Synthesis, Growth of Crack-free Large-size BaGa4Se7 Crystal and

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Synthesis, Growth of Crack-free Largesize BaGa4Se7 Crystal and Annealing Studies Yangwu Guo, Zhuang Li, Zuotao Lei, Xiaoyu Luo, Jiyong Yao, Chunhui Yang, and Yicheng Wu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01681 • Publication Date (Web): 21 Dec 2018 Downloaded from http://pubs.acs.org on December 24, 2018

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Crystal Growth & Design

Synthesis, Growth of Crack-free Large-size BaGa4Se7 Crystal and Annealing Studies Yangwu Guo,†,‡ Zhuang Li,†,‡ Zuotao Lei,‖ Xiaoyu Luo,†,‡ Jiyong Yao,*,† Chunhui Yang‖ and Yicheng Wu†,§

†Beijing

Center for Crystal Research and Development, Key Laboratory of Functional Crystals and

Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P.R. China ‡University ‖School

of Chinese Academy of Sciences, Beijing 100049, P.R. China

of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001, PR

China §Institute

of Functional Crystal Materials, Tianjin University of Technology, Tianjin 300384, P.R.

China

ABSTRACT:

The newly developed IR nonlinear optical (NLO) material BaGa4Se7

(BGSe) has aroused intensive research interest owing to its excellent overall properties and outstanding IR laser output performance. In this paper, the growth of high quality large size BGSe was investigated. To overcome the difficulty of realizing large-scale complete reaction among the highly active metal Ba, the liquid metal Ga, and the non-metal with high vapor pressure Se, two temperature-zone synthetic technique was developed, and over 300 g BGSe polycrystalline raw material with high purity were synthesized at one time. To avoid the crystal cracking and increase the usage for preparing NLO device, a crystal seed with appropriate orientation was

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

selected for vertical Bridgman technique and high-quality crystals with dimensions up to Φ 40 mm × 150 mm were grown successfully. The BGSe crystals exhibits high transmittance over a wide transparent range and the absorption coefficient was estimated around 0.04 cm-1 in the range of 1–13 μm . Moreover, via the two zone thermal annealing under the atmosphere of BGSe powder vapor, the transmittance of BGSe has been significantly improved.

INTRODUCTION Due to the continuous development of military and civilian applications, the demand for high performance infrared nonlinear optical (IR NLO) crystals is growing urgently.1–4 At present, commercial IR NLO materials are AgGaS2 ,AgGaSe2 and ZnGeP2.5–7 However, AgGaQ2 (Q = S, Se) are deficient for the high power IR laser output owing to their low laser damage thresholds (LDTs), ZnGeP2 can’t be pumped by conventional 1064 nm laser (Nd:YAG) due to its harmful multi-photon absorption at 1−2 μm.8,9 These inherent drawbacks severely limit their application. Therefore, numerous efforts has been devoted to the development of new materials to outperform existing commercialized crystals.10,11 The new IR NLO material BaGa4Se7 was first reported by our group in 2010.12 BaGa4Se7 (BGSe) crystallizes in a monoclinic Pc space group (no.7) and possesses a three-dimensional (3D) structure composed of parallel arranged tetrahedral GaSe4 groups by sharing their vertexes. BGSe exhibits a wide bandgap (2.64 eV), wide


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transparent range (0.47−18 μm), large SHG coefficient, large birefringence (∆n = 0.06@2 μm), and large laser damage threshold.13,14 It can be pumped by 1−3 μm lasers to generate wide tunable IR laser up to 18 μm.15–18 Moreover, BGSe has the potential to achieve large aperture sample without the limit of the penetration depth of electron irradiation method used in the postgrowth treatment of ZnGeP2. By the Bridgman–Stockbarger technique, bulk single BGSe crystal with the size of Φ20 × 30 mm were grown previously, and many properties such as thermal conductivity coefficients, thermal expansion coefficients, and the LDT were measured.13 Furthermore, the wide range IR laser output has been realized through various OPA, OPO, DFG processes (intracavity/extravity, cw/pulse pumping).16,17,19–23 In particular, in frequency down-conversion OPOs pumped by the conventional 1μm laser, BGSe has realized stable IR laser output with the highest power and widest wavelength range so far.18 When pumped by the 2.09 μm laser, BGSe has output 1.55 W “3–5μm” mid-IR and 0.31W “8–9μm” far-IR lasers, demonstrating its great potential for realizing IR laser output.16 In order to get wider application of BGSe, the growth of crystals with larger size and better qualities is crucial because the large device-aperture is beneficial to the angle tuning during laser output and the longer device can help to improve photon conversion efficiency and reduce the OPO output threshold.24–27 To grow large crystal, large-scale synthesis of highly pure polycrystalline raw material is the first important step. However, the synthesis of polycrystalline BGSe raw material was proved to be difficult due to the high chemical reactivity and corrosiveness of metal



Ba, low melting point and fluidity of Ga, and the high vapor pressure produced by Se, which would lead to the deviation from stoichiometric composition and even the explosion of quartz tubes. Moreover, many problems would exist during the growth of large crystal like crystal cracking, twinning, and absorption caused by defects and so on. Here, we report our efforts on the development of two temperature-zone large scale synthesis of BGSe polycrystalline raw material with high purity, growth of crack-free large-size BGSe crystals with high usage via the seeded Bridgeman technique, as well as the thermal annealing studies to further improve its transmittance.

EXPERIMENTS Synthesis of polycrystalline material. Over 300 g high-purity BGSe polycrystalline powder could be obtained in one run by two temperature-zone synthetic method.28 High purity Ba (3N), Ga (8N) and Se (6N) in the stoichiometric ratio of Ba/Ga/Se = 1:4:7 were placed in a long quartz tube. The Ba and Ga were put into the PBN crucible in high temperature zone, and the Se was put at low temperature zone. The tube was sealed off under high vacuum of 10-5 Pa and then inserted into the horizontal furnace. Figure 1 shows the temperature-time profile of BGSe synthesis. The schematic of the furnace and the temperature profile for the BGSe synthesis is shown in Figure 2. The synthesis process is mainly divided into three steps. First, the cold and the hot


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zone rise to 500 °C and 930 °C simultaneously, and maintained at this temperature for about 20 hours. During this process, selenium evaporated and then transported to the hot zone where BGSe was formed in the PBN crucible. In the temperature gradient region, a small amount of binary gallium selenide would form at the same time. Next, the cold zone is increased to 950 °C and the hot zone is reduced to 900 °C. The binary gallium selenides in the gradient zone were transported to the high temperature region, where reacted with the remaining barium to form the homogenized BGSe. After that, the furnace was cooled to room temperature within 24 hours. Crystal growth A PBN crucible was first washed with aqua regia, then with deionized water, and dried. The quartz ampoule for crystal growth was washed with dichromic acid solution, acetone, and deionized water successively. To increase the crystal usage for NLO device fabrication and to avoid crack during the growth process, a Φ 3mm × 30mm crystal seed along the a direction was used to grow BGSe single crystal by Bridgman–Stockbarger method. In a typical growth attempt, 900 g polycrystalline BGSe raw material was loaded in the PBN crucible with the crystal seed at the bottom. Afterward, the crucible was transferred into the tube and sealed under a high vacuum of 10-5 Pa. The sealed ampoule was placed in a vertical six-zone furnace, the schematic diagram of the furnace and the temperature profile was shown in Figure 3. Since the melting point of BGSe is 1020 °C, the temperatures of the upper zone and the lower



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zone were set to about 1030-1040 °C and 930-950 °C, respectively. Before crystal growth commenced, the BGSe polycrystalline charge and part of the seed crystal were melted via adjusting the position of the furnace and homogenized for 48 h. Then the ampule was pulled down slowly to crystallize BGSe melt with the growth rate about 0.4-0.6mm/h. After complete solidification, the grown crystal was slowly cooled at 20 °C/h to room temperature. Two-zone-annealing The

thermal

annealing

effect

of

BGSe

crystal

was

studied

via

the

two-zone-annealing technique.29 The furnace used for the two-zone-annealing is similar to that of two temperature zone synthesis. The PBN crucible filled with BGSe powder was placed at one end of the quartz tube (source-zone) and the crystal was placed at the other end (annealing-zone). The BGSe crystals used for thermal annealing experiments were cut from a smaller-sized crystal ingot which was previously grown. After evacuated and sealed under a high vacuum of 10-5 Pa, the tube was placed into the furnace. To get better results, it’s necessary to ensure that the powder located in the high temperature zone and the crystal located in the low temperature zone by adjusting the position of the tube. Instruments for characterization Powder X-ray diffraction (PXRD) patterns were recorded on an automated Bruker D8 X-ray diffractometer (Cu Kα radiation) with the scan step width was 0.02° in the 2θ range of 10−70°. The fixed counting time was 0.1 s/step. A PerkinElmer UV–


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vis-NIR spectrometer (Lambda 900) was used to measure the optical transparency in the visible and near IR range (0.4–3 μm) and a VERTEX 80 V FTIR spectrometer measured the transmission spectrum in the middle IR range (2–25 μm).

RESULTS AND DISCUSSION BGSe synthesis and XRD analysis Previously, we used a single temperature zone method to synthesize BGSe polycrystalline raw materials: the raw elements Ba, Ga, and Se are put together in the one end of the quartz tube and heated at about 1000 °C. However, the highly reactive Ba metal is prone to corrode the quartz tube during the heating process. What’s more, when heated to a high temperature, the vapor pressure of Se would be very large. The interaction of these factors may led to the cracking and even explosion of the quartz tube. At the same time, the raw materials can not be mixed evenly and fully reacted, resulting in the introduction of impurities and making the products inhomogeneous. Moreover, the amount of the raw material synthesized for a single run is about 25 g, with careful design of the heating profile to avoid the cracking/explosion of the quartz tube. Even so, the success rate is only about 50%. As the crystals become large, the total amount of raw material reaches above 500 g for a growth cycle. Impurity will be easily introduced into the charge during the multiple synthesis and transfer process. These shortcomings make the single-temperature zone synthesis of raw materials far from meeting the needs of large crystal growth.



When the two temperature-zone synthetic technique was applied, these problems could be solved well. The Ba and Ga materials were placed in the PBN boat, avoiding direct contact with the quartz tube, thereby preventing the quartz tube from being corroded. In the reaction stage, the Se vaporized at the cold zone with a much lower vapor pressure and then transported from cold zone to the hot zone, where the BGSe compound was synthesized and homogenized. Figure 4a shown the as-synthesized yellow BGSe polycrystalline with a mass of 315 g, resulting in a synthetic mass an order of magnitude higher than the single-zone synthetic method. The PXRD pattern of as-synthesized BGSe polycrystalline sample was shown in Figure 4b, which matched the simulated one perfectly. This result indicated that the as-synthesized BGSe polycrystalline, prepared by the introduced two temperature-zone synthetic technique, has a very high purity and could be used for crystal growth. BGSe Crystal and characterization Large-size and high-quality BGSe single crystal was grown by the seeded Bridgman method. Figure 5 shows a photograph of a Ф40 mm × 150 mm BGSe crystal and a typical OPO device fabricated from the large BGSe crystal (size: 6× 6× 40 mm3). The transmission spectra of BGSe sample, 8.7 mm in thickness, was shown in Figure 6. BGSe crystals exhibits high transmittance from 0.47 μm to 18 μm, which covers the two atmospheric windows of 3–5 μm and 8–12 μm, except for a multiphonon absorption peak at around 15 μm (Figure 6). Using the following


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expression,30 the optical absorption coefficient could be calculated:

α = ―

― T2 + T4 + 4Ttotal2R2 1 ) ln( l 2TtotalR2

Where Ttotal is the transmissivity measured by the instrument, l is the thickness of the sample, T = 1 – R, and R = (n–1)2/ (n+1)2 is the Fresnel power reflection coefficient. The refractive indices for the different wavelengths were derived from Sellmeier equation.31 The absorption coefficients of BGSe at 4 μm is calculated to be 0.042 cm-1, which indicated that the optical quality have been significantly improved than before. Two-zone-annealing Initially, we tried many different annealing atmospheres such as Ar gas, Se vapor and BGSe powder, as well as different annealing methods. When using the BGSe powder as the annealing source, the best annealing effect so far can be obtained by the two-zone-annealing method. The temperature of annealing zone and the source zone were chosen to be 500 °C and 950 °C, respectively. At the same time, the annealing time was kept for 120 h. The transmission spectra of a polished 10× 10× 15 mm3 BGSe sample were measured before and after annealing (Figure 7). It can be clearly seen that the transmittance of BGSe has been significantly improved after annealing, especially above 4 μm. The absorption coefficient drops from 0.15 cm-1 to 0.03 cm-1 at 10 μm. Generally, the absorption intensity in the crystal increases with the increase



of the defect concentration. In the two zone annealing experiment, the BGSe crystal and the source were separated in different regions, which could appropriately compensate the volatile component of crystals. The mechanism of thermal annealing and the study of crystal defects will be our next work.

CONCLUSION Two temperature-zone vapor transfer can be successfully used for large-scale synthesis of BGSe polycrystalline material with high purity. By using a crystal seed in the vertical Bridgman crystal growth process, large-size BGSe single crystal with dimension up to Φ40 mm × 150 mm were grown successfully and device with length up to 40 mm can be fabricated. In addition, the optical properties of BGSe has been significantly improved by the two zone annealing technique under the BGSe powder vapor atmosphere. The combination of larger size, lower absorption and higher LDT of BGSe crystal may realize higher power output of mid-far IR laser. In the future, the crystal processing technique, in particular the polishing and coating methods, need to be optimized. It has been proved that laser damage threshold of IR NLO crystals can be more than doubled by improvement in crystal polishing. Besides, coating procedures suitable for the specific physicochemical properties of BGSe will greatly reduce the reflection loss of input laser while at same time maintain high laser-damage threshold.

ACKNOWLEDGMENTS


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This research was supported by the National Natural Science Foundation of China (No. 51472251 and No. 91622123).

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Figure Captions Figure 1 Temperature-time profile of BGSe synthesis. Figure 2 Schematic of furnace for BGSe synthesis and temperature profiles. Figure 3 Schematic of furnace for BGSe growth and temperature profiles. Figure 4 (a) The as-synthesized 315 g polycrystalline BGSe prepared by two-temperature method. (b) X-ray powder diffraction patterns of BGSe: experimental (red) and simulated (black). Figure 5 (a) BGSe single crystal ingots: Ф40 mm × 150 mm (b) The photograph of BGSe device with the size of 6× 6× 40 mm3 Figure 6 Transmittance spectra of the BGSe crystal (8× 8× 8.7 mm3) Figure 7 The transmission spectra of BGSe before (black) and after (red) annealing (crystal size: 10× 10× 15 mm3).




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Figure 1. Temperature-time profile of BGSe synthesis.

Figure 2. Schematic of furnace for BGSe synthesis and temperature profiles.



Figure 3. Schematic of furnace for BGSe growth and temperature profiles


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(a)

(b) Figure 4. (a) The as-synthesized 315 g polycrystalline BGSe prepared by two-temperature method. (b) X-ray powder diffraction patterns of BGSe: experimental (red) and simulated (black).



(a)


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(b)

Figure 5. (a) BGSe single crystal ingots: Ф40 mm × 150 mm (b) The photograph of BGSe device with the size of 6× 6× 40 mm3



Figure 6. Transmittance spectra of the BGSe crystal (8× 8× 8.7 mm3)

Figure 7. The transmission spectra of BGSe before (black) and after (red) annealing (crystal size: 10× 10× 15 mm3).

For Table of Contents Use Only Synthesis, Growth of Crack-free Large-size BaGa4Se7 Crystal and Annealing Studies Yangwu Guo,†,‡ Zhuang Li,†,‡ Zuotao Lei,‖ Xiaoyu Luo,†,‡ Jiyong Yao,*,† Chunhui Yang‖ and Yicheng Wu†,§ †Beijing

Center for Crystal Research and Development, Key Laboratory of Functional Crystals and

Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P.R. China ‡University

of Chinese Academy of Sciences, Beijing 100049, P.R. China


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‖School

of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001, PR

China §Institute

of Functional Crystal Materials, Tianjin University of Technology, Tianjin 300384, P.R.

China

Two temperature-zone vapor transfer have been successfully used for large scale synthesis of high purity BaGa4Se7 polycrystalline material. By the seeded Bridgeman technique, large-size BaGa4Se7 single crystal with dimension up to Φ40 mm × 150 mm were grown successfully and device with length up to 40 mm can be fabricated.


Synthesis, Growth of Crack-free Large-size BaGa4Se7 Crystal and

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