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Crystal Growth and Linear and Nonlinear Optical Properties of KIO3·Te(OH)6 Hongping Wu,†,‡ Hongwei Yu,† Weiguo Zhang,† Jacqueline Cantwell,§ Kenneth R. Poeppelmeier,§ Shilie Pan,*,‡ and P. Shiv Halasyamani*,† †

Department of Chemistry, University of Houston, 112 Fleming Building, Houston, Texas 77204, United States Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, 40-1 South Beijing Road, Urumqi 830011, China § Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3133, United States ‡

S Supporting Information *

ABSTRACT: A single crystal of the nonlinear optical material KIO3·Te(OH)6 (KTI) with dimensions of 37 × 7 × 5 mm3 was successfully grown at room temperature by slow evaporation. Linear and nonlinear optical measurements were performed on these crystals. Rocking curve measurements indicate that the single crystal is of high quality with a full width at half-maximum (fwhm) of 0.023° (82 arcseconds) from the (010) reflection. Refractive index measurements revealed a birefringence of 0.0545 @ 1064 nm. Through the refractive index measurements and the fitted Sellmeier equations, we determined the Type I and Type II phase-matching wavelength ranges. KTI is Type I (Type II) phasematchable with a fundamental wavelength range from 674−3266 nm (880−2260 nm). Powder second-harmonic generation (SHG) measurements indicate an SHG intensity of 1.2× KH2PO4 (KDP). SHG coefficients were determined by the Maker fringe method on cut and polished (100) and (010) single crystal wafers. The d31 = 0.24 pm/V and d32 = 0.73 pm/V were determined. Laser damage threshold (LDT) measurements were also performed, which indicates that KTI has an LDT of 731 MW/cm2 at 1064 nm with a 6 ns pulse width.



INTRODUCTION

In this paper, we report on the large crystal growth and linear and nonlinear optical properties of KIO3·Te(OH)6 (KTI). The crystal structure of KTI has been reported;44 however, no functional properties were measured. We have grown centimeter size single crystals of KTI that enabled us to measure the refractive indices, NLO coefficients, and laser damage threshold, and determine the phase-matching angles and wavelength ranges. In addition, the crystal quality was investigated through rocking curve measurements.

Non-centrosymmetric (NCS) compounds have attracted considerable interest for their important technological properties as piezoelectricity, ferroelectricity, pyroelectricity, and especially nonlinear optical (NLO) behavior.1−9 In order to fully investigate the functional properties of these materials, large crystalseveral millimeters in each dimension are needed. This has been accomplished for a few materials, namely, β-BaB 2 O 4 (BBO),10 LiB 3 O 5 (LBO), 11 KH 2 PO 4 (KDP),12 KTiOPO4 (KTP),13 LiNbO3 (LN),14 ZnGeP2,15 and AgGaSe2.16 Large single crystals, that have been indexed, enable one to measure accurately a host of physical properties including refractive indices, and thus birefringence,17−21 NLO coefficients,18−20 NLO properties including phase-matching angles at second-order and higher harmonic generation,22−24 polarization magnitude, 25,26 phase-matching wavelength ranges,18−20,27 thermal properties including thermal expansion, specific heat, thermal diffusivity, and thermal conductivity.28−30 There are a variety of methods in which large single crystals can be grown including Czochralski,31,32 Bridgman,33−35 topseeded solution growth,18−20,36−38 transport,39,40 and hydrothermal methods.41−43 However, no single method is suitable for growing all types of crystals. © 2017 American Chemical Society



EXPERIMENTAL SECTION

Reagents. KIO3 (Alfa Aesar, 99%) and H6TeO6 (Alfa Aesar, 99%) were used as received. Crystal Growth. A seed crystal of KTI was obtained by slow evaporation of an aqueous solution at room temperature. Stoichiometric amounts of KIO3 (2.140 g, 1 mmol) and H6TeO6 (2.296 g, 1 mmol) were dissolved in 100 mL of H2O. This solution was stirred for 30 min until it became clear. After about 1 week, millimeter-sized KTI crystals were observed on the bottom of the beaker (see Figure S1). With these seed crystals, larger KTI crystals were grown at room temperature. Received: May 18, 2017 Revised: June 30, 2017 Published: July 6, 2017 4405

DOI: 10.1021/acs.cgd.7b00704 Cryst. Growth Des. 2017, 17, 4405−4412

Crystal Growth & Design

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To grow the larger KTI crystal, 6.420 g (3 mmol) of KIO3 and 6.888 g (3 mmol) of H6TeO6 were dissolved in 500 mL of H2O. The solution was stirred until it became clear. The solution was placed in air for 4 days. During these 4 days, some small crystals formed and grew to a big enough size for observing them on the bottom of the beaker. These crystals were filtered out, and the remaining solution was transferred into another beaker for crystal growth. A KTI seed crystal was suspended into this solution by using a thin platinum wire. To reduce the evaporation of water, the beaker was covered with a polythene sheet with dozens of millimeter-size holes (see Figure S2). After 3 weeks, a centimeter-sized KTI crystal was pulled out of the solution. High-Resolution X-ray Diffraction Measurement. A polished (010) KTI wafer with dimensions 8 × 6 × 2 mm3 was used for the high-resolution X-ray diffraction measurement. The wafer was placed on a Rigaku High Resolution ATXG with a 4-bounce Ge-220 monochromator set for Cu−Kα radiation (λ = 1.54056 Å). The scan range and speed were 0.2° and 0.001°/s, respectively. The measurement was made by changing the angle between the X-ray beam and the wafer surface (the ω scan) around the Bragg diffraction peak position θ. Powder X-ray Diffraction. To determine if the crystals were indeed KTI, powder X-ray diffraction (PXRD) was performed on a PANalytical X’Pert PRO diffractometer equipped with a diffractedbeam monochromator set for Cu Kα (λ = 1.54056 Å) radiation in the 2θ range from 10° to 70°. The scanning step width was 0.02°, and the fixed counting time was 1s per step. The experimental PXRD pattern on the ground crystal matches well with the calculated one of the compound simulated from single-crystal data (Figure S3). Thermal Property Analysis. Thermogravimetric (TG) and differential thermal analyses (DTA) were carried out on an EXSTAR TG/DTA 6300 thermal analyzer instrument (SII Nano Technology Inc.). Polycrystalline KTI was placed in a platinum pan and heated/ cooled at a rate of 10 °C/min in an atmosphere of flowing N2 from 25 to 750 °C. UV−vis-NIR Transmission and Infrared Spectra. UV−vis-NIR transmission spectrum for KTI was collected on a Varian Cary 5000 scan spectrophotometer from 200 to 2500 nm. A 2.0 mm thick (100) crystal wafer was used to measure the transmission spectrum. Refractive Index Measurements. The refractive indices of KTI were determined using a Metricon model 2010/M prism coupler (Metricon Co.) at five different wavelengths: 450.2, 532, 636.5, 829.3, and 1062.6 nm. For the measurement, a (010) wafer was polished with the Unipol-300 grinding/polishing machine (MTI Co.). Powder Second Harmonic Generation (SHG) Measurement. The powder SHG (PSHG) response was measured by the Kurtz-Perry method46 using a pulse Nd:YAG laser of wavelength 1064 nm (Quantel Laser, Ultra 50). Polycrystalline KTI was ground and sieved into distinct particle size ranges (80% from 300 to 1505 nm, with a UV absorption edge and IR transmission cutoff edges of 274 and 1751 nm, respectively (Figure S9). In addition, it is noteworthy that the KTI crystal is stable and nonhygroscopic in air even though it was grown from an aqueous solution. The KTI crystal used for the transmission measurement was left in air for 10 days, and the transmission spectrum was remeasured. The transmission spectra before and after 10 days are almost identical, indicating that KTI is stable and nonhygroscopic in air. Refractive Indices. KTI crystallizes in orthorhombic space group Pna21, that belongs to a biaxial crystal system with three independent principle refractive indices, nx, ny, and nz. The three refractive indices can be measured by the prism coupling method.18 In the measurement, a 6 × 6 × 2 mm3 (010) crystal wafer was used (Figure S10). The measured refractive indices at wavelengths 450.2, 532, 636.5, 829.3, and 1062.6 nm are listed in Table 1. By convention,56,57 the selection of optical axes should result in nx < ny < nz. As seen in Table 1, nz − ny > ny − nx, thus KTI is a positive biaxial optical crystal.58 The birefringence, Δn = nz − nx, ranges from 0.0545 to 0.0617 over the measured wavelength region, 450.2−1062.6 nm. To describe the dispersion of the refractive indices, Sellmeier equations were fit by the least-squares method.

Figure 7. Phase-matching angles, ϕ and θ, with respect to the fundamental wavelength for KTI. The type I (type II) PM curves are shown in black (red). Note that the PM wavelength range is consistent with the refractive index data (Figure 6). The type I (type II) PM wavelength ranges are 674−3266 nm (880−2260 nm). The black circles indicate 1064 nm.

Figure 8. PM angles, θ and ϕ, for KTI at 1064 nm.

grown crystals.18,19 Thus, we investigated the impact of seed directions on KTI crystal morphology. The seed directions can be controlled by attaching different crystal faces to the bottom of the beaker (Figure S6). An (010)-seed was initially tried, and a 13 × 5 × 5 mm3 of KTI crystal was grown (Figure 2c). Clearly, the grown crystal using the (010)-seed has a plate-like morphology and exhibits prominent {100}, {010}, {110}, and {011} faces (Figure S7a). Next, a (110)-seed was used, and a 16 × 5 × 4 mm3 of the KTI crystal was obtained with prominent {110} and {111} faces (Figure S7b). Generally, for crystal in orthorhombic system, the (100), (010), and (001) faces are more important for property measurements. Therefore, the crystals with (100), (010), or (001) faces appearing on morphology as the largest prominent faces would be preferable in consideration of easier processing and higher utilization of crystal. On the basis of above analysis, for the KTI crystal growth, the (010) seed direction is the best seed direction. To determine the crystal quality, rocking curve measurements were

ni2 = A +

B − Dλ 2 λ2 − C

where λ is the wavelength in microns, and A, B, C, and D are the Sellmeier parameters. The fitted coefficients for each refractive index are shown in Table 2. The refractive-index dispersion curves for KTI based on the fitted Sellmeier 4408

DOI: 10.1021/acs.cgd.7b00704 Cryst. Growth Des. 2017, 17, 4405−4412

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Figure 9. (a) Orientation of the KTI and KDP crystal wafers for measuring the NLO coefficients. Experimental and theoretical Maker fringes for (b) d31 and (c) d32 of KTI, (d) d36 of KDP (black solid lines: experimental fringes; red and blue solid lines: fit and envelop, respectively, of the Maker fringe).

include two parts: 0−13.65° and 58.85−90° in the xz-plane. Whereas in the xy-plane (yz-plane), ϕ (θ) ranges from 0 to 90°. With the PM data, we calculated the PM angles for 1064 nm radiation. As seen in Figure 8, the PM angles for Type I PM range from (ϕ = 90°, θ = 23.45°) to (ϕ = 0°, θ = 65.85°), and the PM angles for Type II PM range from (ϕ = 90°, θ = 68.25°) to (θ = 90°, ϕ = 60.65°). NLO Coefficient Measurements. KTI crystallizes in crystal class mm2 and has three independent nonzero SHG coefficients, d31, d32, and d33.47 These coefficients can be measured by using the Maker fringe technique.47 The schematic of the Maker fringe measurement system and calculations have been reported previously.18−20 In the orthorhombic system, the crystallophysical axes x, y, z correspond to the crystallographic a, b, and c axes, respectively.48,49 For the SHG coefficient measurement, the orientation of the crystals and the relationships of Pω and P2ω are shown in Figure 9a. The Maker fringes for the d31 and d32 coefficients of KTI and d36 coefficient of KDP were obtained (see Figure 9b−d); however the Maker fringe for d33 is too weak to be observed. By fitting the experimental Maker fringes, the NLO coefficients of KTI relative to d36(KDP) were determined. The results indicate that d31 = 0.62 × d36(KDP) and d32 = 1.86 × d36(KDP). As the d36 coefficient of KDP is 0.39 pm/V,60 the absolute NLO coefficients of KTI are d31 = 0.24 pm/V and d32 = 0.73 pm/V. Laser Damage Threshold. The laser-induced damage threshold is also an important parameter in the application of NLO materials.11,61 For the KTI crystal, the measured laser

equations, and measured refractive indices are shown in Figure 5. It is clear that they are in an excellent agreement. Phase Matching (PM) Calculation. On the basis of above Sellmeier equations, the PM wavelength ranges and PM angles at each wavelength can be calculated (Figure 6 and Figure 7). On the basis of the PM conditions, n(ω) = n(2ω) and n(2ω) = 1/2(n(ω)slow + n(ω)fast) for type I and type II PM, respectively, must be satisfied.59 The type I PM wavelength region can be obtained from the intersection of the nz(ω) and nx(2ω) curves (Figure 6). The type I PM wavelength range for fundamental (second harmonic) light is 674−3266 nm (337−1633 nm). The type II PM wavelength range can be obtained from the intersection of the 1/2(nx(ω) + nz(ω)) and nx(2ω) curves (Figure 6). The type II PM wavelength range for fundamental (second harmonic) light is 880−2260 nm (440−1130 nm). The limits of type I and type II PM SHG wavelength are 337 and 440 nm, respectively. Thus, the KTI crystal can achieve 532 and 355 nm light by direct type I SHG and third harmonic generation (THG), from a 1064 nm laser. Furthermore, the relationship of the PM angles in the three principle planes vs wavelengths is also calculated (Figure 7). In the xy- and yz-planes, KTI can achieve both type I and type II PM, whereas in xz-plane, only type I PM can be achieved. As seen in Figure 7, the type I and type II PM wavelength ranges are consistent with the data presented in Figure 6. The type I PM wavelength range for fundamental light is 674−3266 nm, while the type II PM wavelength range for fundamental light is 880−2260 nm. Figure 7 also shows the PM angles of θ ranges 4409

DOI: 10.1021/acs.cgd.7b00704 Cryst. Growth Des. 2017, 17, 4405−4412

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power was set at 250 mW and available area is 0.38 cm2. On the basis of the equation:

(Grant No. 2014CB648400), the Outstanding Young Scientists Project of CAS, the National Natural Science Foundation of China (Grant Nos. U1303392, 51425206), the Western Light Foundation Program of CAS (Grant No. 2016-QNXZ-A-2), P.S.H., H.Y., and W.Z. thank the Welch Foundation (Grant E1457) and the NSF (DMR-1503573) for support. J.C. and K.R.P thank the NSF (DMR-1608218) for support. This work made use of the J.B.Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Materials Research Center of Northwestern University and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205).

Pth = E /(t . S) where S is the available area, t is the pulse width in ns, and E is the laser energy in Joule. The laser damage threshold of KTI was measured to be 731 MW/cm2 at 1064 nm with 6 ns pulse width, which is comparable with other iodates.62



CONCLUSION A large, 37 × 7 × 5 mm3, high quality (fwhm = 0.023°) crystal of NLO KTI has been successfully grown by slow evaporation from an aqueous solution at room temperature. The relationships between the morphology of grown crystals and the seed directions were investigated. The UV−vis-NIR transmission spectrum reveals that KTI is transparent from 274−1751 nm. Refractive index measurements indicate that KTI is a positive biaxial crystal with the birefringence from 0.0545 to 0.0617 in the wavelength range of 450.2−1062.6 nm. On the basis of measured refractive index, the Sellmeier equations were fitted and phase-matching (PM) wavelengths were determined. KTI has a Type I PM fundamental (second-harmonic) wavelength range from 674 to 3266 nm (337−1633 nm), and a Type II PM fundamental (second harmonic) wavelength range from 880 to 2260 nm (440−1130 nm). The Type I PM limit is 337 nm, which indicates KTI can achieve 532 and 355 nm light generation by direct SHG and THG from a 1064 nm laser, respectively. The SHG PM angles (θ, ϕ) at 1064 nm are θ = 23.45° (ϕ = 90°) to θ = 65.85° (ϕ = 90°) for Type I; θ = 68.25° (ϕ = 90°) to θ = 90° (ϕ = 60.65°) for type II. Furthermore, the NLO coefficients of KTI were also determined by Maker fringe measurements, which reveal that d31 = 0.24 pm/V and d32 = 0.73 pm/V.





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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.7b00704. Some millimeter-sized KTI crystals were obtained at the bottom of the beaker; the beaker was covered with a polythene sheet with dozens of millimeter-size holes; the structure of the KTI; the morphology of grown crystal; the seed directions for the KTI crystal growths are controlled through attaching the different crystal face on the bottom of the beaker; the PXRD of the residues of KTI after the DTA analysis; the transmission spectrum of KTI crystal (PDF)



REFERENCES

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (S.P.). *E-mail: [email protected] (P.S.H.). ORCID

Shilie Pan: 0000-0003-4521-4507 P. Shiv Halasyamani: 0000-0003-1787-1040 Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS This work is supported by Youth Innovation Promotion Association CAS (Grant 2015353), 973 Program of China 4410

DOI: 10.1021/acs.cgd.7b00704 Cryst. Growth Des. 2017, 17, 4405−4412

Crystal Growth & Design

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DOI: 10.1021/acs.cgd.7b00704 Cryst. Growth Des. 2017, 17, 4405−4412

Crystal Growth & Design

Article

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DOI: 10.1021/acs.cgd.7b00704 Cryst. Growth Des. 2017, 17, 4405−4412