Crystal Growth and Optical Properties of Beryllium-Free Nonlinear

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Crystal Growth and Optical Properties of BerylliumFree Nonlinear Optical Crystal KBaLiAlBO F 3

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Bingqing Zhao, Lei Bai, Bingxuan Li, Sangen Zhao, Yaoguo Shen, Xianfeng Li, Qingran Ding, Chengmin Ji, Zheshuai Lin, and Junhua Luo Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01594 • Publication Date (Web): 28 Dec 2017 Downloaded from http://pubs.acs.org on December 30, 2017

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Crystal Growth & Design

Crystal Growth and Optical Properties of Beryllium-Free Nonlinear Optical Crystal K3Ba3Li2Al4B6O20F Bingqing Zhao,†,§ Lei Bai,‡ Bingxuan Li,‡ Sangen Zhao,*,† Yaoguo Shen,† Xianfeng Li,† Qingran Ding,† Chengmin Ji,† Zheshuai Lin,‡ and Junhua Luo*,† †

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the

Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China ‡

Beijing Center for Crystal R&D, Key Lab of Functional Crystals and Laser

Technology of Chinese Academy of Sciences, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China §

College of Chemistry, Fuzhou University, Fuzhou 350116, China

KEYWORDS: Nonlinear optics, crystal growth, top-seeded solution method

ABSTRACT: A beryllium-free nonlinear optical (NLO) crystal K3Ba3Li2Al4B6O20F (KBLABF) with sizes up to 18× 13× 8 mm3 is successfully grown by the top-seeded solution growth method using LiOH-H3BO3-BaF2 flux. The key limiting factors on the crystal morphologies and sizes are carefully analyzed. Meanwhile, by using the minimum deviation technique, the refractive index dispersion is measured and fitted well by the Sellmeier equations. The results suggest that KBLABF is a negative 1 ACS Paragon Plus Environment

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uniaxial crystal with moderate birefringence of 0.06050 – 0.06834 at a wavelength range from 363 nm to 852.1 nm. Furthermore, the type-І phase matching range for fundamental (second harmonic) light is down to 486 (243 nm) in theory, which indicates that KBLABF crystal could achieve 532 nm and 266 nm light generation by direct second-harmonic generation. As compared with the famous NLO crystals β-BaB2O4 and CsLiB6O10, KBLABF crystal exhibits a smaller walk-off angle and larger acceptance angle at the wavelength of 532 nm while having a comparable short absorption edge, sufficient birefringence, moderate NLO response. Furthermore, in contrast to highly hygroscopic CsLiB6O10, it is non-hygroscopic. These attributes make KBLABF a promising candidate for the practical applications in UV light generation.

INTRODUCTION Lasers in the UV region have a lot of important applications in the fields of

photolithography, high-resolution photoelectron spectroscopy, micromachining, and laser prototyping.1 Compared with other UV lasers, all-solid-state UV lasers possess obvious advantages in maintenance cost, system size, and efficiency.2 Up to now, the best way to produce UV coherent light is through a cascaded frequency conversion using a series of nonlinear optical (NLO) crystals.3-12 However, the current NLO crystals that can practically apply in the UV region have more or less disadvantages, although intensive efforts in this field have been made for more than 30 years.13-16 It is well known that borate possesses moderate NLO coefficients, wide transparency

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range, and sufficient birefringence, and as a result is the hotspot of NLO researches for a long time. A series of famous borate NLO crystals,17-22 such as β-BaB2O4 (BBO),23 CsLiB6O10 (CLBO),24 and KBe2BO3F2 (KBBF)25 have been discovered in the past decades. BBO crystals have a high NLO coefficient (d22 = 2.2 pm/V) but its birefringence is too large (∆n = 0.12 @532 nm). CLBO crystal has a moderate NLO coefficient (d36 = 0.95 pm/V) and sufficient birefringence (∆n = 0.75 @532 nm), but it is highly hygroscopic. KBBF crystal is the sole NLO crystal that can practically generate deep-UV coherent light by direct second-harmonic generation (SHG), whereas it contains highly toxic beryllium element and shows a serious layering tendency in single-crystal growth.26,27 Therefore, the practical applications of these NLO crystals are to some extent limited, and it is still in great demand to develop new UV NLO crystals.28-30

In 2016, our group designed a new beryllium-free borate K3Ba3Li2Al4B6O20F (KBLABF),31 which exhibits a layered crystal structure analogous to that of KBBF. KBLABF preserves the structural merits of KBBF and overcomes the structural instability problem present in the notable KBBF-family member Sr2Be2B2O7.32 As a result, it possesses desirable optical properties, including deep-UV transparency, phase-matchability, and sufficiently large SHG response (1.5× KH2PO4). These attributes make KBLABF an attractive NLO material with potential application in the UV and deep-UV spectral regions. However, there is still lack of bulk single KBLABF crystals, and thus hindered the practical applications of KBLABF. In this paper, we selected the top-seeded solution method and self-flux system to grow 3 ACS Paragon Plus Environment


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KBLABF crystal because of its incongruently melting behavior. Consequently, a bulk transparent KBLABF single crystal was successfully grown. With the large single crystal, based on the minimum deviation technique, the refractive index dispersion of KBLABF was measured at different wavelengths from UV to visible range. Finally, the Sellmeier equations were determined and the phase-matching curves were also calculated.

EXPERIMENTAL SECTION Crystal Growth. According to our previous report, KBLABF melts incongruently.

Thus, bulk KBLABF crystal should be grown by the flux method under its decomposition temperature. LiOH-H3BO3-BaF2 was used as the suitable flux after our many attempts. A mixture (110 g) of polycrystalline KBLABF, LiOH·H2O, H3BO3 and BaF2 (at a molar ratio of 1: 4.5: 5: 0.5) was finely ground, and then transferred to a Φ 45 mm × 45 mm platinum crucible in batches, and finally melted at 850 °C in a temperature-programmable electric furnace. It was quickly heated to 850 °C and held at this temperature for 48 h. Subsequently, a platinum wire tied to a corundum pole was descended slowly till immersing into the surface of the melt. The melt was cooled to 750 °C at once and subsequently cooled slowly until KBLABF crystals crystallized on the platinum wire. The platinum wire was then lifted out of the melt surface before being cooled to ambient temperature in 72 h. The crystals separated from the platinum wire were used as seed crystals to grow bulk single crystals.


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Similar to the seed growth, a high-quality single crystal was grown in the same mixture. Firstly, the saturation temperature (~735 °C) was detected by using a tentative seed crystal method. A seed crystal was fixed to a corundum rod with the aid of platinum wire, which was slowly immersed into the melt at 745 °C and then held at this temperature for 2 h to dissolve the uneven surfaces of the seed crystal. Secondly, the temperature was decreased quickly to 735 °C within 2 h and then cooled slowly at a rate of 0.16 °C per day until the desired crystal sizes were obtained. During crystal growth, the seed crystal was rotated at 27 rpm rates, with the rotation direction inverted every 30 s. After ~30 days of crystal growth, the crystal was lifted out of the melt and the temperature was slowly lowered to ambient temperature. The as-grown crystal is as large as 18 mm × 13 mm × 8 mm (Figure 1b).

X-ray Crystallography. Power X-ray diffraction (PXRD) was used to determine whether the as grown crystals were KBLABF. The parameters of a scanning step width of 0.02° and a scanning rate of 0.14° min−1 in the 2θ range of 7°−70° were set for collecting the powder XRD patterns. This data collection was performed on a Rigaku MiniFlex II diffractometer (Cu Kα radiation) at ambient temperature. The result shows good consistency with that deduced from single-crystal XRD analysis (Figure S1).

Refractive Index Measurements. A SpectroMaster UV-VIS-IR (Trioptics, Germany) was used to measure the refractive indices of KBLABF by a right-angle prism with an apex angle of 29.7753(70)° (Figure 2). The experimental temperature 5 ACS Paragon Plus Environment


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was controlled at 26 °C with a fluctuation within 0.5 °C. Nine different wavelengths: 363 nm, 404.7 nm, 435.8 nm, 480 nm, 546.1 nm, 587.5 nm, 643.8 nm, 706.5 nm, 852.1 nm, covering from UV to Visual region were selected for refractive measurements. The results are listed in Table 2.

RESULTS AND DISCUSSION Flux Selection. The flux growth technique is particularly preferable because it

readily allows crystal growth at a temperature well below the melting point of the solution. Meanwhile, crystals grown from flux have a euhedral habit and a reasonably lower degree of dislocation density.33 Thus, the selection and ratio of the flux for KBLABF crystal growth is very important.

Table 1. Experimental results of flux ratios. Molar ratio Crystal Results Quality (KBLABF:LiF:H3BO3:BaF2) morphology 1: 1: 3: 1 platelike KBLABF poor 1: 4: 3: 0.5 strip KBLABF poor 1: 4: 3: 1 clastic KBLABF poor 1: 6: 3: 0.5 platelike K2Al2B2O7 1: 3: 3: 1.5 platelike K2Al2B2O7 1: 5: 3: 0.5 platelike K2Al2B2O7 Molar ratio Crystal Results Quality (KBLABF:LiOH:H3BO3:BaF2) morphology 1: 7: 6: 0.5 parallelepiped KBLABF good 1: 4.5: 4: 0.5 parallelepiped KBLABF good 1: 2: 2: 2 clastic KBLABF poor 1: 1: 2: 1.5 clastic KBLABF poor 1: 4: 2: 1.5 clastic KBLABF poor 1: 6: 2: 2 clastic LiBaO3 1: 7: 1: 2 clastic LiBaO3 1: 1: 2: 1.5 clastic KBLABF poor 1: 3: 2: 1 clastic KBLABF poor 1: 4: 3: 1 platelike KBLABF poor 6 ACS Paragon Plus Environment

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Generally, the morphology and size of the crystals are mainly affected by growth rates, flux ratio, and direction of seed crystal.34-36 Different flux ratio experimental results are listed in Table 1. The suitable molar ratio of KBLABF: LiOH: H3BO3: BaF2 to grow large KBLABF crystal is 1: 4.5: 4: 0.5. Subsequently, we tried to grow crystals by different rates, such as 0.33 °C per day, 0.25 °C per day, and 0.16 °C per day, and we found that 0.16 °C per day is suitable to grow transparent KBLABF single crystals. As shown in Figure 1a, the KBLABF crystal obtained by spontaneous crystallization and its morphology is regular hexagonal prisms. When using the molar ratio flux of 1: 7: 6: 0.5 to grow crystal (Figure S2), the shape of crystal basically keeps the hexagonal prisms, but the solution was easy to volatilize. As a result, multiple growth twins and white inclusions readily appeared in the as-grown crystal.37 When using a molar ratio flux of 1: 4.5: 4: 0.5, the white inclusions and multiple growth twins were largely overcame, and finally a large and transparent KBLABF crystal was successfully grown (Figure 1b). As large KBLABF single crystal growth will lay a foundation for the next work to measure the Maker fringes and crystal NLO devices, we will continue this work and try to grow larger KBLABF crystals of high quality.



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Figure 1. (a) The KBLABF crystal was grown by spontaneous crystallization. Scale bar, 5 mm. (b) The KBLABF crystal grown from the molar ratio flux of 1: 4.5: 4: 0.5. Scale bar, 5 mm.

Refractive Indices. Refractive indices and determination of the dispersion curves are crucial for further estimation of the phase-matching, which are significant needs for frequency doubling and sun-frequency mixing.38,39 Using the minimum deviation technique,40 the refractive index dispersion was measured at nine different monochromatic sources from 363 nm to 852.1 nm. Because KBLABF is a uniaxial crystal, it is feasible to measure the values of refractive indices for both the ordinary (no) and the extraordinary (ne) polarizations using one prism. The prism (11 × 11 × 5 mm3) was cut with an apex angle 29.7753° (Figure 2a, b). The values of refractive indices for no and ne are summarized in Table 2.

Figure 2. (a) Photograph of KBLABF prism for measurements of refractive indices. Scale bar, 5 mm. (b) Sketch map of crystal wedge with (001) and (100) faces for refractive indices characterization. (c) Experimental refractive indices and fitted refractive index dispersion curves of KBLABF.


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Table 2. The birefringence, ∆n = no – ne, is 0.060508 – 0.068344 over the measured wavelength region, which indicates that KBLABF is a negative uniaxial crystal. Meanwhile, the experimental data were fitted to the following Sellmeier equations: ne2 = 2.3283 + 0.01416 / (λ2 – 0.005452) – 0.001050λ2

(1)

no2 = 2.5126 + 0.01775 / (λ2 – 0.007743) – 0.006443λ2

(2)

where λ is the wavelength expressed in micrometers.41 As shown in Figure 2c, the theoretical values agree quite well with the experimental data. Calculations show that the deviation between the experimental values and the theoretical ones is less than 1

× 10-4. Thus, the Sellmeier equations are well convinced.

Table 2. Comparison of the refractive indices between the experimental and calculated values for KBLABF. Wavelength

ne

ne (Calculated)

no

no

(nm)

(Experimental)

Error

(Experimental)

Error

∆n=no–ne

363.0

1.562106

1.562136

0.000030

1.630450

1.630488

(Calculated)

0.000038

0.068344

404.7

1.554936

1.554853

-0.000083

1.621503

1.621395

-0.000108

0.066567

435.8

1.550747

1.550762

0.000015

1.616282

1.616302

0.000020

0.065535

480.0

1.546238

1.546288

0.000050

1.610670

1.610733

0.000063

0.064432

546.1

1.541519

1.541541

0.000022

1.604782

1.604808

0.000026

0.063263

587.5

1.539351

1.539356

0.000005

1.602056

1.602064

0.000008

0.062705

643.8

1.537057

1.537035

-0.000022

1.599151

1.599123

-0.000028

0.062094

706.5

1.535104

1.535073

-0.000031

1.596641

1.596600

-0.000041

0.061537

852.1

1.532033

1.532050

0.000017

1.592541

1.592563

0.000022

0.060508

Phase Matching (PM) Calculation. Based on the Sellmeier equations, we calculated the type-І and type-ІІ PM for SHG. For type-І PM the condition, n(ώ) = n(2ώ), must be satisfied.42 As shown in Figure 3, the type-І PM cutoff wavelength for



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fundamental light is 486 nm and the second harmonic light is 243 nm. The type-ІІ PM limit is at a fundamental wavelength 688 nm, which means the SHG limit is 344 nm at harmonic generation wavelength. These results indicate that single crystal KBLABF could achieve 532 nm and 266 nm light generation by direct SHG and has a wide phase-matching range in the UV wavelength.43 Meanwhile, the SHG PM angle at 1064 nm and 532 nm for type-І (type-ІІ) are θ = 30.5° (44.2°) and θ = 67.5° (90.0°) respectively.44

Figure 3. Second harmonic phase-matching angle as a function of fundamental wavelength for single crystal of KBLABF.

As we know, BBO and CLBO crystals are good materials for producing SHG of Nd-based laser at 532 nm.45 As the Table 3 shows, BBO crystals exhibit a high NLO coefficient but have unfavorable properties such as too large birefringence that can create walk-off issues. Spatial walk-off angle is an important parameter which effectively reduces the gain length for SHG, and thus effects the attainment of maximum SHG output power and efficiency.46 On the basis of the refractive indices,


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walk-off angle (α) and acceptance angle (δθ) can be theoretically calculated by following equations47,48: 1  ne2 − no2 ) ( α = arctan  2 2 sin 2 θ  2 2  2 no sin θ + ne cos θ 

δθ =

λ

−1

 no ( 2ω ) − ne ( 2ω )  sin −1 2θ m l 

(3)

(4)

Where θm is phase-matching angle at 532 nm, θ is an angle between the wave vector and the main optical axis, and l is the length of interaction between the fundamental wave and the frequency multiplication wave. The walk-off angle of BBO is up to 85.3 mard @532 nm49, which results in too small acceptance angle and exceedingly reduce the efficiency of SHG conversion in practical applications. In addition, CLBO has a moderate SHG response and birefringence for SHG @532 nm, but its high hygroscopicity limits its applications. As compared with BBO and CLBO, KBLABF possesses moderate birefringence, sufficiently large SHG (1.5 × KH2PO4), slight hygroscopicity, and short UV absorption edge. As shown in Table 3, its walk-off angle is smaller and acceptance angle is larger than those of BBO and CLBO, and thus the effect of dispersion on crystals is relatively small, which is favorable to achieve an efficiency of SHG conversion as high as possible in the practical application. Therefore, KBLABF is a promising candidate for practical applications in UV light generation.

Table 3. Comparison of NLO properties among BBO, CLBO, and KBLABF @532 nm.



Crystal

Birefrin gence

BBO

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Phase-matc hing angle (θ /°)

deff (pm/V)

Walk-off angle (mrad)

Acceptance angle (mrad ×rad)

0.120

47.5

1.75

85.3

0.16

190

slight

CLBO

0.053

61.5

0.75

32.9

0.48

180

serious

KBLABF

0.063

67.5

1.5×KH2 PO4

32.0

1.03

190

slight

UV Hygrosco absorption picity edge (nm )

CONCLUSION In summary, a large and transparent KBLABF single crystal with sizes up to 18×

13× 8 mm3 has been grown by the top-seeded solution method. It is found that KBLABF-LiOH-H3BO3-BaF2 with a molar ratio of 1: 4.5: 4: 0.5 is suitable for crystal growth. Refractive index measurements suggest that KBLABF is a negative uniaxial crystal with moderate birefringence of 0.060508 – 0.068344 at wavelengths ranging from 353 to 852.1 nm. Meanwhile, based on the Sellmeier equations, KBLABF single crystal could achieve 532 nm and 266 nm light generation by direct SHG. In addition, the SHG PM angle at 1064 nm and 532 nm for type-І (type-ІІ) are θ = 30.5° (44.2°) and θ = 67.5° (90.0°). As compared with BBO and CLBO, KBLABF crystal exhibits smaller walk-off angle and larger acceptance angle at the wavelength of 532 nm while having a short absorption edge, sufficient birefringence, moderate NLO response, and non-hygroscopicity. These attributes make KBLABF a promising candidate for the practical applications in UV light generation.

ASSOCIATED CONTENT

Supporting Information 12 ACS Paragon Plus Environment

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The Supporting Information is available free of charge on the ACS Publications website at DOI: ******.

Figures S1 – S2, power X-ray diffraction and morphology photograph of K3Ba3Li2Al4B6O20F crystal.

AUTHOR INFORMATION

Corresponding Author *E-mail: [email protected].

*E-mail: [email protected].

Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Notes The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENT

This work was supported by the NSFC (21571178, 21525104, 91622118, 51502288, 51402296, and 91422301), the Strategic Priority Research Program of Chinese Academy of Sciences (XDB20000000). S.Z. is grateful for the support from NSF for Distinguished Young Scholars of Fujian Province (2016J06012).

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For Table of Contents Use Only Crystal Growth and Optical Properties of Beryllium-Free Nonlinear Optical Crystal K3Ba3Li2Al4B6O20F Bingqing Zhao,†,§Lei Bai,‡ Bingxuan Li,‡ Sangen Zhao,*,† Yaoguo Shen,† Xianfeng Li,† Qingran Ding,† Chengmin Ji,† Zheshuai Lin,‡ and Junhua Luo*,† A large and transparent beryllium-free nonlinear optical crystal K3Ba3Li2Al4B6O20F with sizes up to 18× 13× 8 mm3 is successfully grown. Remarkably, K3Ba3Li2Al4B6O20F exhibits a smaller walk-off angle and larger acceptance angle at 532 nm while having comparable short absorption edge, sufficient birefringence, moderate NLO response, and non-hygroscopicity as compared with β-BaB2O4 and CsLiB6O10, which make it a promising NLO material.

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Crystal Growth and Optical Properties of Beryllium-Free Nonlinear

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