Top-Seeded Solution Crystal Growth and Linear and Nonlinear

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Top-Seeded Solution Crystal Growth, Linear and Nonlinear Optical Properties of Ba4B11O20F (BBOF) Hongping Wu, Hongwei Yu, Weiguo Zhang, Jacqueline Cantwell, Kenneth R. Poeppelmeier, Shilie Pan, and P. Shiv Halasyamani Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01857 • Publication Date (Web): 26 Jan 2017 Downloaded from http://pubs.acs.org on January 28, 2017

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Crystal Growth & Design

Top-Seeded Solution Crystal Growth, Linear and Nonlinear Optical Properties of Ba4B11O20F (BBOF) Hongping Wu,a Hongwei Yu,b Weiguo Zhang,b Jacqueline Cantwell,c Kenneth R. Poeppelmeier, c Shilie Pan,a* and P. Shiv Halasyamani b* a

Key Laboratory of Functional Materials and Devices for Special Environments of CAS;

Xinjiang Key Laboratory of Electronic Information Materials and Devices, Xinjiang Technical Institute of Physics & Chemistry of CAS, 40-1 South Beijing Road, Urumqi 830011 , China b

Department of Chemistry, University of Houston, 136 Fleming Building, Houston, Texas

77204, United States c

Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois

60208-3133, United States

ABSTRACT: A single crystal of Ba4B11O20F (BBOF) with dimensions of 20 × 17 × 12 mm3 was successfully grown using the top-seeded solution growth method. BBOF melts incongruently, as such several flux systems are discussed. The morphologies and growth habits of BBOF crystals grown with differently oriented seeds, [100], [010] and [001], were investigated. Using the [010]-oriented seed, the single crystal exhibits (200) and (010) faces. Rocking curve measurements indicate that the single crystal is of high quality with a full width at half-maximum (fwhm) of 0.017° (61 arcseconds) from the (010) reflection. The transmission

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spectrum and the refractive indices from the UV to the near infrared region are reported. BBOF is transparent from 190 - 2500 nm, and exhibits a birefringence of 0.0146 at 1064 nm. The type-I phase matching wavelength region was determined based on the fitted Sellmeier equations to the refractive index data. BBOF is type-I phase-matchable with fundamental (second-harmonic) wavelength ranges from 1049 - 2348 nm (524.5 - 1174 nm). In addition, the nonlinear optical coefficients for BBOF were measured using the Maker fringe method. For BBOF at 1064 nm, d31 = 1.57 pm/V, d32 = 0.27 pm/V, and d33 = 0.46 pm/V.


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INTRODUCTION Nonlinear optical (NLO) materials are a key constituent in solid-state lasers, and have enabled revolutionary achievements in the field of material processing and optical communication.1-8 Over the last thirty years there has been a surge in scientific interest in the design, discovery, and characterization of new NLO materials.9-13 Borates represent a large class of NLO materials. This is attributable to their structural variety, wide transmission range, and large laser damage threshold.14-19 The famous NLO material β-BaB2O41 (β-BBO) is widely used to generate coherent light from the ultraviolet to the infrared region. More recently, KBe2BO3F2 (KBBF) has been shown to be the sole NLO material that can generate deep-UV coherent light, < 200 nm, through cascading second-harmonic generation (SHG).20 However KBBF suffers from two drawbacks. First highly toxic and carcinogenic BeO must be used in the synthesis. Second, KBBF crystals layer along their optic axis complicating their large, high quality crystal growth. As such, new NLO materials that do not require BeO in their synthesis, and can be grown as large, high quality crystals are needed. In 2013, a new borate NLO material Ba4B11O20F (BBOF)17 was discovered. BBOF exhibits a large second harmonic generation (SHG) response of 10 × KDP and short UV cutoff wavelength (175 nm) that makes it a promising candidate for frequency conversion applications in the visible and UV regions. To further evaluate its applications, the growth of high quality large single crystals is necessary. In the original report, BBOF was shown to melt incongruently, thus the selection of a suitable flux system is critical for crystal growth. We investigated large number of flux systems and discuss the effects of the flux on the crystal growth of BBOF. We determined that a complex Na2CO3-K2CO3-H3BO3 flux is needed to grow large, high quality crystals of BBOF. The impact of seed orientation on crystal morphology and quality were also studied


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through rocking curve measurements. In addition, with the large single crystal, the refractive indices from UV to NIR were measured. With these measurements, the Sellmeier equations were determined, and the type-I phase-matching wavelength region was calculated. Finally, using Maker fringe method, the NLO coefficients of BBOF were measured. EXPERIMENTAL SECTION Crystal Growth. As BBOF melts incongruently, the crystal growth requires a flux. As the name indicates, the top-seeded solution growth method requires a seed for crystal growth.21,22 A BBOF seed crystal was grown by combining PbO (4.464 g, 20 mmol), BaF2 (1.753 g, 10 mmol), and H3BO3 (3.092 g, 5 mmol). The mixture was put into a Pt crucible that was placed into a programmable furnace. To form a homogenous melt, the mixture was heated to 850 °C, and held for 15 h. The temperature was reduced at 10 °C /h after a Pt wire was placed into the melt. At 805°C, we observed a crystal in the melt. The melt was then cooled slowly at 2 °C/day. In this manner, a few transparent seed crystals were grown on the Pt wire (Figure S1). However, the flux - PbO:BaF2:H3BO3 - is not suitable for large, high-quality crystal growth as yellow inclusions are observed. To grow a high-quality BBOF single crystal, BaF2 (14.027 g, 0.08 mol), H3BO3 (27.824 g, 0.45 mol), Na2CO3 (4.240 g, 0.04 mol) and K2CO3 (4.837 g, 0.035 mol), were combined. Similar to the seed growth, this mixture was placed in a Pt crucible and heated to 830 °C for 24 h to form a homogeneous melt. The melt was cooled in 20 °C/steps and the Pt wire was dipped into the melt for 30 minutes. If after 30 minutes, no crystals appear the melt was cooled an additional 20 °C and the process was repeated. We observed crystals in the melt at 720 °C indicating this temperature is slightly lower than the saturation temperature. We determined a saturation


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temperature of 730 °C by introducing a BBOF seed crystal to the melt and holding it for 48h. During this time the seed crystal did not grow or dissolve, and no additional crystals were formed. At 735 °C a BBOF seed crystal was introduced into the melt and held for 2h that allowed the seed crystal surface to melt. The melt was cooled to the saturation temperature, 730 °C, over 1h. A large BBOF crystal was gown by cooling the melt at a rate of 0.2 °C/d to 726 °C and the seed crystal rotates at 10 rpm. The rotation rate is computer controlled. The crystal was removed from the solution and cooled at 10 °C/h to room temperature. The total time for crystal growth was 26 d. X-ray Crystallography. Powder x-ray diffraction (PXRD) was used to determine if the crystals were BBOF. A PANalytical X’Pert PRO diffractometer equipped with monochromatic Cu Kα (λ= 1.54056 Å) radiation was used for the PXRD. The 2θ scanning range was from 10° to 70°, with a scanning step width of 0.02° and a fixed counting time of 1 s/step. The experimental and calculated powder patterns are in excellent agreement (Figure S2). High-resolution X-ray Diffraction Measurement. A (010) BBOF polished wafer with dimensions 5 × 5 × 2 mm3 was used for the high-resolution X-ray diffraction measurement. The measurement was done using a Rigaku High Resolution ATXG with a 4-bounce Ge-220 monochromator with Cu−Kα radiation (λ = 1.54056 Å). The scan speed and range were 0.001°/s and 0.2° respectively. The measurement was performed, around the Bragg diffraction peak position θ, by changing the angle between wafer surface and the the X-ray beam. Transmission Spectroscopy. A Shimadzu SolidSpec-3700DUV spectrophotometer was used to measure the transmission spectrum, from 165nm to 2600nm, of the BBOF crystal under flowing nitrogen.


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Refractive Index Measurements. A Metricon Model 2010/M prism coupler (Metricon Co.) was used to determine the indices of BBOF. Five different wavelengths: 450.2, 532, 636.5, 829.3, and 1062.6 nm were used. A Unipol-300 grinding/polishing machine (MTI Co.) was used to polish the (010) BBOF wafer. Based on the space group of BBOF, the crystallographic a, b and c-axis are the three optic axes for BBOF. NLO Coefficient Measurements. The Maker Fringe technique was used to measure the NLO coefficients of BBOF.23,24 Using the group symmetry for point group C2v-mm2 and the Kleinman approximation, there are three non-zero NLO coefficients, d31 (= d15), d32 (= d24) and d33.25,26 Wafers perpendicular to a- and b- axes were cut for the measurements. For the fundamental light, a Q-switched Nd:YAG laser (Quantel Laser, Ultra 50) was used. A photomultiplier tube (PMT) (Zolix Instruments, PMTH-S1-CR131) was used to detect the second harmonic signal produced from the sample. A 2.0 mm thick (110) crystal wafer of KH2PO4 (KDP) (Crystrong Photoelectric Tech. Co., Ltd. China) was used to measure the reference d36 NLO coefficient. RESULTS AND DISCUSSION Flux Selection. As BBOF melts incongruently, the selection of the flux for crystal growth is critical (Table S1). For the growth of a large, high quality BBOF crystal, the high melting temperature and high viscosity of any possible flux needs to be avoided. We initially considered a self-flux to avoid introducing any impurities, i.e. B2O3, BaCO3, BaF2, or BaCO3 and B2O3. Our attempts at using these self-fluxes were unsuccessful. Adding B2O3 increased the viscosity, whereas adding more BaCO3 or BaF2 increased the melting temperature. To decrease the melting temperature, we considered adding PbO or PbF2. We were successful in growing a 28 × 15 × 5 mm3 (Figure S3) crystal of BBOF using a PbO:BaF2:H3BO3 system with the molar ratio 2:1:5.


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As seen in Figure S3, the crystal has yellow inclusions presumably from the incorporation of Pb2+. We noticed that the B:Ba ratio in BBOF is 2.75 that is similar to the B:Ba ratio in β-BaB2O4 (β-BBO). β-BBO has been grown by TSSG methods through a Na2O-B2O3 flux.27,28 Our attempts to grow a BBOF crystal using a Na2CO3-B2O3-BaF2 flux failed. We decided to try a more complex flux, Na2CO3:K2CO3:H3BO3:BaF2. Our thinking was that the addition of K2CO3 would not only reduce the viscosity, but also the melting temperature. After several experiments, we determined that a molar ratio of 0.4:0.35:0.8:4.5 of Na2CO3:K2CO3:H3BO3:BaF2 is required to grow a large, high quality BBOF crystal. Crystal Growth and Morphology of the BBOF Crystal. In the TSSG method, the seed orientation has a significant impact on the crystal growth rate, quality, and morphology.29-33 The theoretical morphology of a BBOF crystal based on the Bravais-Friedel and Donnay-Harker (BFDH) method34 is shown in Figure 1a. The predicted morphology exhibits {110}, {111}, and {100} faces, suggesting that the growth rates of these faces are slower than the {001} and {010} faces. The crystals shown in Figure 2 were grown under the same conditions - temperature, rotation rate, growth time (see Experimental Section) - but using different oriented seeds. Using the [001]- and [100]-oriented seeds, regular shaped BBOF crystals were obtained (Figures 2a and 2b). Using [001]-oriented seeds, the crystal exhibits (200), (110) and (001) faces and has a size of 20 × 20 × 5 mm3, whereas using the [100]-oriented seeds, the crystal exhibits (100), (010) and (111) faces with a size of 23 × 12 × 5 mm3. The crystal grown with a [010]- oriented seed exhibits (200) and (010) faces and has a size of 10 × 6 × 5 mm3. Clearly the crystals grown with the [100]- and [001]-oriented seed grows faster compared with the crystal grown from the [010]oriented seed. However, using the [100]- and [001]-oriented seeds, the crystal is not transparent


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and crystals that are grown exhibit thin habits. Specifically, the crystal grown using [100]oriented seed exhibits two layers (Figure 2b). The bottom layer of the crystal exhibits inclusions, whereas the top layer is transparent. However, the top layer is thin - about 2mm. Clearly, the seed orientation impacts greatly the crystal morphology and quality, whereas the cooling rate and rotation speed has minimal effect. Thus, we chose [010]-oriented seeds for large crystal growth. The ideal BBOF crystals are as shown in Figures 1b and 2c. To determine the crystal quality, rocking curve measurements were performed. A FWHM of 0.017° (61 arcseconds) was measured from the (010) reflection, indicating the crystal is of high quality (Figure 3).

Figure 1. (a) The simulated morphology of a BBOF crystal and the (b) grown crystal of BBOF


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(a)

(b)

(c)

Figure 2. Photographs and morphologies of the BBOF crystals with different seed orientations: (a) [001]-oriented seed, (b) [100]-oriented seed, and (c) [010]-oriented seed.

Figure 3. High-resolution X-ray diffraction rocking curve for the BBOF wafer (left). A FWHM of 0.017° is observed, indicating a high quality crystal was grown. The crystal used for the measurement is shown on the right.


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UV-Vis-IR Transmission Spectrum. A polished BBOF crystal about 2 mm thick was used. As seen in Figure 4, the BBOF crystal has a large transmission window (80%) to about 2500nm, with an absorption edge of 190nm. This is comparable with the transmission of β-BBO.1 The wide transparency window suggests that BBOF is amenable to frequency conversion and other NLO parametric processes.

Figure 4. The transmission spectrum of BBOF is shown. As seen BBOF has a large transmission window (80%) to nearly 2500nm. Refractive Indices. BBOF crystallizes in the orthorhombic crystal system Cmc21, i.e., a biaxial crystal system. The refractive indices along the a, b and c axes were measured at five wavelengths, 450.2, 532, 636.5, 829.3, and 1062.6 nm, using a polished (100) crystal wafer (Table 1). BBOF is a biaxial crystal with the optical principle axes x, y, z parallel to the crystallographic axes, c, b, a, respectively (Table 1). Since nz-ny > ny-nx, BBOF is a positive biaxial optical crystal,35 and the birefringence, ∆n = nz - nx, is 0.0146 - 0.0160 over the measured


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wavelength region. Using the least squares method, the Sellmeier equation can be fit,19 and the dispersion parameters of the refractive index ni, and the calculated dispersion parameters are listed in Table 2.

ni2 = A +

B

λ2 − C

− Dλ2

Where λ is the wavelength in microns, and A, B, C and D are the Sellmeier parameters. Table 1. Experimental and calculated refractive indices for BBOF.

nx λ/µm

ny

nz

∆n = nz- nx

Exp.

Calc.

Exp.

Calc.

Exp.

Calc.

0.4502

1.6307

1.63047

1.6366

1.63644

1.6467

1.6467

0.0160

0.5320

1.6231

1.62314

1.6292

1.62978

1.6389

1.63893

0.0158

0.6365

1.6177

1.61764

1.6248

1.62407

1.6332

1.63316

0.0155

0.8293

1.6123

1.61233

1.6175

1.61789

1.6274

1.62743

0.0151

1.0626

1.6089

1.60889

1.6139

1.62349

0.0146

1.61380

1.6235

Table 2. Sellmeier coefficients derived from the measured refractive indices. A

B

C

D

nx

2.58366

0.01355

0.0263

0.00657

ny

2.59004

0.02242

-0.04994

0.00416

nz

2.63310

0.01450

0.02233

0.00927

Based on the Sellmeier equation fit, the calculated refractive indices are obtained (Table 1) that match well with the experimental data (Figure 5).


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Figure 5. Refractive-index data for single crystal BBOF are shown and a birefringence of 0.0146 is observed at 1064nm. The curves are the fits given by the Sellmeier equations. Phase Matching (PM) Calculations. Based on the Sellmeier equations, the refractive index curves of the second harmonic light can be obtained (Figure 6). For type-I phase-matching (PM) the condition, n(ω) = n(2ω), must be satisfied. The 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 1049 - 2348nm (524.5 - 1174nm). Thus, the SHG limit is 524.5 nm, thus a BBOF crystal can achieve 532 nm light generation by direct SHG from a 1064 nm laser. As BBOF is biaxial, two PM angles, φ and θ, for the three principle planes (xy, yz, and xz) for SHG can also be calculated. For BBOF, type I PM can only be observed in the xy- and yzplanes. PM is not possible in the xz-plane as the birefringence, ∆n = ny - nx, is too small. Figure 7a shows the PM angles, φ and θ, as a function of fundamental wavelength. As seen in Figure 7a, the type-I PM wavelength range is consistent with the data presented in Figure 6, i.e., the type-I PM wavelength range is from 1049 – 2348 nm. Figure 7a also shows that in the PM wavelength


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range, the PM angle φ ranges from 30.55 - 90° in the xy-plane, whereas θ ranges from 44.95 90° in the yz-plane. With this data, we calculated the PM angles for 1064 nm radiation (Figure 7b). As seen in Figure 7b, when θ = 90°, φ = 77.05°, and when φ = 90°, θ = 79.30°. When θ and φ = 90°, the values of φ and θ are relatively close to 90° that suggests BBOF may be non-critically phase-matched.35 With non-critical phase-matching, the walk-off angle is zero and the intensity of the secondharmonic beam is maximized.

Figure 6. Refractive index dispersion curves for fundamental (red solid lines) and the second harmonic (green dashed lines) light. The type I PM conditions are satisfied when nz(ω) and nx(2ω) intersect. The type I PM wavelength range for fundamental (second harmonic) light is 1049 – 2348 nm (524.5 – 1174 nm).


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Figure 7. (a) Calculated type I PM angles, φ and θ, of BBOF. Note that the PM wavelength range is consistent with the refractive index data (Figure 6). The red circles indicate 1064 nm. (b) The PM angles, φ and θ, at 1064nm. Note that when φ = 90°, θ = 79.30°, and when θ = 90°, φ = 77.05°, indicating BBOF may be non-critically phase-matched.


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NLO Coefficient Measurements. The NLO coefficients for BBOF were measured using the Maker fringe technique.23,24 A schematic of the Maker fringe measurement system and calculations have been reported earlier.37,25 To obtain Maker fringes of BBOF and KDP, based on the space group and Kleinman symmetry of BBOF,38,39 we can deduce the relationship between crystallographic and optical axes in BBOF. The optical principle axes x, y, z are parallel to the crystallographic axes a, b, c, respectively. In principle, for crystal class mm2, three nonzero NLO coefficients - d31, d32 and d33 - are observed. The (100)- and (010)-wafers of BBOF (5 mm × 5 mm × 2 mm) were used to measure d31, d32 and d33, respectively, whereas a (110)-cut KDP wafer (8 mm × 8 mm × 2.4 mm) was used to measure the reference d36 (see Figure 8).

Figure 8. Orientation of the BBOF and KDP crystal wafers for measuring the NLO coefficients (a) d31 (BBOF); (b) d32 (BBOF); (c) d33 (BBOF); (d) d36 (KDP). On the right are the (010) and (100) crystal wafers of BBOF used in the Maker Fringe measurements


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Using these crystal wafers, the Maker fringes of BBOF and KDP were obtained (Figure 9). By fitting the calculated Maker fringes, the NLO coefficients of BBOF relative to d36(KDP) were determined. For BBOF, d31 = 4.03 d36(KDP), d32 = 0.70 d36(KDP), and d33 = 1.18 d36(KDP). Since the absolute value of d36 KDP is 0.39 pm/V,40 the absolute NLO coefficients of BBOF are d31 = 1.57 pm/V, d32 = 0.27 pm/V, and d33 = 0.46 pm/V. Table 3 compares BBOF to other technological relevant NLO materials with respect to their absorption edge, birefringence, shortest phase-matching wavelength, and SHG coefficients. As seen, BBOF compares well to the technologically relevant NLO materials with respect to the SHG coefficients. Table 3. List of relevant NLO materials, their absorption edge, birefringence, shortest phasematching wavelength, and SHG coefficients. Compound

Absorption Edge (nm)

Birefringence at 1064nm

Shortest Phase-Matching Wavelength (nm) for SHG

SHG Coefficients (dij) pm/V

KBe2BO3F2 (KBBF)41

14742

0.07743

17043

d11=0.4944

KH2PO4 (KDP)45

17645

0.066146

27246

d36 = 0.3947

CsLiB6O10 (CLBO)48

180nm49

0.04948

23848

d36=0.9548

K3B6O10Cl (KBOC)16

18031

0.046450

27250

Not reported

β-BaB2O4 (β-BBO)1

1891

0.112751

20551

d11=1.6052

Ba4B11O20F (BBOF)

190

0.0146

524.5

d31 = 1.57, d32 = 0.27, d33 = 0.46

Finally, a 0.1765 g BBOF wafer was soaked in water for one week. The weight of this wafer did not change upon removing from the water. Moreover, the crystal faces were still lucent and transparent (Figure S4). Clearly, the BBOF crystal is nonhygroscopic, very deliquescenceresistant, and not soluble in water.


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Figure 9. Experimental and theoretical Maker fringes for (a) d31, (b) d32 and (c) d33 of BBOF, (d) d36 of KDP (Experimental fringes: black solid lines; Fitted envelope and curve of the Maker fringe: blue solid and red dashed lines respectively) CONCLUSION Large, centimeter size crystals of BBOF have been grown by the TSSG method. The crystal morphology and growth habits reveal that the [010]-oriented seed is ideal for the BBOF crystal growth. Rocking curve measurements indicated a FWHM of 0.017° (61 arcseconds) for the (010) reflection indicting a high quality crystal. Refractive index measurements indicate that BBOF is a positive biaxial crystal with birefringence of 0.0146 at 1064nm. BBOF has a type-I PM fundamental (second-harmonic) wavelength range from 1049 to 2348 nm (524.5 to 1174 nm). The SHG limit is thus 524.5 nm that indicates single crystal BBOF can achieve 532 nm light


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generation by direct SHG from a fundamental 1064 nm laser. The SHG PM angles (θ, φ) at 1064nm are θ = 79.30° (φ = 90°) to θ = 90° (φ = 77.05°) suggesting that BBOF may be noncritically phase-matched. In addition, Maker fringe measurements reveal that the NLO coefficients of BBOF are d31 = 1.57 pm/V, d32 = 0.27 pm/V, and d33 = 0.46 pm/V. ASSOCIATED CONTENT Supporting Information. Different flux systems for BBOF crystal growth; Seed crystals grown on Pt wire; The PXRD of BBOF crystal; The photo of BBOF crystal grown in PbO flux; The photos of BBOF crystal before and after being dipped in water. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author *[email protected]; [email protected]. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work is supported by 973 Program of China (Grant No. 2014CB648400), the National Natural Science Foundation of China (Grant Nos. U1303392, 51425206), the Youth Innovation Promotion Association CAS (Grant 2015353) and the Outstanding Young Scientists Project of CAS. PSH, HY, and WZ thank the Welch Foundation (Grant E-1457) and the NSF (DMR1503573) for support. J.C. and K.R.P. thank the National Science Foundation (DMR-1307698). 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.


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Table of Contents Use Only

Top-Seeded Solution Crystal Growth, Linear and Nonlinear Optical Properties of Ba4B11O20F (BBOF) Hongping Wu,a Hongwei Yu,b Weiguo Zhang,b Jacqueline Cantwell,c Kenneth R. Poeppelmeier, c Shilie Pan,a* and P. Shiv Halasyamani b*

A single crystal of Ba4B11O20F (BBOF) with dimensions of 20 × 17 × 12 mm3 was grown using the top-seeded solution growth method. The refractive indices from the UV to the near IR are reported. BBOF is type-I phase-matchable with fundamental (second-harmonic) wavelength ranges from 1049 - 2348 nm (524.5 - 1174 nm). The nonlinear optical coefficients were measured using the Maker fringe method.


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Top-Seeded Solution Crystal Growth and Linear and Nonlinear

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