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Controlled Growth of Layered Acentric CdTeMoO6 Single Crystals with Linear and Nonlinear Optical Properties Conggang Li, Xiangxin Tian, Zeliang Gao, Qian Wu, Peng Zhao, Youxuan Sun, Chengqian Zhang, Shaojun Zhang, Deliang Cui, and Xutang Tao Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00085 • Publication Date (Web): 02 May 2018 Downloaded from http://pubs.acs.org on May 5, 2018

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Crystal Growth & Design

Controlled Growth of Layered Acentric CdTeMoO6 Single Crystals with Linear and Nonlinear Optical Properties Conggang Li, Xiangxin Tian, Zeliang Gao*, Qian Wu, Peng Zhao, Youxuan Sun, Chengqian Zhang, Shaojun Zhang, Deliang Cui and Xutang Tao* State Key Laboratory of Crystal Materials & Institute of Crystal Materials, Shandong University, No. 27 Shanda South Road, Jinan 250100, P. R. China ABSTRACT: Acentric compounds with layered structure are of current interest owing to their advanced functional properties for technical applications. However, the growth of bulk single crystals of acentric materials with quasi-two-dimensional structure is challenging, which severely hinders the intrinsic properties investigation and optoelectronic applications of these materials. Herein, we report the controlled growth of bulk CdTeMoO6 single crystals with layered structure and the investigation of its linear and nonlinear optical properties. High quality CdTeMoO6 single crystals with dimensions of ~26 × 10 × 9 mm3 were successfully grown through the modified top-seeded solution growth (TSSG) method using TeO2-MoO3 as a flux. The transparent range of CdTeMoO6 single crystals is in the range of 0.345-5.40 µm, and with large birefringence (∆n = no − ne = 0.2868−0.2219 from 514 nm to 1.5467 µm). In addition, the nonlinear optical (NLO) coefficient d36 of CdTeMoO6 single crystals was measured to be 8.5 pm/V using Maker Fringe (MF) techniques. We also found CdTeMoO6 is type I phase-matchable based on the calculated phase-matching curves. Our results indicated that CdTeMoO6 single crystal is an excellent birefringent material combined with a promising NLO material for optoelectronic applications.

INTRODUCTION Design and growth of noncentrosymmetric inorganic single crystals continue to attract much attention to the scientific and industrial applications owing to their excellent optoelectronic properties.1-6 However, understanding of the outstanding properties exhibited by a host of layered materials has been limited by the difficulty in obtaining bulk single crystals, for example, due to obvious layered growth habits.7-14 These have been demonstrated by a number of layered acentric inorganic oxide single crystals, such as oxyborate crystals (KBBF, Ba2Zn(BO3)2), molybdate crystals (Bi2MoO6, ATMoO6 (A=Mg, Cd, Zn)) and tungstate crystals (Bi2WO6, Sb2WO6). Researchers have made tremendous efforts to grow such layered materials, but these bulk single crystals are extremely difficult to obtain. For example, over decades studies, the thickness of KBBF single crystals is still smaller than 5 mm since its layering tendency,15 which limited the coherent light output power. To circumvent the issue on obtaining bulk layered single crystals, a traditional and effective strategy was put forward to develop some KBBF derivates based on beryllium borates with reinforced interlayer bonding. For instance, several single crystals including Sr2Be2B2O7,16 Na2CsBe6B5O15,17 NaBeB3O6 and ABe2B3O7 (A = K, Rb),18 Na2Be4B4O11 and LiNa5Be12B12O3319 were found by Chen, et al. However, most of these materials are with layered growth habit and not easy to obtain bulk crystals. Acentric molybdate and tungstate single crystals have been extensively studied for frequency conversion, piezoelectricity, electro-optic and Raman shift, etc.20-27 The availability of single crystals with large size and high quality is essential for further progress in the investigation of functional properties and potential technological applications. Among the layered molybdate materials mentioned above, uniaxial molybdate crystal CdTeMoO6 (CdTM) possessed the excellent optoelec-

tronic properties.11,28 CdTM was first synthesized in the late 1970s by Forzatti et al.29,30 In 2001, Y. Laligant determined its structure with the tetragonal space group P-421m using both powder X-ray diffraction (PXRD) and electronic diffraction analysis (EDA).31 However, in previous studies, it was mainly concentrated on its intriguing catalytic properties.32-34 Recently, Zhao et al. reported the growth of flake CdTeMoO6 crystals with a remarkable powder SHG activity as twice as that of KTP and high calculated deff values, which means this crystal a promising nonlinear optical crystal.11,28 Unfortunately, to date, no large single crystals have been reported because of strong layered growth tendency, which are unsuitable for optical and other physical investigations. Inspired by this, we decide to solve this problem based on our rich flux growth experience of molybdate and tungstate crystals grown in our research group.35-41 In this work, we systematically demonstrated the controlled growth of high quality CdTM single crystals with dimensions of 26 × 10 × 9 mm3 by the modified top-seeded solution growth (TSSG) slow cooling method for the first time. Further, the effect parameters of relevant growth processes on the crystal quality and morphology were discussed and explored. In addition, the single-crystal X-ray diffraction experiments, rocking curve, thermal stability, linear and nonlinear optical properties, as well as the relationships between structure and physical properties are investigated in detail. Our large single crystals provide an ideal platform for further studies of the titled material, and pave the way for other important layered materials in laser science and technology EXPERIMENTAL SECTION CdTeMoO6 synthesis. The pure phase of CdTM was synthesized through high-temperature solid-state reaction method. The raw reactants CdO (Aladdin, 99.99%), TeO2 (Sinopharm Chemical Reagent Co., Ltd, 99.99%), and MoO3 (Alfa Aesar, 99.95%)

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were mixed in stoichiometric proportions, and then pressed into a pellet, and afterwards precalcined at 600 °C for 72 hours with several re-grindings. White powder products were obtained. Powder X-ray Diffraction. Powder X-ray diffraction data were collected on a BrukerAXS D8 ADVANCE X-ray diffractometer equipped with monochromated Cu Kα radiations of λ = 1.54056 Å in the 2θ range from 10° to 80° with each scan step of 0.02°/0.4s at room temperature. Single Crystal growth of CdTeMoO6. Single crystals of CdTM were first grown from its stoichiometric melts by Zhao et al. in 2013.11 But unfortunately, the typical crystal sizes of CdTM obtained are lesser than millimeter range in thickness due to its strong layered habit. In order to increase the crystal dimensions, we devoted to employ the modified top-seeded solution growth (TSSG) method to grow bulk single CdTM crystals. To eliminate the effects of impurities, the self-flux system TeO2-MoO3 was prior adopted. A Pt crucible consisting of CdTM, TeO2 and MoO3 in molar ratios (1:4:4) was loaded in the center of a programmable temperature furnace. The mixture was progressively heated up to 750 °C, stirring with a platinum stirrer for 20 h, and held for 2 days to ensure that the powders melt into a homogeneous solution. In the first growth run, a Pt wire was dipped into the solution, and many small flaky CdTM crystals were gained using spontaneous nucleation induced by the Pt wire during the slow cooling process. And then, some small high quality crystals were selected as seeds to grow large-scale single crystals via a top-seeded solution growth (TSSG) method. A crystallization temperature of 665 °C was determined precisely within a range less than 0.5 °C by observing the growth or dissolution of a test seed crystal on the surface of solution. A regular shaped CdTM seed was cut and attached to a platinum rod with platinum wire, and dipped into the melt at a temperature 3 °C above the saturation point. The temperature was held for 1 h in order to reduce the surface defects, and the solution was then cooled to the saturation point in half an hour. From the crystallization temperature, the melt was cooled at a rate of 0.1~0.5 °C /day while the seed rod rotated at a constant rate of 25 rpm until the desired size was gained. When the growth was completed, the single crystal was slightly drawn out and hung over the melt, after that, the temperature dropped at a rate less than 20 °C/h to the room temperature. Viscosity Measurements. The viscosity of the growth solution was measured using the rotary high-temperature viscometer (Orton RSV-1600, USA). The mixture in the furnace heated progressively up to 750 °C and kept for 10 hours to obtain complete solution. Afterwards, with temperature drop (1 °C/min), the curve of viscosity versus temperature was tested. Single-crystal X-ray Diffraction. A transparent single crystal of CdTM (0.15 mm×0.14 mm×0.11 mm) was selected and affixed to a glass fiber and installed on a Bruker SMART three-circle diffractometer equipped with an APEX II CCD area detector and Mo Kα1 radiation (λ=0.71073 Å). Data processing was integrated using the SAINT program of the APEX2 software for data integration and cell refinement. The SCALE program for area detector were utilized in the multi-scan absorption corrections.42 The structure was solved directly with Shelxtl-97 and refined by full matrix least-squares techniques on F2 with anisotropic thermal parameters and the refinements converged for I > 2σ (I). The crystallographic data were analyzed using the SHELXTL software package for calculations.43 High-Resolution X-ray Diffraction. High-resolution X-ray diffraction (HRXRD) were implemented on a Bruker-AXS D5005HR diffractometer equipped with a two-crystal Ge (220) monochromator set for Cu-Kα1 radiation (λ = 1.54056 Å). The accelerating voltage and tube current were 30 kV and 30 mA, and the step time and step size were 0.1 s and 0.001°, respectively.

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Two pieces of wafers of the same size, 6 mm × 6 mm × 2 mm, having faces (003) and (220) oriented wafers of CdTM mechanically polished were used as the test samples. Chemical and Thermal Stability Analysis. The chemical stability of CdTM at room temperature was studied and two thin CdTM single crystals with weights of ~0.15 and ~0.35 g were immerged into distilled water and diluted HNO3 solution for 2 day. To evaluate the thermal stability of CdTM crystal, DSC and TGA were carried out and a platinum crucible contained the CdTM powder sample (~0.0205 g) was heated over the temperature range of 30-950 °C (at a heating rate of 5K/min and with a flow of N2 atmosphere) by using a TGA/DSC1/1600HT analyzer. Linear Optical Measurements. Room temperature optical transmittance spectrums of CdTM were measured by using a Hitachi U-4100 UV-vis-IR spectrometer in the range of 300−1500 nm and a Nicolet NEXUS 670 FTIR spectrometer from 1500 to 6000 nm, respectively. Two 1.0 mm-thick along different orientations (001) and (110) slabs of the CdTM crystal polished on both sides were used to do the measurement. Second-Harmonic Generation (SHG). The powder SHG intensities of CdTM was evaluated by using the method of KurtzPerry.44 As the SHG efficiency depends directly on particle size, polycrystalline samples of CdTM were ground and sieved into specific particle size ranges (350−250, 250−150, 150−109, 109−75, 75−48 and 48−28 µm) for the test. The microcrystalline KTiOPO4 powders with the corresponding particle size ranges were served as a standard. In order to further evaluate the SHG intensity of CdTM and KTP, the comparative SHG signals at the same powder size (250−350 µm) of KTP and CdTM were performed. The measurements were carried out with a pulsed beam generated by a Q-switched Nd:YAG solid-state laser (10 ns, 1 Hz). Refractive Index Measurements. The refractive indices of CdTM were determined at room temperature. A wafer with both sides polished along a-axis was prepared by using the Unipol-300 grinding/polishing machine (MTI Co.). As a uniaxial crystal, the two optical axes of x- and z-axes are completely consistent with the crystallographic a- and c-axes respectively, based on the designation of axes in the crystallographic system. Accordingly, the other one optical axis, y, is perpendicular to the crystallographic ac-plane. The refractive index data of CdTM were recorded by a prism coupler (Metricon 2010, USA) with the He-Ne laser at five different wavelengths: 514, 636, 964.8, 1311, and 1546.7 nm. Maker Fringe Measurements. The NLO coefficients of CdTM were carefully determined by Maker Fringe technique.45,46 According to the group symmetry of point group -42m and the Kleinman approximation, there is only one independent non-zero NLO coefficients, d36 (=d14).47,48 The (110) crystal wafer was cut and polished for the measurements. We measured the second harmonic signal employing the fundamental light source produced by a Q-switched Nd:Yttrium lithium fluoride laser (1053 nm, 1 Hz). The detection of required signal averaged by a fast-gated integrator and boxcar average from the crystal wafer was carried out on a photomultiplier tube (PMTH-S1V1-CR131). The coefficient d36 = 0.39 pm/V in potassium dihydrogen phosphate KH2PO4 is used as the standard reference.49

RESULTS AND DISCUSSION Synthesis of Polycrystalline CdTeMoO6. Pure and polycrystalline CdTM was prepared by conventional solid-state reaction. XRD analysis was applied to confirm the phase purity of the white resultant. Figure 1 shows the experimental and calculated powder XRD patterns of the polycrystalline CdTM. The experimental XRD pattern of CdTM matches well with the calculated pattern. The calculated XRD patterns were obtained from the single crystal structure data through the Mercury 3.3 program.


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Figure 1. Experimental and calculated powder X-ray diffraction patterns of CdTeMoO6 polycrystalline. Thermal and Chemical Stability. The DSC and TGA curves of polycrystalline CdTM are shown in Figure S1 (Supporting Information). As shown in Figure S1, obviously there is one endothermic peak on the heating curve for DSC and a slight weight loss on the curve for TGA, which indicates that CdTM potentially melts congruently. Nevertheless, it is worth noting that powder XRD patterns of the product after test of DSC and TGA undoubtedly demonstrate that CdTM decomposed into CdMoO4 and other phase (Figure S2). This result indicates that CdTM melts incongruently, in sharp contrast to previous work by Zhao et al.11 The chemical stability of CdTM was also characterized. As shown in Figure S3, there is no change in weight by means of measuring the weight of CdTM crystal in distilled water, whereas a slight change in distilled HNO3 solution, indicating CdTM crystal has good chemical stability. Growth and Morphology of the CdTeMoO6 Crystals. Our experiments suggest that CdTM melts incongruently. Therefore, a modified TSSG was employed to grow CdTM crystals. In our preliminary trial, an unavoidable common problem during growth is the appearance of floating crystals, which makes it always crystallize in the solution of crucible instead of the platinum wire. Considering this situation, we try to adopt a narrow thermal gradient distribution of the homemade vertical resistive furnace. Taking advantage of spontaneous crystallization on a platinum wire dipped into the solution, some plate-like single crystals were obtained from the homogeneous melt and verified using powder Xray diffraction, which obviously exhibits plate-like crystal morphology and shows strong layered habits (Figure 2a-b). Whether the flux technique can be successful depend mainly upon employing a suitable flux system. Many attempts have been made to determine flux systems that allows CdTM crystals to be grown better and easier, such as MoO3, TeO2, and MoO3–TeO2 mixtures. With each self-flux agent, mixtures of CdTM and flux in different match were studied sufficiently. When solely taking MoO3 as flux, CdTM crystals can be smoothly obtained from the mixture, however the undesirable results were emerged as the surface and interior of the as-grown CdTM crystals contain inclusions of flux or veils (Figure S4). Considering the lower melting point, TeO2 system seems more suitable than MoO3 and was employed followed. According to the crystal growth with many times, however, a host of new spontaneous nuclei were always formed and attached to the seed during CdTM growth, which prevents the growth of large and high quality crystals (Figure S5). Later, MoO3 and TeO2 were investigated as fluxes. Several ratios of MoO3 : TeO2 were chosen to grow CdTM crystals. According to having a great deal of attempts, the favorable molar ratio of CdTM: MoO3: TeO2 was obtained for the growth of CdTM single crystals. Based on our

optimized experimental growth conditions, regularly shaped and transparent single crystals of centimetre-sized CdTM were grown successfully from solution using non-oriented seeds (Figure 2c). As shown in Figure 2d, the CdTM crystal obtained with nonoriented seed has well-developed {001}, {110} and {010} facets, but the CdTM shows obvious layered growth habit. To improve upon the negative situation, we adopted slower cooling rate and used different oriented seeds to overcome layered growth habit. Using seeds oriented along the [001], the quality of the crystal grown was poor, which contained multiple polycrystal layers as shown in Figure S6. Obviously, the seed orientation along the [001] is unfavorable for the growth of CdTM crystals. Subsequently, using the [010]- and [110]-oriented seeds, well-shaped and colorless single crystals of CdTM were successfully grown with slow cooling rates respectively. As can be seen, Table 1 lists the detailed growth conditions and the results of growth, and both the pictures and morphologies of as-grown CdTM crystals are exhibited in Figure 3a-f. Analyzation of the theoretical morphology of the CdTM crystal is done using its structural parameters by the Materials Studio Modeling program50, based on BravaisFriedel and Donnay-Harker (BFDH) theory.51,52 When adopting a seed along [010], a CdTM crystal with dimensions up to 25 × 15 × 4 mm3 was obtained with dominating facets {001}, {010}, {110} and {011} (Figure 3a-c). When adopting [110]-oriented seed, a CdTM crystal with dimensions of 25 × 10 × 9 mm3 was gained successfully and exhibited the {001}, {011} and {110} facets (Figure 3e-f). It's worth noting that, after several circles of crystals growth, we find that the cooling rate of the melt has a significant impact on not only the crystal quality but also morphology. We also found that the thicker crystals could be obtained with lower cooling rates, which is in agreement with YBa2Cu3Ox and YBa2Cu3O7−x.53,54 Furthermore, clearly the dimension of the crystal obtained with the [110]-oriented seed is more thicker than that of the crystal obtained using the [010]-oriented seed. And it indicates that the problem of layer growth habit of CdTM is improved by the narrow thermal gradient distribution and the selection of a suitable flux with slower cooling rate using the [110]-oriented seed. Thus, to grow the bulk single crystals of the layered CdTM, a narrow thermal gradient distribution, a suitable flux, slower cooling rate and a [110] oriented seed should be adopted. In order to quantify the crystalline quality of the obtained CdTM crystal, rocking curve measurement was performed. The FWHM of the rocking curves along (003), (220) are 39.28'' and 63.46'' respectively (Figure 4), indicating the obtained crystal is of high quality.

Figure 2a-d. (a-b) Photographs of the as-grown CdTeMoO6 crystals through spontaneous crystallization; (c-d) Pictures and simulated morphologies of the obtained CdTeMoO6 crystals using non-oriented seed.



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Figure 3. Morphology and simulated morphologies of the obtained CdTeMoO6 crystals when using different oriented seeds: (a), (b) and (c) for [010]-oriented seed; (d), (e) and (f) for [110]-oriented seed. Table 1 Growth conditions of CdTeMoO6 crystals grown by the modified top-seeded solution growth method. crystal samples Figure 2c

seed orientation --

crystal size (mm3)

raw material ratio

cooling rate (°C/ day)

crystal weight (g)

1:4:4

1.0-1.2

0.68

12 × 12× 1

Figure 3a

[010]

1:4:4

0.8-1.0

1.15

15 × 10× 2

Figure 3b

[010]

1:4:4

0.4-0.6

7.42

25 × 15× 4

Figure 3d

[110]

1:4:4

0.4-0.6

14.49

32 × 15× 5

Figure 3e

[110]

1:4:4

0.2-0.4

14.25

25 × 10× 9

Figure 4. Rocking Curves and corresponding High-resolution X-ray diffractions for (003) and (220) CdTeMoO6 crystal wafers. Viscosity Measurements. Viscosity is a very important physiture is presented in Figure S7, which indicated the measured viscal quantity reflecting the momentum transport in the reaction cosity data was moderate for CdTM crystal growth. melt. Diverse viscosities have a significant effect on quality of Crystal Structure Determination. The structure of CdTM has crystals. The measured viscosity curves as a function of temperabeen confirmed through PXRD and EDA and belongs to the te-


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tragonal space group of P-421m.31 In 2013, Zhao et al. also reported the crystal structure of CdTeMoO6.11 Single-crystal X-ray diffraction data were recorded to reconfirm the crystal structure with the unit cell parameters are a = 5.283(14) Å, c = 9.061(2) Å, and Z = 2. (Table S1–S2). And these values are similar with the reported result.11 As shown in Figure 5, there are one crystallographically independent Cd atom, one independent Mo atom, one independent Te atom, and three independent O atoms within the asymmetric unit. The Cd is viewed as four-coordinated forming inerratic polyhedra, with equal Cd–O bond lengths at 2.228(3) Å. The Mo is a distorted tetrahedral coordination geometry connected to four oxygen atoms, with the Mo–O bond lengths of 1.706(4)-1.867(3) Å. The Te is coordinated to four O atoms in a seesaw environment with the Te–O bond lengths of 1.863(3)-2.152(3) Å. In the structure of CdTM, the Cd–O, Mo–O and Te–O bond lengths are in the normal ranges. For CdTM, it has three types of NCS chromospheres, i.e. CdO4, MoO4 tetrahedra and TeO4 polyhedra with a stereochemically active lone-pair. It is obvious that CdTM shows a distinct neutral layered structure made up of CdO4 tetrahedra connected to asymmetric MoO4 and TeO4 polyhedras. The MoO4 tetrahedra and the TeO4 polyhedra are linked by sharing edges to further form long chains along the c axis. All the chains are interconnected by the CdO4 tetrahedra to form neutral layers in two dimensions (Figure 6d), stacking along the crystallographic c-axis direction. Furthermore, a 3D framework was formed as these layers are further held together (Figure 6e). Therefore it is easy to envision that crystal growth is very difficult along the c axis. In other words, the habit of growth can be ascribed to the two-dimensional structure of CdTM. The crystal growth of CdTM exhibits obviously anisotropic because of the weak force between adjacent layers, which is consistent with the previous crystal growth characteristic.11 Nevertheless, the habit of growth was significantly improved using the modified TSSG method. Further, the distance of interlayers for CdTM was also measured and calculated to be 1.27 Å. Considering the same situation occurs in the crystal growth of MgTeMoO6 and ZnTeMoO6 with interlayer distances of 1.33 Å and 1.27 Å respectively,55 it is observed that the problem of growth existed in the ZnTeMoO6 and MgTeMoO6 will be solved through the modified TSSG method.

Figure 5. View of CdTeMoO6 unit cell and the representation of ball-and-stick.

Figure 6. (a) CdO4 tetrahedra, (b) TeO4 polyhedral, (c) MoO4 polyhedral, (d) two-dimensional layered structure, (e) 3D framework structure of the CdTeMoO6 crystal. Optical Measurements. Zhao et al. reported UV and IR transmittance spectra of the CdTeMoO6 crystal obtained from its stoichiometric solution through a spontaneous nucleation method.11 It is necessary to investigate the transmittance spectra based on different crystal axis directions, which reflects on the quality of the single crystalline samples with the polished surfaces. The UV– vis-NIR transmission spectra and infrared (IR) transmission spectrum of the CdTM crystal at room temperature with respect to the crystal plane (110) and (001) are presented in Figure 7. The UVVis-NIR spectrum indicates that the CdTM crystal exhibits a high transparency ranging from 400 to 1500 nm with the UV cut-off wavelength around 345 nm. And for the mid-IR range, the CdTM crystal also shows a good transparency up to 5.0 µm with the long-wavelength absorption edge around 5.4 µm. Therefore, the transparency of CdTM crystal possesses a very broad region from 0.345 to 5.4 µm. Furthermore, the results are comparable to those of many other molybdate/tungstate oxide crystals, including BaTeMo2O9 (0.4-5.4 µm),35 Cs2TeMo3O12 (0.43-5.38 µm),37 MgTeMoO6 (0.36-5.2 µm),10 Na2Te3Mo3O16 (0.42-5.4 µm),56 Cs2TeW3O12 (0.41-5.31 µm).39 The NLO investigations of CdTM was made by the technique of Kurtz and Perry.44 The SHG effect of the CdTM has been measured with KTP as a reference, and found to be as twice as that of KTP. The strong SHG effect can be attributed to the cooperation effects of the TeO4, MoO4 and CdO4, and the orbital character from the valence band edge.28 Figure S8 shows the curves of measured SHG intensity versus particle sizes, indicating the CdTM is a phase-matching NLO material.



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Figure 7. UV-vis-NIR (a) and mid-IR (b) transmittance spectrum of the CdTeMoO6 crystal along the (110) and (001) planes. Table 2. Experimental refractive index no, ne at different wavelengths for single crystal CdTeMoO6. Wavelength (µm)

no

ne

∆n=no-ne

0.514

2.2945

2.0077

0.2868

0.636

2.2394

1.9807

0.2587

0.9648

2.1876

1.9538

0.2338

1.311

2.1681

1.9457

0.2222

1.5467

2.1617

1.9398

0.2219

Table 3. Sellmeier coefficients derived from the measured refractive indices of single crystal CdTeMoO6. Sellmeier coefficients

A

B

C

D

no

4.63967

0.13561

0.04816

0.01097

ne

3.76733

0.05538

0.05653

0.01088

Table 4. Space group, transmission, birefringence (∆n), and NLO coefficients (dij) of CdTM comparing with other NLO materials. Birefringence(∆n) (nmax-nmin)

SHG Coefficients (dij) pm/V

Crystal

Space group

Transmission (µm)

CdTeMoO6 (CdTM)

P-421m

0.345-5.40

0.2219 – 0.2868 (1546.4 – 514 nm)

d36=8.5

P63

0.43-5.38

0.131 – 0.204 (2325 – 480 nm)

d31=6.8, d33=6.5

KTiOPO4 (KTP)67-69

Pna21

0.35-4.50

0.1277 – 0.0921 (435.8 – 1064 nm)

d31=2.2, d33=14.6

d32=3.7,

LiB3O5 (LBO)48,70,71

Pna21

0.16 - 2.6

0.0457 – 0.0399 (253.7 – 1064.2 nm)

d31=0.96, d33=0.06

d32=1.04,

β-BaB2O4 (BBO)72,73

R3c

0.19 - 3.5

0.1247 – 0.1128 (404.7 – 1014 nm)

Cs2TeMo3O12 (CTM)37,58


d11=2.26, d31=0.113, d22 < d31

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Refractive Index Measurements. The CdTM crystal with the space group P-421m, i.e., a uniaxial crystal system, possesses two principal refractive index data, ne and no. The refractive index data of CdTM crystal was measured by using A Metricon Model 2010/M prism coupler, which has an estimated accuracy of 2 × 10-4 for measuring refractive index. The experimental values for no and ne at 5 different wavelengths - 514, 636, 964.8, 1311 and 1546.7 nm are listed in Table 2. The measured and fitted refractive index data is shown in Figure 8. And the Sellmeier equations fitted with the experimental data, are as follows:57

no2 = 4.63967 + ne2 = 3.76733 +

0.13561

λ2 - 0.04816 0.05538

λ2 − 0.05653

− 0.01097λ2

(1)

− 0.01088λ2

(2)

where λ is the wavelength in micrometers (µm). The Sellmeier parameters (A, B, C, and D) for each refractive index are listed in Table 3. According to the refractive indices (no > ne) at corresponding wavelengths, the conclusion is that CdTM belongs to a negative uniaxial optical crystal. The birefringence value of tetragonal CdTM is large (∆n = 0.2219-0.2868 from 1546.4 nm to 514 nm), that is larger than that of other d0 transition metal tellurites that exhibit large birefringence, such as β-BaTeMo2O9 (∆n = 0.150- 0.226 from 4358 nm – 1068 nm),35 α-BaTeMo2O9 (∆n = 0.194 - 0.305 from 2325 nm to 404.7 nm),36 Cs2TeMo3O12 (∆n = 0.131 - 0.204 from 2325 nm to 480 nm),58 Cs2TeW3O12 (∆n = 0.145 - 0.220 from 2325 nm to 480 nm),59 Na2TeW2O9 (∆n = 0.147 - 0.207 from 1062.6 nm to 450.2 nm).60 Moreover, the birefringence of CdTM is comparable with many advanced birefringent materials such as TiO2 (∆n = 0.333 – 0.252 from 454 nm to 1330 nm),61 LiNbO3 (0.0836 @ 633 nm),62 CaCO3 (0.171 @ 633 nm),63 α-BaB2O4 (0.1222 @ 532 nm),64 YVO4 (0.225 @ 633 nm),65 which are the most commonly used birefringent materials. Significantly, our group has reported the design of wide-band polarized prisms for biaxial α-BaTeMo2O9.66 Considering that it exhibits large birefringence, wide transparency, uniaxial molybdate CdTM may be a more attractive candidate for the prism materials.

 e n θ m ( I ) = arcsin  2o  n  1

 (n2o ) 2 − (n1o ) 2    ×  (n o ) 2 − (n e ) 2  2 2   2

0.5

(3)

Where n1o and n2o , n2e represent the refractive indices at the fundamental and harmonic wavelengths, respectively. The PM angels in the transmission range of CdTM are listed in Figure 9. It is obviously that PM can be realized in CdTM in a wide transmission range. At 1064 nm, the PM angle is shown to be 34.6°.

Figure 9. Type-I PM angels versus wavelengths for CdTM. NLO Coefficient Measurements. The Maker fringe method was used to test the NLO coefficients for CdTM. CdTM is a acentric compound belonging to crystal class -42m. Accordingly, CdTM possesses only one nonzero second-order NLO coefficient, d14=d36, after Kleinman symmetry is considered. The determination of d36 uses 110-cut CdTM samples with thickness of 1.0 mm. The following figure indicates the theoretical and experimental Maker Fringes of CdTM (Figure 10). It can be seen that the shapes of the experimental Maker Fringes are compared well with that of theoretical Maker Fringes. The NLO coefficient of CdTM relative to d36 (KDP) was measured through fitting the calculated Maker fringes. Considering the absolute value of d36 (KDP) is 0.39 pm/V,49 the corresponding NLO coefficient of d36 for CdTM is calculated to be 8.5 pm/V. As can be seen, Table 4 lists the some widely used NLO crystals, it is obvious that the NLO coefficients are much larger than those of β-BaB2O4 and LiB3O5. Moreover, the symmetry of CdTM (P-421m) is higher than that of LiB3O5 (Pna21) and KTP (Pna21), which makes the crystal processing and device design more advantageous. Taking further into account the wide transmission region, CdTM is an outstanding candidate for nonlinear optical applications.

Figure 8. Calculated curves through the Sellmeir fits and dispersion curves of the refractive index date for CdTM crystal. Phase Matching (PM) Calculations. It is crucial to achieve the phase matching for NLO materials.74 From the refractive indices of CdTM, the phase-matching angles can be calculated based on the Sellmeier equations. And the results indicated that the typeI PM can be realized in CdTM over a broad wavelength range. According to Eq. (3), the PM angels at different wavelengths can be calculated.



Figure 10. Samples for measurements on CdTM using the MF technique and Measured and calculated Maker Fringe patterns as a function of the incidence angle θ and fitted envelope for CdTM.

CONCLUSIONS In summary, based on the interest of improving the layering growth tendency of CdTM crystals, we succeeded in improving significantly the dimensions of CdTM single crystals through the modified TSSG technique under controlled conditions. It is concluded that the thicker high quality crystals could be grown at lower cooling rates. The crystal morphology and growth habits demonstrate that the seed along [110] is ideal for the CdTM growth. The measured FWHM of the CdTM crystal along (003) is 39.28''. In addition, CdTM has stable thermal and chemical properties, a remarkable SHG efficiency (2 × KTP), large birefringence, a broad transmission window region from 345 to 5400 nm, and large NLO coefficients of d36 = 8.5 pm/V. All these physical properties support the potential of CdTM as a NLO material as well as a birefringent material. These successful growth of large CdTM single crystals also provide a reference for other layered materials which are difficult to grow bulk crystals.

ASSOCIATED CONTENT Supporting Information

Page 8 of 11

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AUTHOR INFORMATION

X. MgTeMoO6: A neutral layered material showing strong second-

Corresponding Author

harmonic generation. J. Mater. Chem. C 2012, 22, 9921-9927.

*E-mail: [email protected]; [email protected]

(11) Zhao, S.; Jiang, X.; He, R.; Zhang, S.-Q.; Sun, Z.; Luo, J.; Lin, Z.;

Author Contributions

Hong, M. A combination of multiple chromophores enhances second-

All authors have given approval to the final version of the manuscript.

harmonic generation in a nonpolar noncentrosymmetric oxide:

Funding Sources Notes

(12) Zhao, S.; Luo, J.; Zhou, P.; Zhang, S.-Q.; Sun, Z.; Hong, M.

The authors declare no competing financial interest.

CdTeMoO6. J. Mater. Chem. C 2013, 1, 2906−2912. ZnTeMoO6: a strong second-harmonic generation material originating from three types of asymmetric building units. RSC Adv. 2013, 3,

ACKNOWLEDGMENT

14000−14006.

This work is financially supported by the National Natural Science Foundation of China (Grant Nos. 51572155, 51321091, 11504389), Independent Innovation Foundation of Shandong University, IIFSDU, Shandong Provincial Natural Science Foundation, China (ZR2014EMM015), National key Research and Development Program of China (2016YFB1102201), the Foundamental Research Founds of Shandong University (2017JC044).We greatly thank, Dianxing Ju for assistance in in collecting singlecrystal X-ray diffraction data and structural refinements; and Dr. Yangyang Dang for helpful discussions.

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For Table of Contents Use Only Controlled Growth of Layered Acentric CdTeMoO6 Single Crystals with Linear and Nonlinear Optical Properties Conggang Li, Xiangxin Tian, Zeliang Gao*, Qian Wu, Peng Zhao, Youxuan Sun, Chengqian Zhang, Shaojun Zhang, Deliang Cui and Xutang Tao* State Key Laboratory of Crystal Materials & Institute of Crystal Materials, Shandong University, No. 27 Shanda South Road, Jinan 250100, P. R. China CORRESPONDING AUTHOR EMAIL ADDRESS: [email protected]

High quality and large-sized CdTeMoO6 crystals were successfully grown and their linear and nonlinear optical properties were investigated. CdTeMoO6 has a remarkable SHG efficiency, large birefringence and is type I phase-matchable. Nonlinear optical coefficient of d36 = 8.5 pm/V was determined using Maker fringe techniques. Our results indicate that CdTeMoO6 is a promising NLO material and an excellent birefringent material.

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