熔体法生长大尺寸有机晶体

摘要/Abstract

摘要： 大尺寸有机晶体在太赫兹波产生、中子探测、微波激射等多个关系国计民生、涉及国家安全的领域具有重要应用前景。但大尺寸有机单晶生长一直是国际公认的难题,无论是在生长理论、生长方法还是生长设备方面都远远落后,在整个人工晶体领域相对小众;而且有机晶体硬度低、脆性高、易解理等本征特性为加工和后期应用带来了很多困难,制约了相关领域的发展。有机分子晶体的物化性质决定了其生长方法多采用溶液或气相方法,熔体生长方法在结晶质量控制方面难度更大;但针对上述应用所需的大尺寸单晶和掺杂要求,熔体生长方法相比溶液和气相方法更具优势。本文对熔体法生长大尺寸有机晶体进行分类总结,对影响生长过程和晶体质量的原料提纯、籽晶生长、安瓿设计、固液界面控制、生长及降温速度调控、加热温区等因素进行分析,结合本课题组近年来利用熔体法生长大尺寸有机晶体的实际经验,旨在为大尺寸有机晶体的生长研究提供理论基础和实践经验,突破高质量、大尺寸有机单晶生长的国际难题。

关键词: 有机晶体, 大尺寸, 生长方法, 熔体法, 布里奇曼法

Abstract: Large-sized organic single crystals play an indispensable role in many fields such as terahertz generation, neutron detection and maser, which are essential to national security and welfare. However, the growth of large-sized organic crystals has always been a big challenge and moreover, due to the intrinsic characteristics of organic crystals such as low hardness, frangibility, and easy-to-cleavage, processing and application of organic crystals are also hard tasks. Considering the lack of available large-sized organic single crystals has seriously hampered the development of the related fields in our country, a full summary and analysis of organic crystals growth methods is necessary. Comparing with growth methods based on gas phase and liquid phase, growth of bulk and doped organic crystals from melt is superior in terms of size and doping control. However, regulating accurately the growth process of bulk-sized and hig-quality crystal from organic melt is difficult to realize due to the low crystallization capacity and thermal stability of organic melts. In order to provide theoretical basis and practical experience, the research progress of bulk organic crystals via melt growth is summarized in this paper. From the aspects of raw materials refining, seed crystals selection, ampoule design, solid-liquid interface control, growing and cooling rate, and thermal field optimization, both scientific problems and technical issues in melt growth of bulk organic single crystals are specifically analyzed.

Key words: organic crystal, large-sized, growth method, melt growth, Bridgman method

中图分类号:

O734

蒋金科, 崔双月, 刘阳, 陶绪堂. 熔体法生长大尺寸有机晶体[J]. 人工晶体学报, 2021, 50(4): 603-618.

JIANG Jinke, CUI Shuangyue, LIU Yang, TAO Xutang. Melt Growth of Bulk Organic Crystals[J]. Journal of Synthetic Crystals, 2021, 50(4): 603-618.

参考文献

[1] WU H, MIRKHANOV S, Ng W, et al. Invasive optical pumping for room-temperature masers, time-resolved EPR, triplet-DNP, and quantum engines exploiting strong coupling[J]. Optics Express, 2020, 28(20): 29691-29702.
[2] MANIVANNAN S, DHANUSKODI S, TIWARI S K, et al. Laser induced surface damage, thermal transport and microhardness studies on certain organic and semiorganic nonlinear optical crystals[J]. Applied Physics B, 2008, 90(3/4): 489-496.
[3] CHEN T L, SUN Z H, SONG C, et al. Bulk crystal growth and optical and thermal properties of the nonlinear optical crystal l-histidinium-4-nitrophenolate 4-nitrophenol (LHPP)[J]. Crystal Growth & Design, 2012, 12(5): 2673-2678.
[4] RAMACHANDRAN K, RAJA A, MOHANKUMAR V, et al. Experimental and theoretical approach of organic 4, 4′-dimethylbenzophenone (DMBP) single crystal for NLO application[J]. Optics & Laser Technology, 2019, 119: 105640.
[5] THIRUPUGALMANI K, KARTHICK S, SHANMUGAM G, et al. Second- and third-order nonlinear optical and quantum chemical studies on 2-amino-4-picolinium-nitrophenolate-nitrophenol: a phasematchable organic single crystal[J]. Optical Materials, 2015, 49: 158-170.
[6] BABU B, CHANDRASEKARAN J, MOHANBABU B, et al. Growth, physicochemical and quantum chemical investigations on 2-amino 5-chloropyridinium 4-carboxybutanoate-an organic crystal for biological and optoelectronic device applications[J]. RSC Advances, 2016, 6(112): 110884-110897.
[7] RAMACHANDRAN K, RAJA A, MOHANKUMAR V, et al. Growth and characterization of 4-methyl-3-nitrobenzoic acid (4M3N) single crystal by using vertical transparent Bridgman-Stockbarger method for NLO applications[J]. Physica B: Condensed Matter, 2019, 562: 82-93.
[8] DENNIS RAJ A, JEEVA M, PURUSOTHAMAN R, et al. 1-((4-methylpiperazin-1-yl)(phenyl)methyl)naphthalen-2-ol: a novel Mannich base organic NLO crystal for the analysis of electro-optic applications[J]. Journal of Materials Science: Materials in Electronics, 2017, 28(11): 7802-7810.
[9] LI Y, ZHANG J X, ZHANG G Q, et al. Growth and characterization of DSTMS crystals[J]. Journal of Crystal Growth, 2011, 327(1): 127-132.
[10] KARTHICK S, SANTHA A, GANESH D, et al. Growth, spectral, laser damage and hirshfeld surface studies on configurationally locked 2-(3-(4-hydroxystyryl)-5, 5-dimethylcyclohex-2-enylidene) malononitrile (OH1) single crystal- a potential terahertz emitter[J]. Journal of Molecular Structure, 2021, 1224: 129065.
[11] KALAIVANAN R, SRINIVASAN K. Synthesis, growth and characterization of organic nonlinear optical material: N-benzyl-2-methyl-4-nitroaniline (BNA)[J]. Optics & Laser Technology, 2017, 90: 27-32.
[12] CAO L F, TENG B, FENG K, et al. Growth and defects of DAST crystal in high concentration solution[J]. Journal of Crystal Growth, 2015, 412: 20-24.
[13] 李亮,尹建红,曹珺,等.非线性光学有机晶体材料的研究进展[J].化学通报,2011,74(5):402-407.
LI L, YIN J H, CAO J, et al. The research progress of nonlinear optical organic crystals[J]. Chemistry, 2011, 74(5): 402-407(in Chinese).
[14] TANIUCHI T, OKADA S, NAKANISHI H. Widely tunable terahertz-wave generation in an organic crystal and its spectroscopic application[J]. Journal of Applied Physics, 2004, 95(11): 5984-5988.
[15] 石宗仁.探测快中子的新技术[J].核电子学与探测技术,1997,17(5): 390-396.
SHI Z R. New techniques used for detecting fast neutrons[J]. Nuclear Electronics & Detection Technology, 1997, 17(5): 390-396(in Chinese).
[16] 陶绪堂,王善朋,王蕾,等.晶体材料研究:从体块晶体到微纳米晶体[J].人工晶体学报,2019,48(5):763-786.
TAO X T, WANG S P, WANG L, et al. Research in crystal materials: from bulk crystals to micro-nano crystals[J]. Journal of Synthetic Crystals, 2019, 48(5): 763-786(in Chinese).
[17] STONE R. Researchers rise to challenge of replacing helium-3[J]. Science, 2016, 353(6294): 15-16.
[18] DURBIN M, WONDERS M A, FLASKA M, et al. K-Nearest neighbors regression for the discrimination of gamma rays and neutrons in organic scintillators[J]. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2021, 987: 164826.
[19] BRADLEY D. Room temperature maser; a solid state result: electronic materials[J]. Materials Today, 2012, 15(10): 424.
[20] OXBORROW M, BREEZE J D, ALFORD N M. Room-temperature solid-state maser[J]. Nature, 2012, 488(7411): 353-356.
[21] SUTHAN T, RAJESH N P. Growth and characterization of organic material 4-nitrobenzaldehyde single crystal using modified vertical Bridgman technique[J]. Journal of Crystal Growth, 2010, 312(21): 3156-3160.
[22] STANCULESCU A, STANCULESCU F, ALEXANDRU H. Melt growth and characterization of pure and doped meta-dinitrobenzene crystals[J]. Journal of Crystal Growth, 1999, 198/199: 572-577.
[23] ARULCHAKKARAVARTHI A, SANTHANARAGHAVAN P, RAMASAMY P. Crystal growth of trans-stilbene by vertical Bridgman technique with modified growth vessels and its characterisation[J]. Journal of Crystal Growth, 2001, 224(1/2): 89-94.
[24] VIJAYAN N, BALAMURUGAN N, RAMESH BABU R, et al. Bulk growth of benzimidazole single crystals by vertical Bridgman technique (VBT)[J]. Journal of Crystal Growth, 2004, 267(1/2): 218-222.
[25] 王文礼,王快社,王文,等.4-氨基二苯甲酮晶体的定向生长及光学性能研究[J].人工晶体学报,2009,38(4):1046-1050.
WANG W L, WANG K S, WANG W, et al. Oriented growth and optical properties of 4-aminobenzophenone crystal[J]. Journal of Synthetic Crystals, 2009, 38(4): 1046-1050(in Chinese).
[26] LAL R B, ZHANG H W, WANG W S, et al. Crystal growth and optical properties of 4-aminobenzophenone crystals for NLO applications[J]. Journal of Crystal Growth, 1997, 174(1/2/3/4): 393-397.
[27] FUKUDA T, SANO T, HOSOYA S, et al. Growth of 2-methyl-4-nitroaniline (MNA) crystals by the bridgman method[J]. Crystal Research and Technology, 1994, 29(7): 971-974.
[28] SELVAKUMAR S, SIVAJI K, BALAMURUGAN N, et al. Growth and studies on SSVBT grown p-terphenyl single crystals[J]. Journal of Crystal Growth, 2005, 275(1/2): e265-e271.
[29] BHAGAVANNARAYANA G, BUDAKOTI G C, MAURYA K K, et al. Enhancement of crystalline, piezoelectric and optical quality of LiNbO₃ single crystals by post-growth annealing and poling[J]. Journal of Crystal Growth, 2005, 282(3/4): 394-401.
[30] VIJAYAN N, BHAGAVANNARAYANA G, RAMESH BABU R, et al. Single, Bridgman-grown, fourier transform infrared, laser damage, and second-harmonic generation measurements[J]. Crystal Growth and Design, 2006, 6(6): 1542-1546.
[31] NIEMAX J, PFLAUM J. Bulk crystals of tetracene grown by the vapor-Bridgman technique[J]. Applied Physics Letters, 2005, 87(24): 241921.
[32] VIJAYAN N, BALAMURUGAN N, RAMESH BABU R, et al. Growth and characterization studies of organic NLO crystals of benzimidazole by melt technique[J]. Journal of Crystal Growth, 2005, 275(1/2): e1895-e1900.
[33] VIJAYAN N, BHAGAVANNARAYANA G, BALAMURUGAN N, et al. Studies on the growth and characterization of benzimidazole single crystals—vertical Bridgman technique[J]. Journal of Crystal Growth, 2006, 293(2): 318-323.
[34] RAI R N, VARMA K B R. Growth and characterization of single crystal of pentachloropyridine[J]. Journal of Crystal Growth, 2005, 285(1/2): 111-116.
[35] SUTHAN T, RAJESH N P, DHANARAJ P V, et al. Growth and characterization of naphthalene single crystals grown by modified vertical Bridgman method[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2010, 75(1): 69-73.
[36] ANANDHA BABU G, RAMASAMY P. Growth and characterization of organic molecular single crystal ethyl p-amino benzoate by selective self seeding from vertical Bridgman technique[J]. Journal of Crystal Growth, 2010, 312(16/17): 2423-2426.
[37] BABU R R, SUKUMAR M, VASUDEVAN V, et al. Growth and properties of benzil doped benzimidazole (BMZ) single crystals[J]. Materials Research Bulletin, 2010, 45(9): 1194-1198.
[38] SHERWOOD J N, THOMSON S J. Growth of single crystals of anthracene[J]. Journal of Scientific Instruments, 1960, 37(7): 242-245.
[39] 北京玻璃研究所.有机闪烁晶体的制备[J].原子能科学技术,1966(3):187-191.
BEIJING GLASS RESEARCH INSTITUTE CO., LTD. Synthesis of organic scintillator[J]. Atomic Energy Science and Technology, 1966(3): 187-191(in Chinese).
[40] ARULCHAKKARAVARTHI A, JAYAVEL P, SANTHANARAGHAVAN P, et al. Growth of organic molecular single crystal trans-stilbene by selective self seeding from vertical Bridgman technique[J]. Journal of Crystal Growth, 2002, 234(1): 159-163.
[41] 俞嗣皎,申敬廉,唐祖梅.有机闪烁体——茋晶体制备[J].核电子学与探测技术,1984,4(1):25-29+34.
YU S J, SHEN J L, TANG Z M. Organic scintillator—preparation of stilbene crystal[J]. Nuclear Electronics & Detection Technology, 1984, 4(1): 25-29+34(in Chinese).
[42] SUTHAN T, RAJESH N P, MAHADEVAN C K, et al. Growth and characterization of organic material 2-methylamino-5-chlorobenzophenone single crystal by modified vertical Bridgman technique[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2011, 79(5): 1443-1448.
[43] PRABHAKARAN S, BABU R R, VELUSAMY P, et al. Studies on the growth, structural, optical, mechanical properties of 8-hydroxyquinoline single crystal by vertical Bridgman technique[J]. Materials Research Bulletin, 2011, 46(11): 1781-1785.
[44] BALA SOLANKI S S, PERUMAL R N, SUTHAN T, et al. Growth and characterization of organic single crystal benzyl carbamate[J]. Journal of Crystal Growth, 2015, 427: 24-28.
[45] SUTHAN T, RAJESH N P, MAHADEVAN C K, et al. Growth and characterization of 2-hydroxy-4-methoxybenzophenone single crystal using modified vertical Bridgman technique[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2011, 78(2): 771-776.
[46] CUI S Y, LIU Y, LI G L, et al. Growth regulation of pentacene-doped p-terphenyl crystals on their physical properties for promising maser gain medium[J]. Crystal Growth & Design, 2020, 20(2): 783-792.
[47] JASINSKI T, WITT A F, ROHSENOW W M. Heat transfer analysis of the Bridgman-Stockbarger configuration for crystal growth[J]. Journal of Crystal Growth, 1984, 67(2): 173-184.
[48] NAUMANN R J, LEHOCZKY S L. Effect of variable thermal conductivity on isotherms in Bridgman growth[J]. Journal of Crystal Growth, 1983, 61(3): 707-710.
[49] ARIVANANDHAN M, SANKARANARAYANAN K, RAMAMOORTHY K, et al. A novel way of modifying the thermal gradient in vertical Bridgman-Stockbarger technique and studies on its effect on the growth of benzophenone single crystals[J]. Crystal Research and Technology, 2004, 39(8): 692-698.
[50] BARAT C, DUFFAR T, GARANDET J P. Estimation of the curvature of the solid-liquid interface during Bridgman crystal growth[J]. Journal of Crystal Growth, 1998, 194(1): 149-155.
[51] ARULCHAKKARAVARTHI A, LAKSHMANAPERUMAL C K, SANTHANARAGHAVAN P, et al. Investigations on the growth of anthracene and trans-stilbene single crystals using vertical Bridgman technique[J]. Materials Science and Engineering: B, 2002, 95(3): 236-241.
[52] ARIVANANDHAN M, HUANG X M, UDA S, et al. Directional growth of organic NLO crystal by different growth methods: a comparative study by means of XRD, HRXRD and laser damage threshold[J]. Journal of Crystal Growth, 2008, 310(21): 4587-4592.
[53] BALAMURUGAN N, ARULCHAKKARAVARTHI A, RAMASAMY P. Growth of 2, 5-diphenyloxazole-doped naphthalene crystal by Bridgman method and its fluorescence studies[J]. Journal of Crystal Growth, 2008, 310(7/8/9): 2115-2119.
[54] KOJIMA K. Photoplastic effect in anthracene crystals[J]. Applied Physics Letters, 1981, 38(7): 530-531.
[55] KANNAN V, JAYAPRAKASAN M, BAIRAVA GANESH R, et al. Single-crystal growth of 4-hydroxy-3-methoxy benzaldehyde by the Bridgman technique and its characterization[J]. Physica Status Solidi (a), 2006, 203(10): 2488-2495.
[56] ARULCHAKKARAVARTHI A, LAKSMANAPERUMAL C K, SANTHANARAGHAVAN P, et al. Preparation of high-quality anthracene crystals using double run selective self-seeding vertical Bridgman technique (DRSSVBT)[J]. Journal of Crystal Growth, 2002, 246(1/2): 85-89.
[57] SELVAKUMAR S, SIVAJI K, ARULCHAKKARAVARTHI A, et al. Enhanced fluorescence and time resolved fluorescence properties of p-terphenyl crystal grown by selective self seeded vertical Bridgman technique[J]. Materials Letters, 2007, 61(25): 4718-4721.
[58] BALAMURUGAN N, ARULCHAKKARAVARTHI A, RAMASAMY P. Luminescence properties and growth of pure and anthracene-doped naphthalene crystals[J]. Physica Status Solidi (a), 2007, 204(10): 3502-3508.
[59] AGGARWAL M D, WANG W S, CHOI J, et al. Modified Bridgman-Stockbarger growth of a novel NLO organic crystal (2-methoxyphenyl)-methylene-propanedinitrile[J]. Journal of Crystal Growth, 1996, 166(1/2/3/4): 542-544.
[60] AI Q, CHEN P F, FENG Y X, et al. Growth of pentacene-doped p-terphenyl crystals by vertical bridgman technique and doping effect on their characterization[J]. Crystal Growth & Design, 2017, 17(5): 2473-2477.
[61] YOKOO A, TOMARU S, YOKOHAMA I, et al. A new growth method for long rod-like organic nonlinear optical crystals with phase-matched direction[J]. Journal of Crystal Growth, 1995, 156(3): 279-284.
[62] SANKARANARAYANAN K, RAMASAMY P. Microtube-Czochralski technique (μT-Cz): a novel way of seeding the melt to grow bulk single crystal[J]. Journal of Crystal Growth, 1998, 193(1/2): 252-256.
[63] AGGARWAL M D, WANG W S, TAMBWE M. Modified czochralski growth of nonlinear optical organic crystals[J]. Materials Research Bulletin, 1992, 27(4): 431-437.
[64] BLEAY J, HOOPER R M, NARANG R S, et al. The growth of single crystals of some organic compounds by the Czochralski technique and the assessment of their perfection[J]. Journal of Crystal Growth, 1978, 43(5): 589-596.
[65] 刘秀华,谭昭怡,袁永刚,等.有机晶体闪烁体生长的熔体法及其特点[J].中国材料进展,2017,36(9):676-680.
LIU X H, TAN Z Y, YUAN Y G, et al. Melt method and its characteristics for the growth of organic crystal scintillator[J]. Materials China, 2017, 36(9): 676-680(in Chinese).
[66] AGGARWAL M D, WANG W S, TAMBWE M. Czochralski and modified Bridgman-Stockbarger growth of pure, Cd²⁺ and Nd³⁺ doped benzil single crystals[J]. Journal of Crystal Growth, 1993, 128(1/2/3/4): 891-896.
[67] RAMACHANDRAN K, VIJAYAKUMAR P, RAJA A, et al. Investigations on 4-methyl benzophenone (4MB) single crystal grown by Czochralski method and its characterization[J]. Journal of Materials Science: Materials in Electronics, 2018, 29(10): 8571-8583.
[68] YADAV H, SINHA N, TYAGI N, et al. Enhancement of optical, piezoelectric, and mechanical properties in crystal violet dye-doped benzophenone crystals grown by Czochralski technique[J]. Crystal Growth & Design, 2015, 15(10): 4908-4917.