG Measurements. Li3VO4 is asymmetric, so it is worthy to study its SHG properties. The polycrystalline samples of Li3VO4 were ground into powder with different sizes and loaded into a quartz cell. Polycrystalline samples of KDP and AgGaS2 were used as the references at 1064 and 2090 nm, respectively. The curves of SHG signal as function of particle size are shown in Figure 4. It can be seen that the SHG intensity of Li3VO4 increases with the increase of particle size until it reaches the highest value in the two curves. According to the rule proposed by Kurtz and Perry77, Li3VO4 is type-I phase-matchable. The Li3VO4 exhibits a large SHG response, which is about 9.5 × KDP, the benchmark at 1064 nm and 1.6 × AgGaS2, the 11



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benchmark at 2090 nm. Therefore, Li3VO4 possess very promising application as good MID-IR NLO material due to its high thermal stability, wide transmission range, relatively superior crystal growth method and large SHG response. LDT Measurements. The damage energy of Li3VO4 (6.3 mJ) is much larger than that of AgGaS2 (0.4 mJ), thus a smaller spot diameter (0.8 mm) is selected for Li3VO4 in the measurement. The results indicate that Li3VO4 exhibits a large LDT value of 125.5 MW/cm2 (1064 nm, 10 ns, 10 Hz) and AgGaS2 powders show an LDT of 5.1 MW/cm2 under the same conditions, which implies that the LDT of Li3VO4 is about 25 times that of AgGaS2. The experimental results of powder LDTs for Li3VO4, AgGaS2 and some other selected IR NLO crystals are summarized in Table 1 and they all have identical laser conditions with AgGaS2. From the table we can see that the LDT of Li3VO4 is the largest among them, which implies that Li3VO4 is an excellent candidate for high power NLO applications in the Mid-IR region. Structure-Property Relationships. The excellent SHG properties of Li3VO4 at 1064 and 2090 nm prompt us to investigate the relationship between the functional units and the SHG responses. The dipole moments of the LiO4 and VO4 tetrahedra were calculated using the Debye equation. The detailed calculation results are summarized in Table S4. Dipole moments of the VO4 and LiO4 tetrahedra along the (001) direction are consistent and thus reinforce each other, while dipole moments of them along the (100) and (010) directions are almost canceled. As a result, their vector sum results in an enhanced net polarization moment in the (001) direction (see Figure 5) and this direction is consistent with the defined polar direction in crystal class mm292. These enhanced arrangements of dipole moments might lead to the excellent SHG response 12


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of Li3VO4. As shown in Table S4, the VO4 tetrahedra are the main contributors to the macroscopic polarity, while the LiO4 tetrahedra also provide considerable part contribution for the polarity of Li3VO4 along the (001) direction. Therefore, the SHG efficiency of the compound originates from the cooperative effect of the LiO4 tetrahedra and the VO4 tetrahedra in this system. It is well known that the LDT of the crystal can be greatly reduced if there are inclusions in the crystal structure. The crystal lattice of Li3VO4 is composed by infinite∞1[LiO4] and

1 ∞[LiVO7]

chains, which intercross forming compact network

structure. That is to say that the staggered gap between the chains is small so that only the Li+ cations can enter them. This strcutral fearthure ensure that the crystal lattice of Li3VO4 is inclusion-free even if grown by flux method. As a consequence, the favorable structure is useful for improving the LDT. In additional, the Li3VO4 crystal structure is so compact and particles (such as electrons, ions etc.) are not easy to be producted and transfered even if radiated by the intense laser. Therefore the structure of Li3VO4 is conducive to generate large LDT. Electronic Structure and the Calculated Optical Properties. Using the method described above, the electronic structures of Li3VO4 was obtained. As shown in Figure 6 (a), Li3VO4 is found to be an indirect band gap semiconductor with band gap 3.93 eV, which is in good agreement with the experimental value (4.27 eV) determined by optical transmittance spectrum. The calculated projected density of states (PDOS) of Li3VO4 is shown in Figure 6 (b). It is clearly shown that at the top of valence band and bottom of conduction band, there are mainly O-p states, V-p and V-d states. Since the optical properties are determined by the electron transition among the top of valence band and the bottom of 13



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conduction band, the overlap states found nearby Fermi level imply that the V-O groups may play an important role in determining the linear and nonlinear optical properties. It is interesting to investigate the refractive indices and the birefringence of a NLO material because the birefringence plays an important role in determining the phasematching conditions. Using the first-principles method described above, the refractive indices and the birefringence of Li3VO4 were also obtained. As shown in Figure S5, the birefringence is just 0.01 from 500 to 1100 nm. The small birefringence of Li3VO4 may have relation with the tetrahedral V-O groups which plays an important role in optical properties. For comparison, the SHG tensors of Li3VO4 have also been obtained. As shown in Table 2, the obtained SHG tensors d15, d24 and d33 are 5.85, 5.99, and -11.99 pm/V, respectively. According to the expression of effective SHG coefficients of mm2 point group93, the nonzero SHG tensor d15 is suggested to be the main contribution to the total effective SHG coefficients. The obtained nonzero SHG tensor d15 is about 5.85 pm/V which is approximately 15.0 times of that of KDP (d36 = 0.39 pm/V), indicating qualitatively consistent with the experimental measurements. To better understand the contribution from ion (or ionic groups) to the second order susceptibility, a so-called SHG-density technique was adopted. It was performed by using the effective SHG of each band (occupied and unoccupied) as weighting coefficient (after normalized with total VE or VH value) to sum the probability densities of all occupied or unoccupied states. More details about the SHG-density technique can be found elsewhere94. Herein only SHG-density of the virtual-electrons and virtual-hole process of the effective SHG tensor d15 are presented here. As shown 14


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in Figure 7, the SHG-density mainly distributes around the VO4 groups, indicating that the VO4 groups give main contribution to the SHG tensors. While compared with the VO4 groups, distribution of SHG density can not be found around the Li ions, implying that the Li ions give very small contribution to the SHG tensors. In order deeply analysize the role played by different ions, the respective contribution was further investigated by the real-space atom-cutting method86. During the calculation, according to the rule of keeping the cutting spheres in contact and avoiding overlap, the cutting radii of Li, V, O were set as 0.60, 1.22 and 1.10 Å, respectively. It clearly shows that main contribution to SHG coefficients are from the VO groups, while the Li ions give very small contribution to the total SHG coefficients. Conclusions In summary, the crystal of Li3VO4 with sizes up to 25 mm × 14 mm× 3 mm has been grown by the TSSG method using self flux in the open system. It overcomes the difficulty in the growth of high quality crystals by traditional Bridgman-Stockbarger technique. The SHG intensity of the crystal is about 9.5 × KDP at 1064 nm and 1.6 × AgGaS2 at 2090 nm and is type-I phase-matchable. Remarkably, the LDT of Li3VO4 is about 25 × AgGaS2, which may be due to the inclusion-free compact crystal lattice of Li3VO4. It can be seen that Li3VO4 has an wonderful balance between large NLO coefficient and high LDT. The calculations of the dipole moments and electronic structure reveal that the SHG response mainly derives from the VO4 tetrahedra polarities, which is also confirmed by SHG-density technique. In summary, the crystal presents chemical characteristics of being easy to grow large-sized crystal and having simple chemical composition. More importantly, it shows large SHG conversion 15



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efficiency, high LDT and wide transparent regions. We therefore believe that Li3VO4 is a promising Mid-IR NLO material and we will follow up the growth of large-sized and high quality crystals for the late stage performances. Acknowledgment. This work is supported by the science research projects in Universities

of

Xinjiang

Education

Department

(Nos.

XJEDU2012I07,

XJEDU2014S073), “National Natural Science Foundation of China” (Grant Nos. 51462033, 51562036). The Natural Science Foundation of Xinjiang Uygur Autonomous Region of China (No. 2015211C251), Shihezi University (RCZX201511, 2015ZRKXYQ07), the Doctoral Program of Xinjiang University (Project BS110132). Supporting Information Available: CCDC 430658 contains the supplementary crystallographic data of this paper. These data can be obtained free of charge from The

Cambridge

Crystallographic

Data

Centre

via

www.ccdc.cam.ac.uk/data_request/cif. Include CIF file, tables of crystal data and structure refinement, tables of atomic coordinates and equivalent isotropic displacement parameters and the bond valence sums of each atom, tables of bond lengths and bond angles, tables of the local dipole moments for the LiO4 tetrahedra and the VO4 tetrahedra, XRD patterns, the refractive indices and the birefringence curves, TG and DSC curves, photograph of the Li3VO4 crystal.

References (1) 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. (2) Lin, Z. S.; Lin, J.; Wang, Z. Z.; Chen, C. T.; Lee, M. H. Mechanism for Linear and 16


Page 17 of 41

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Nonlinear Optical Effects in LiB3O5, CsB3O5, and CsLiB6O10 Crystals. Phys. Rev. B: Condens. Matter Mater. Phys. 2000, 62, 1757−1764. (3) Lu, H. C.; Gautier, R.; Donakowski, M. D.; Tran, T. T.; Edwards, B. W.; Nino, J. C.; Halasyamani, P. S.; Liu, Z. T.; Poeppelmeier, K. R. Nonlinear Active Materials: An Illustration of Controllable Phase Matchability. J. Am. Chem. Soc. 2013, 135, 11942−11950. (4) Welk, M. E.; Norquist, A. J.; Stern, C. L.; Poeppelmeier, K. R. The StructureDirecting Properties of [VOF5]2-. Inorg. Chem. 2000, 39, 3946−3947. (5) Yu, H. W.; Zhang, W. G.; Young, J.; Rondinelli, J. M.; Halasyamani, P. S. Bidenticity-Enhanced Second Harmonic Generation from Pb Chelation in Pb3Mg3TeP2O14. J. Am. Chem. Soc. 2015, 138, 88−91. (6) Wang, Y.; Pan, S. L. Recent Development of Metal Borate Halides: Crystal Chemistry and Application in Second-Order NLO Materials. Coord. Chem. Rev. 2016, 323, 15−35. (7) Chung, I.; Kanatzidis, M. G. Metal Chalcogenides: A Rich Source of Nonlinear Optical Materials. Chem. Mater. 2013, 26, 849−869. (8) Lin, H.; Chen, L.; Zhou, L. J.; Wu, L. M. Functionalization Based on the Substitutional

Flexibility:

Strong

Middle

IR

Nonlinear

Optical

Selenides

AXII4XIII5Se12. J. Am. Chem. Soc. 2013, 135, 12914−12921. (9) Li, L.; Wang, Y.; Lei, B. H.; Han, S. J.; Yang, Z. H.; Poeppelmeier, K. R.; Pan, S. L. A New Deep-Ultraviolet Transparent Orthophosphate LiCs2PO4 with Large Second Harmonic Generation Response. J. Am. Chem. Soc. 2016, 138, 9101−9104. 17



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(10) Zou, G. H.; Huang, L.; Ye, N.; Lin, C. S.; Cheng, W. D.; Huang, H. CsPbCO3F: A Strong Second-Harmonic Generation Material Derived from Enhancement via p−π Interaction. J. Am. Chem. Soc. 2013, 135, 18560−18566. (11) Zhao, S. G.; Kang, L.; Shen, Y. G.; Wang, X. D.; Asghar, M. A.; Lin, Z. S.; Xu, Y. Y.; Zeng, S. Y.; Hong, M. C.; Luo, J. H. Designing a Beryllium-Free Deep-Ultraviolet Nonlinear Optical Material without a Structural Instability Problem. J. Am. Chem. Soc. 2016, 138, 2961−2964. (12) Hu, Z. G.; Higashiyama, T.; Yoshimura, M.; Yap, Y. K.; Mori, Y.; Sasaki, T. A New Nonlinear Optical Borate Crystal K2Al2B2O7 (KABO). Jpn. J. Appl. Phys. 1998, 37, L1093−L1094. (13) Dong, X. Y.; Jing, Q.; Shi, Y. J.; Yang, Z. H.; Pan, S. L.; 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. (14) Yu, H. W.; Wu, H. P.; Pan, S. L.; Yang, Z. H.; Hou, X. L.; Su, X.; Jing, Q.; Poeppelmeier, K. R.; Rondinelli, J. M. Cs3Zn6B9O21: A New Member in the KBBF Family without Layer Habits yet Exhibiting the Largest Second Harmonic Generation Response. J. Am. Chem. Soc. 2014, 136, 1264−1267. (15) Wu, H. P.; Yu, H. W.; Yang, Z. L.; Hou, X. L.; Pan, S. L.; Su, X.; Poeppelmeier， K. R.; Rondinelli, J. M. Designing A Deep Ultraviolet Nonlinear Optical Material with Large Second Harmonic Generation Response. J. Am. Chem. Soc. 2013, 135, 4215−4218. 18


Page 18 of 41

Page 19 of 41

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(16) Xia, M. J.; Jiang, X. X.; Lin, Z. S.; Li, R. K. “All-Three-in-One”: A New Bismuth-Telluriu-Borate Bi3TeBO9 Exhibiting Strong Second Harmonic Generation Response. J. Am. Chem. Soc. 2016, 138, 14190−14193. (17) Huang, H. W.; Yao, J. Y.; Lin, Z. S.; Wang, X. Y.; He, R.; Yao, W. J.; Zhai, N. X.; Chen, C. T. NaSr3Be3B3O9F4: A Promising Deep-Ultraviolet Nonlinear Optical Material Resulting from the Cooperative Alignment of the [Be3B3O12F]10‑ Anionic Group. Angew. Chem., Int. Ed. 2011, 50, 9141−9144. (18) Jiang, X. X.; Molokeev, M. S.; Gong, P. F.; Yang, Y.; Wang, W.; Wang, S. H.; Wu, S. F.; Wang, Y. X.; Huang, R. J.; Li, L. F.; Wu, Y. C.; Xing, X. R.; Lin, Z. S. NearZero Thermal Expansion and High Ultraviolet Transparency in a Borate Crystal of Zn4B6O13. Adv. Mater. 2016, 28, 7936–7940. (19) Chen, C. T.; Wang, G. L.; Wang, X. Y.; Xu, Z. Y. Deep-UV Nonlinear Optical Crystal KBe2BO3F2-Discovery, Growth, Optical Properties and Applications. Appl. Phys. B: Lasers Opt. 2009, 97, 9−25. (20) Simon, U.; Benko, Z.; Sigrist, M. W.; Curl, R. F.; Tittel, F. K. Design Considerations of an Infrared Spectrometer Based on Difference-Frequency Generation in AgGaSe2. Appl. Opt. 1993, 32, 6650−6655. (21) Ding, Y. J. High-Power Tunable Terahertz Sources Based on Parametric Processes and Applications. IEEE J. Quantum Electron. 2007, 13, 705−720. (22) Wang, L. S.; Cao, Z. S.; Wang, H. A.; Zhao, H.; Gao, W.; Yuan, Y. D.; Gao, X. M. A Widely Tunable (5-12.5 µm) Continuous-Wave Mid-Infrared Laser Spectrometer Based on Difference Frequency Generation in AgGaS2. Opt. Commun. 2011, 284, 358 19



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

−362. (23) Dezaki, H.; Tanabe, T.; Oyama, Y. Continuously Tunable Ultra Broadband Terahertz Generation Implemented with 1.2 µm NIR. J. Jpn. Inst. Met. 2011, 75, 315− 319. (24) Smektala, F.; Quemard, C.; Leneindre, L.; Lucas, J.; Barthelemy, A.; De Angelis, C. Chalcogenide Glasses with Large Nonlinear Refractive Indices. J. Non-Cryst. Solids. 1998, 239, 139−142. (25) Bindra, K. S.; Bookey, H. T.; Kar, A. K.; Wherrett, B. S.; Liu, X.; Jha, A. Nonlinear Optical Properties of Chalcogenide Glasses: Observation of Multiphoton Absorption. Appl. Phys. Lett. 2001, 79, 1939−1941. (26) Gopinath, J. T.; Soljacic, M.; Ippen, E. P.; Fuflyigin, V. N.; King, W. A.; Shurgalin, M. Third Order Nonlinearities in Ge-As-Se-Based Glasses for Telecommunications Applications. J. Appl. Phys. 2004, 96, 6931−6933. (27) Ikuta, R.; Kusaka, Y.; Kitano, T.; Kato, H.; Yamamoto, T.; Koashi, M.; Imoto, N. Wide-Band Quantum Interface for Visible-to-Telecommunication Wavelength Conversion. Nat. Commun. 2011, 2, 193−198. (28) Töpfer, T.; Petrov, K. P.; Mine, Y.; Jundt, D.; Curl, R. F.; Tittel, F. K. RoomTemperature Mid-Infrared Laser Sensor for Trace Gas Detection. Appl. Opt. 1997, 36, 8042−8049. (29) Willer, U.; Saraji, M.; Khorsandi, A.; Geiser, P.; Schade, W. Near-and MidInfrared Laser Monitoring of Industrial Processes, Environment and Security Applications. Opt. Laser Eng. 2006, 44, 699−710. 20


Page 20 of 41

Page 21 of 41

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(30) Huff, T. B.; Shi, Y.; Fu, Y.; Wang, H.; Cheng, J. X. Multimodal Nonlinear Optical Microscopy and Applications to Central Nervous System Imaging. IEEE J. Quantum Electron. 2008, 14, 4−9. (31) Adur, J.; Pelegati, V. B.; Thomaz, A. A. D.; Baratti, M. O.; Almeida, D. B.; Andrade, L. A.; Bottcher-Luiz, F.; Carvalho, H. F.; Cesar, C. L. Optical Biomarkers of Serous and Mucinous Human Ovarian Tumor Assessed with Nonlinear Optics Microscopies. PLoS One. 2012, 7, e47007. (32) Mouras, R.; Bagnaninchi, P.; Downes, A.; Elfick, A. Multimodal, Label-Free Nonlinear Optical Imaging for Applications in Biology and Biomedical Science. J. Raman Spectrosc. 2013, 44, 1373−1378. (33) So, P. T.; Yew, E. Y.; Rowlands, C. High-Throughput Nonlinear Optical Microscopy. Biophys. J. 2013, 105, 2641−2654. (34) Harasaki, A.; Kato, K. New Data on the Nonlinear Optical Constant, PhaseMatching, and Optical Damage of AgGaS2. Jpn. J. Appl. Phys. 1997, 36, 700−703. (35) Tell, B.; Kasper, H. M. Optical and Electrical Properties of AgGaS2 and AgGaSe2. Phys. Rev. B 1971, 4, 96−105. (36) Kasper, H. M. Preparation and Properties of Silver Gallium Selenide, AgGaSe2. J. Electrochem. Soc. 1972, 119, C96−&. (37) Airoldi, G.; Beucherie, P.; Rinaldi, C. Growth and Characterization of AgGaSe2 Crystals. J. Cryst. Growth. 1977, 38, 239−244. (38) Boyd, G. D.; Buehler, E.; Storz, F. G. Linear and Nonlinear Optical Properties of ZnGeP2 and CdSe. Appl. Phys. Lett. 1971, 18, 301−304. 21



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(39) Sorokina, I. T.; Vodopyanov, K. L. Solid-State Mid-Infrared Laser Sources. Springer Science & Business Media. 2003, 89. (40) Park, S. H.; Roy, A.; Beaupre, S.; Cho, S.; Coates, N.; Moon, J. S.; Moses, D.; Leclerc, M.; Lee, K.; Heeger, A. J. Bulk Hetero Junction Solar Cells with Internal Quantum Efficiency Approaching 100 %. Nat. Photo. 2009, 3, 297−302. (41) Dmitriev, V. G.; Gurzadyan, G. G.; Nikogosyan, D. N. Handbook of Nonlinear Optical Crystals. Springer. 2013, 64. (42) Abbott, B. P.; Abbott, R.; Adhikari, R.; Ajith, P.; Allen, B.; Allen, G.; Amin, R.; Anderson, S.; Anderson, W.; Araya, M. LIGO: The Laser Interferometer Gravitational-Wave Observatory. Rep. Prog. Phys. 2009, 72, 076901. (43) Chen, C.; Lin, Z.; Wang, Z. The Development of New Borate-Based UV Nonlinear Optical Crystals. Appl. Phys. B 2005, 80, 1−25. (44) Liao, J. H.; Marking, G. M.; Hsu, K. F.; Matsushita, Y.; Ewbank, M. D.; Borwick, R.; Cunningham, P.; Rosker, M. J.; Kanatzidis, M. G. α-and β-A2Hg3M2S8 (A = K, Rb; M = Ge, Sn): Polar Quaternary Chalcogenides with Strong Nonlinear Optical Response. J. Am. Chem. Soc. 2003, 125, 9484−9493. (45) Zeng, H. Y.; Zhang, M. J.; Liu, B. W.; Ye, N.; Zhao, Z. Y.; Zheng, F. K.; Guo, G. C.; Huang, J. S. NaIn3S5, a New Compound from the CaS–In2S3/NaBr System. J. Alloys Compd. 2015, 624, 279−283. (46) Isaenko, L.; Yelisseyev, A.; Lobanov, S.; Titov, A.; Petrov, V.; Zondy, J. J.; Krinitsin, P.; Merkulov, A.; Vedenyapin, V.; Smirnova, J. Growth and Properties of LiGaX2 (X = S, Se, Te) Single Crystals for Nonlinear Optical Applications in the Mid22


Page 22 of 41

Page 23 of 41

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


IR. Cryst. Res. Technol. 2003, 38, 379−387. (47)Isaenko, L.; Vasilyeva, I.; Merkulov, A.; Yelisseyev, A.; Lobanov, S. Growth of New Nonlinear Crystals LiMX2 (M = Al, In, Ga; X = S, Se, Te) for the Mid-IR Optics. J. Cryst. Growth. 2005, 275, 217−223. (48)Kim, Y.; Seo, I. S.; Martin, S. W.; Baek, J.; Halasyamani, P. S.; Arumugam, N.; Steinfink, H. Characterization of New Infrared Nonlinear Optical Material with High Laser Damage Threshold, Li2Ga2GeS6. Chem. Mater. 2008, 20, 6048−6052. (49) Lekse, J. W.; Moreau, M. A.; McNerny, K. L.; Yeon, J.; Halasyamani, P. S.; Aitken, J. A. Second-Harmonic Generation and Crystal Structure of the DiamondLike Semiconductors Li2CdGeS4 and Li2CdSnS4. Inorg. Chem. 2009, 48, 7516−7518. (50) Yin, W.; Feng, K.; Hao, W.; Yao, J.; Wu, Y. Synthesis, Structure, and Properties of Li2In2MQ6 (M = Si, Ge; Q = S, Se): A New Series of IR Nonlinear Optical Materials. Inorg. Chem. 2012, 51, 5839−5843. (51) Lin, X.; Zhang, G.; Ye, N. Growth and Characterization of BaGa4S7: A New Crystal for Mid-IR Nonlinear Optics. Cryst. Growth Des. 2008, 9, 1186−1189. (52) Yin, W. L.; Feng, K.; He, R.; Mei, D. J.; Lin, Z. S.; Yao, J. Y.; Wu, Y. C. BaGa2MQ6 (M = Si, Ge; Q = S, Se): A New Series of Promising IR Nonlinear Optical Materials. Dalton Trans. 2012, 41, 5653−5661. (53) Feng, K.; Kang, L.; Lin, Z. S.; Yao, J. Y.; Wu, Y. C. Noncentrosymmetric Chalcohalide NaBa4Ge3S10Cl with Large Band Gap and IR NLO Response. J. Mater. Chem. C 2014, 2, 4590−4596. (54) Brant, J. A.; Clark, D. J.; Kim, Y. S.; Jang, J. I.; Weiland, A.; Aitken, J. A. 23



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 41

Outstanding Laser Damage Threshold in Li2MnGeS4 and Tunable Optical Nonlinearity in Diamond-Like Semiconductors. Inorg Chem. 2015, 54, 2809−2819. (55) Wu, K.; Yang, Z. H.; Pan, S. L. Na2Hg3M2S8 (M = Si, Ge, and Sn): New Infrared Nonlinear Optical Materials with Strong Second Harmonic Generation Effects and High Laser-Damage Thresholds. Chem. Mater. 2016, 28, 2795−2801. (56) Wu, K.; Yang, Z. H.; Pan, S. L. Na2BaMQ4 (M = Ge, Sn; Q = S, Se): Infrared Nonlinear Optical Materials with Excellent Performances and that Undergo Structural Transformations. Angew. Chem., Int. Ed. 2016, 128, 6825−6827. (57) Li, G. M.; Wu, K.; Liu, Q.; Yang, Z. H.; Pan, S. L. Na2ZnGe2S6: A New Infrared Nonlinear Optical Material with Good Balance Between Large Second-Harmonic Generation Response and High Laser Damage Threshold. J. Am. Chem. Soc. 2016, 138, 7422−7428. (58) Kang, L.; Zhou, M. L.; Yao, J. Y.; Lin, Z. S.; Wu Y. C.; Chen, C. T. Metal Thiophosphates with Good Mid-Infrared Nonlinear Optical Performances: A FirstPrinciples Prediction and Analysis. J. Am. Chem. Soc. 2015, 137, 13049−13059. (59) Cloet, V.; Raw, A.; Poeppelmeier, K. R.; Trimarchi, G.; Peng, H.; Im, J.; Freeman, A. J.; Perry, N. H.; Mason, T. O.; Zakutayev, A.; Ndione, P. F.; Ginley, D. S.; Perkins, J. D. Structural, Optical, and Transport Properties of α- and β-Ag3VO4. Chem. Mater. 2012, 24, 3346−3354. (60) Yeon, J.; Kim, S. H.; Nguyen, S. D.; Lee, H.; Halasyamani, P. S. New Vanadium Selenites:

Centrosymmetric

Ca2(VO2)2(SeO3)3(H2O)2,

Sr2(VO2)2(SeO3)3,

and

Ba(V2O5)(SeO3), and Noncentrosymmetric and Polar A4(VO2)2(SeO3)4(Se2O5)(A = 24


Page 25 of 41

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Sr2+ or Pb2+). Inorg. Chem. 2011, 51, 609−619. (61) Donakowski, M. D.; Gautier, R.; Yeon, J.; Moore, D. T.; Nino, J. C.; Halasyamani, P. S.; Poeppelmeier, K. R. The Role of Polar, Lamdba (Λ)-Shaped Building Units in Noncentrosymmetric Inorganic Structures. J. Am. Chem. Soc. 2012, 134, 7679−7689. (62) Cortese, A. J.; Wilkins, B.; Smith, M. D.; Yeon, J.; Morrison, G.; Tran, T. T.; Halasyamani, P. S; zur Loye, H. C. Crystal Growth of Four Oxovanadium (IV) Tartrates Prepared via A Mild Two-Step Hydrothermal Method: Observation of SpinDimer Behavior and Second Harmonic Generation. Inorg. Chem. 2015, 54, 4011− 4020. (63) Yeon, J.; Sefat, A. S.; Tran, T. T.; Halasyamani, P. S.; zur Loye, H. C. Crystal Growth, Structure, Polarization, and Magnetic Properties of Cesium Vanadate, Cs2V3O8: A Structure–Property Study. Inorg. Chem. 2013, 52, 6179−6186. (64) Sun, C. F.; Hu, C. L.; Xu, X.; Yang, B. P.; Mao, J. G. Explorations of New Second-Order Nonlinear Optical Materials in the Potassium Vanadyl Iodate System. J. Am. Chem. Soc. 2011, 133, 5561−5572. (65) Yang, B. P.; Hu, C. L.; Xu, X.; Sun, C. F.; Zhang, J. H.; Mao, J. G. NaVO2(IO3)2(H2O): A Unique Layered Material Produces a Very Strong SHG Response. Chem. Mater. 2010, 22, 1545−1550. (66) Yang, B. P.; Hu, C. L.; Xu, X.; Huang, C.; Mao, J. G. Zn2(VO4)(IO3): A Novel Polar Zinc (II) Vanadium (V) Iodate with a Large SHG Response. Inorg. Chem. 2013, 52, 5378−5384. 25



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(67) Fan, X. Y.; Pan, S. L.; Hou, X. L.; Tian, X. L.; Han, J.; Haag, J.; Poeppelmeier, K. R. Growth and Properties of Single Crystals of Noncentrosymmetric Na3VO2B6O11. Cryst. Growth Des. 2009, 10, 252−256. (68) Chen, S. J.; Pan, S. L.; Zhao, W. W.; Yu, H. W.; Wu, H. P.; Yang, Z. H.; Yang, Y. A New Noncentrosymmetric Vanadoborate: Synthesis, Crystal Structure and Characterization of K2SrVB5O12. Dalton Trans. 2012, 41, 9202−9208. (69) Shannon, R. D.; Calvo, C. Refinement of the Crystal Structure of Low Temperature Li3VO4 and Analysis of Mean Bond Lengths in Phosphates, Arsenates, and Vanadates. J. Solid State Chem., 1973, 6, 538−549. (70) Sakata, S.; Ueda N.; Fujii I.; Kawazoe H. Preparation of Low-temperature Li3VO4 Single Crystal by Floating Zone Technique. J. Solid State Chem., 1994, 178, 98−102. (71) Higuchi M.; Chuman, Y.; Kitagawa, T.; Kodaira, K. Growth of βII-Li3VO4 Single Crystals by the Heater-in-zone Zone-melting Method Using a Traveling Solvent of LiVO3. J. Crys. Growth. 2000, 216, 322−325. (72) Su, X.; Yang, Z. H.; Han, G. P.; Wang Y.; Wen, M.; Pan S. L. Role of the Metal Cation Types Around VO4 Groups on the Nonlinear Optical Behavior of Materials: Experimental and Theoretical Analysis. Dalton Trans., 2016, 45, 14394−14402. (73) Bruker, A. V. 0 Data Collection and Processing Software. Bruker AXS Inc., Madison, WI. USA, 2008. (74) Smart, B. Version 5.054, and SADABS, Version 2.05; Bruker Analytical X-ray Systems. Inc.: Madison, WI. 2003. 26


Page 26 of 41

Page 27 of 41

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(75) Sheldrick, G. M. Crystal Structure Refinement with SHELXL. Acta Crystallogr. Sect. C: Struct. Chem. 2015, 71, 3−8. (76) Spek, A. L. Single-Crystal Structure Validation with the Program PLATON. J. Appl. Crystallogr. 2003, 36, 7−13. (77) Kurtz, S. K.; Perry, T. T. A Powder Technique for the Evaluation of Nonlinear Optical Materials. J. Appl. Phys. 1968, 39, 3798−3813. (78) Yang, Y.; Pan, S. L.; Li, H. Y.; Han, J.; Chen, Z. H.; Zhao, W. W.; Zhou, Z. X. Li4Cs3B7O14: Synthesis, Crystal Structure, and Optical Properties. Inorg. Chem. 2011, 50, 2415−2419. (79) Maggard, P. A.; Nault, T. S.; Stern, C. L.; Poeppelmeier, K. R. Alignment of Acentric MoO3F33− Anions in a Polar Material: (Ag3MoO3F3)(Ag3MoO4)Cl. J. Solid State Chem. 2003, 175, 27−33. (80) Zhang, M. J.; Jiang, X. M.; Zhou, L. J.; Guo, G. C. Two Phases of Ga2S3: Promising Infrared Second-Order Nonlinear Optical Materials with Very High Laser Induced Damage Thresholds. J. Mater. Chem. C 2013, 1, 4754−4760. (81) Clark, S. J.; Segall, M. D.; Pickard, C. J.; Hasnip, P. J.; Probert, M. I.; Refson, K.; Payne, M. C. First Principles Methods Using CASTEP. Z. Kristallogr. Cryst. Mater. 2005, 220, 567−570. (82) Pfrommer, B. G.; Côté, M.; Louie, S. G.; Cohen, M. L. Relaxation of Crystals with the Quasi-Newton Method. J. Comput. Phys. 1997, 131, 233−240. (83) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. lett. 1996, 77, 3865−3868. 27



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(84) Rappe, A. M.; Rabe, K. M.; Kaxiras, E.; Joannopoulos, J. Optimized Pseudopotentials. Phys. Rev. B 1990, 41, 1227−1230. (85) Lin, J.; Qteish, A.; Payne, M.; Heine, V. Optimized and Transferable Nonlocal Separable ab Initio Pseudopotentials. Phys. Rev. B 1993, 47, 4174−4180. (86) Aversa, C.; Sipe, J. Nonlinear Optical Susceptibilities of Semiconductors: Results with A Length-Gauge Analysis. Phys. Rev. B 1995, 52, 14636−14645. (87) Lin, J.; Lee, M. H.; Liu, Z. P.; Chen, C. T.; Pickard, C. J. Mechanism for Linear and Nonlinear Optical Effects in β-BaB2O4 Crystals. Phys. Rev. B 1999, 60, 13380− 13389. (88) Liang, F.; Kang, L.; Lin, Z. S.; Wu, Y. C.; Chen, C. T. Analysis and Prediction of Mid-IR Nonlinear Optical Metal Sulfideswith Diamond-like Structures. Coordin. Chem. Rev. 2017, 333, 57−70. (89) Brown, I. D.; Altermatt, D. Bond-Valence Parameters Obtained from a Systematic Analysis of the Inorganic Crystal Structure Database. Acta Crystallogr. Sect. B: Struct. Sci. 1985, 41, 244−247. (90) Brese, N. E.; O'keeffe, M. Bond-Valence Parameters for Solids. Acta Crystallogr. Sect. B: Struct. Sci. 1991, 47, 192−197. (91) Reisman, A.; Mineo, J. Compound Repetition in Oxide-Oxide Interactions: the System Li2O-V2O5. J. Phys. Chem. 1962, 66, 1181−1185. (92) Klapper, H.; Hahn, T. Point-Group Symmetry and Physical Properties of Crystals. Springer. 2006, a, 804−808. (93) Dmitriev, V.; Nikogosyan, D. Effective Nonlinearity Coefficients for Three-Wave 28


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Interactions in Biaxial Crystal of mm2 Point Group Symmetry. Opt. Commun. 1993, 95, 173−182. (94) Jing, Q.; Dong, X. Y.; Yang, Z. H.; Pan, S. L.; Zhang, B. B.; Huang, X. C.; Chen, M. W. The Interaction Between Cations and Anionic Groups Inducing SHG Enhancement in a Series of Apatite-Like Crystals: A First-Principles Study. J. Solid State Chem. 2014, 219, 138−142.

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For Table of Contents Use Only Li3VO4 : A Promising Mid-IR Nonlinear Optical Material with Large Laser Damage Threshold Zhaohui Chena*, Zhizhong Zhanga, Xiaoyu Dongc, Yunjing Shic, Yaqin Liua, Qun Jinga,b*

The Li3VO4 crystal possesses excellent performances as potential mid-IR NLO material. The SHG intensity of the crystal is about 9.5 times that of KDP at 1064 nm and 1.6 times that of AgGaS2 at 2090 nm. Remarkably, Li3VO4 shows large LDT and wide transmission range. Furthermore, it can be grown by the TSSG method in the open system.

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Table 1. LDTs and band gap comparision with those of AgGaS2 (as the reference). Eg (eV)

SHG (×AgGaS2)

LDT (×AgGaS2)

AgGaS2

2.64

1

1

ZnGeP2

2.1

5.39

0.075

LiInS2

3.54

1.22

2.5

BaGa4S7

3.54

1

3

Na2ZnGe2S6

3.25

0.9

6

Na2BaSnS4

3.27

0.51

5

Na2BaGeS4

3.7

0.30

8

LiNbO3

3.11

0.41

5.0

Pb17O8Cl18

3.44

2

12.8

Li3VO4

4.27

1.6

25

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Table 2. The obtained SHG tensors of Li3VO4 and the ionic groups. d15 (pm/V)

d24 (pm/V)

d33 (pm/V)

origin

5.85

5.99

-11.99

VO groups

5.81

5.95

-11.92

Li ions

0.06

0.06

0

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Figure captions: Figure 1. Photograph of as-grown Li3VO4 crystals. Figure 2. The crystal structure of Li3VO4: (a) LiO4 tetrahedra (b) VO4 tetrahedra (c) unit cell (d) along the b axis (e) along the c axis. Figure 3. Transmittance spectra of Li3VO4. Figure 4. Phase-matching curves (i.e., SHG response vs particle size) for Li3VO4 at (a) 1064 nm and (b) 2090 nm. Figure 5. Direction of the local dipole moments for the LiO4 and VO4 tetrahedra. Figure 6. Electronic properties of Li3VO4. (a) Band structure. (b) Projected density of states (PDOS). Figure 7. The SHG-density of the virtual-electron and virtual-hole process of Li3VO4.

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Figure 1. Photograph of as-grown Li3VO4 crystals.

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Figure 2. The crystal structure of Li3VO4: (a) LiO4 tetrahedra (b) VO4 tetrahedra (c) unit cell (d) along the b axis (e) along the c axis.

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Figure 3. Transmittance spectra of Li3VO4.

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Figure 4. Phase-matching curves (i.e., SHG response vs particle size) for Li3VO4 at (a) 1064 nm and (b) 2090 nm.

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Figure 5. Direction of the local dipole moments for the LiO4 and VO4 tetrahedra.

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Figure 6. Electronic properties of Li3VO4. (a) Band structure. (b) Projected density of states (PDOS).

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Figure 7. The SHG-density of the virtual-electron and virtual-hole process of Li3VO4.

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Table of Contents

We combine alkali metal lithium and vanadium into one compound, Li3VO4, which possess excellent comprehensive performances as potential mid-IR NLO crystal. The SHG intensity of the crystal is about 9.5 times that of KDP at 1064 nm and 1.6 times that of AgGaS2 at 2090 nm. Remarkably, Li3VO4 shows large LDT is 25 times that of the standard IR NLO materials AgGaS2. Additional, the Li3VO4 crystal can be grown by the TSSG method in the open system and having a wide transmission range (0.29−6.05 μm).


Li3VO4: A Promising Mid-Infrared Nonlinear Optical Material with

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