Growth and Performance of Low-Dislocation 6-Inch GaSb Single Crystal

doi:10.16553/j.cnki.issn1000-985x.2024.0277

Abstract

Abstract: Gallium antimonide has been widely recognized for its superior physical properties and significant application value. The first domestic 6-inch n-type Te-doped GaSb single crystal ingot was successfully grown by the research team using the liquid encapsulated Czochralski method. High-quality 6-inch GaSb wafers are prepared， and the crystal quality and wafer surface properties are studied. The full width at half maximum of the rocking curve for the （400） plane of the GaSb substrate is only 20″， and the average dislocation density is approximately 3 177 cm^-2. The surface roughness （Rq） is 0.42 nm， and the oxide layer thickness is 2.92 nm. These results demonstrate the high crystalline quality and excellent surface morphology of the 6-inch GaSb single crystal. In addition， numerical simulations of the growth process of the 6-inch GaSb single crystal are conducted， revealing the thermal field distribution， flow field distribution， and solid-liquid interface deflection. These findings provide new insights for the high-quality growth of GaSb materials and lay a foundation for the industrial application of large-sized crystals.

Key words: 6-inch; GaSb; liquid encapsulated Czochralski method; dislocation density; numerical simulation; thermal field distribution; oxide layer thickness; surface roughness

CLC Number:

O782⁺.9

YANG Wenwen, LU Wei, XIE Hui, LIU Gang, LYU Xinyu, BAI Yihan, LI Chenhui, PAN Jiaoqing, ZHAO Youwen, SHEN Guiying. Growth and Performance of Low-Dislocation 6-Inch GaSb Single Crystal[J]. Journal of Synthetic Crystals, 2025, 54(5): 784-792.

Figures/Tables 8

Fig.1 Schematic diagram of the GaSb single crystal growth system structure

Table 1 Physical properties of the materials used in simulation

Material	Physical property	Value
GaSb melt	Melting temperature/K	985
	Density/（kg $∙$ m^-3）	5 720
	Heat conductivity/（W $∙$ m^-1 $∙$ K^-1）	17.1
	Specific heat/（J∙K^-1∙kg^-1）	328
	Dynamic viscosity/（Pa $∙$ s）	2.31×10^-3
	Emissivity	0.6
	Latent heat/（J $∙$ kg^-1）	2.606×10⁵
GaSb crystal	Heat conductivity/（W $∙$ m^-1 $∙$ K^-1）	4.57
	Density/（kg $∙$ m^-3）	5 630
	Emissivity	0.6
	Specific heat/（J∙K^-1∙kg^-1）	266
Graphite	Heat conductivity/（W $∙$ m^-1 $∙$ K^-1）	58
	Density/（kg $∙$ m^-3）	2 230
	Emissivity	0.7
	Specific heat/（J∙K^-1∙kg^-1）	720
Steel	Heat conductivity/（W $∙$ m^-1 $∙$ K^-1）	10
	Density/（kg $∙$ m^-3）	7 850
	Emissivity	0.5
	Specific heat/（J∙K^-1∙kg^-1）	500
Felt	Heat conductivity/（W $∙$ m^-1 $∙$ K^-1）	0.16
	Density/（kg $∙$ m^-3）	120
	Emissivity	0.7
	Specific heat/（J∙K^-1∙kg^-1）	200
Quartz	Heat conductivity/（W $∙$ m^-1 $∙$ K^-1）	2
	Density/（kg $∙$ m^-3）	2 650
	Emissivity	0.85
	Specific heat/（J∙K^-1∙kg^-1）	1 232

Table 1 Physical properties of the materials used in simulation

Material	Physical property	Value
GaSb melt	Melting temperature/K	985
	Density/（kg $∙$ m^-3）	5 720
	Heat conductivity/（W $∙$ m^-1 $∙$ K^-1）	17.1
	Specific heat/（J∙K^-1∙kg^-1）	328
	Dynamic viscosity/（Pa $∙$ s）	2.31×10^-3
	Emissivity	0.6
	Latent heat/（J $∙$ kg^-1）	2.606×10⁵
GaSb crystal	Heat conductivity/（W $∙$ m^-1 $∙$ K^-1）	4.57
	Density/（kg $∙$ m^-3）	5 630
	Emissivity	0.6
	Specific heat/（J∙K^-1∙kg^-1）	266
Graphite	Heat conductivity/（W $∙$ m^-1 $∙$ K^-1）	58
	Density/（kg $∙$ m^-3）	2 230
	Emissivity	0.7
	Specific heat/（J∙K^-1∙kg^-1）	720
Steel	Heat conductivity/（W $∙$ m^-1 $∙$ K^-1）	10
	Density/（kg $∙$ m^-3）	7 850
	Emissivity	0.5
	Specific heat/（J∙K^-1∙kg^-1）	500
Felt	Heat conductivity/（W $∙$ m^-1 $∙$ K^-1）	0.16
	Density/（kg $∙$ m^-3）	120
	Emissivity	0.7
	Specific heat/（J∙K^-1∙kg^-1）	200
Quartz	Heat conductivity/（W $∙$ m^-1 $∙$ K^-1）	2
	Density/（kg $∙$ m^-3）	2 650
	Emissivity	0.85
	Specific heat/（J∙K^-1∙kg^-1）	1 232

Fig.2 Photos of 6-inch Te-GaSb single crystal （a） and wafer （b）

Fig.3 Simulation results of thermal field characteristics for 6-inch GaSb growth. （a） Temperature distribution and heat flux direction in the crystallization zone；（b） variation of the solid-liquid interface deflection Y with the radial position X of the crystal under different growth lengths

Fig.4 Distribution of melt plane velocity Vx -Vy and flow patterns for growth diameters of 3-inch （a） and 6-inch （b）

Fig.5 Variation of the solid-liquid interface deflection Y with the radial position X of the crystal under different pulling rates （a） and crystal rotation rates （b）， as well as the melt convection at crystal rotation rates of 2 r/min （c） and 6 r/min （d）

Fig.6 Distribution of dislocation etch pit density （a） and （400） plane rocking curve （b） for 6-inch Te-GaSb single crystal

Fig.7 Distribution of oxide layer thickness （a） and roughness （b） on the surface of 6-inch Te-GaSb （100） wafer

References 29

1	MÜLLER R， GRAMICH V， WAURO M， et al. High operating temperature InAs/GaSb type-Ⅱ superlattice detectors on GaAs substrate for the long wavelength infrared［J］. Infrared Physics & Technology， 2019， 96： 141-144.
2	CRAIG A P， LETKA V， CARMICHAEL M， et al. InAsSb-based detectors on GaSb for near-room-temperature operation in the mid-wave infrared［J］. Applied Physics Letters， 2021， 118（25）： 251103.
3	NISHIMOTO N， FUJIHARA J， YOSHINO K. Biocompatibility of GaSb thin films grown by RF magnetron sputtering［J］. Applied Surface Science， 2017， 409： 375-380.
4	ZHOU X C， LI D S， HUANG J L， et al. Mid-wavelength type Ⅱ InAs/GaSb superlattice infrared focal plane arrays［J］. Infrared Physics & Technology， 2016， 78： 263-267.
5	LOTFI H， LI L， SHAZZAD RASSEL S M， et al. Monolithically integrated mid-IR interband cascade laser and photodetector operating at room temperature［J］. Applied Physics Letters， 2016， 109（15）： 151111.
6	DONG W M， JIANG J， PENG Q W， et al. Study on the facet effect in LEC-GaSb single crystals［J］. Journal of Crystal Growth， 2024， 636： 127706.
7	刘京明，杨　俊，赵有文，等. GaSb单晶研究进展［J］. 人工晶体学报， 2024， 53（1）： 1-11.
	LIU J M， YANG J， ZHAO Y W， et al. Research progress of GaSb single crystal［J］. Journal of Synthetic Crystals， 2024， 53（1）： 1-11 （in Chinese）.
8	REIJNEN L， BRUNTON R， GRANT I R. Comparison of LEC-grown and VGF-grown GaSb［C］// AIP Conference Proceedings. American Institute of Physics， 2004， 738（1）： 360-367.
9	赵有文，段满龙，卢　伟，等. 4 inch低位错密度InP单晶的VGF生长及性质研究［J］. 人工晶体学报， 2017， 46（5）： 792-796.
	ZHAO Y W， DUAN M L， LU W， et al. VGF growth and property of 4 inch diameter InP single crystals with low dislocation density［J］. Journal of Synthetic Crystals， 2017， 46（5）： 792-796 （in Chinese）.
10	YAN B， LIU W H， YU Z J， et al. Temperature dynamic compensation vertical Bridgman method growth of high-quality GaSb single crystals［J］. Journal of Crystal Growth， 2023， 602： 126988.
11	SIM B C， JUNG Y H， LEE J E， et al. Effect of the crystal-melt interface on the grown-in defects in silicon CZ growth［J］. Journal of Crystal Growth， 2007， 299（1）： 152-157.
12	KLIN O， SNAPI N， COHEN Y， et al. A study of MBE growth-related defects in InAs/GaSb type-Ⅱ supperlattices for long wavelength infrared detectors［J］. Journal of Crystal Growth， 2015， 425： 54-59.
13	KOERPERICK E J， MURRAY L M， NORTON D T， et al. Optimization of MBE-grown GaSb buffer layers and surface effects of antimony stabilization flux［J］. Journal of Crystal Growth， 2010， 312（2）： 185-191.
14	ZHU Y B， WEN H H， ZHANG H Y， et al. Real-time in situ observation of extended defect evolution near a crack tip in GaSb crystal under thermal loading［J］. Applied Surface Science， 2020， 515： 145934.
15	杨　俊，段满龙，卢　伟，等. 低位错密度4 inch GaSb（100）单晶生长及高质量衬底制备［J］. 人工晶体学报， 2017， 46（5）： 820-824.
	YANG J， DUAN M L， LU W， et al. Growth of 4 inch diameter GaSb（100） single crystal with low dislocation density and high quality substrate preparation［J］. Journal of Synthetic Crystals， 2017， 46（5）： 820-824 （in Chinese）.
16	NOGHABI O A， JOMÂA M， M’HAMDI M. Analysis of W-shape melt/crystal interface formation in Czochralski silicon crystal growth［J］. Journal of Crystal Growth， 2013， 362： 77-82.
17	ZHOU Y， ZHAO Y W， XIE H， et al. Residual stress distribution and flatness of dislocation-free Te-GaSb （100） substrate［J］. Japanese Journal of Applied Physics， 2021， 60（3）： 035510.
18	BRIGHTUP S， GOORSKY M S. Chemical-mechanical polishing for Ⅲ-Ⅴ wafer bonding applications： polishing， roughness， and an abrasive-free polishing model［J］. ECS Transactions， 2010， 33（4）： 383-389.
19	Inc STR. CGSim software［OL］. STR Inc.，［2024-12-30］. https://str-soft.com/.
20	Inc STR. CGSim theory manual［Z］. v.22.1. Richmond VA： STR Inc.， 2022.
21	Inc STR. CGSim flow module theory manual［Z］. v.24.1. Richmond VA： STR Inc.， 2024.
22	NGUYEN T H T， CHEN J C， HU C， et al. Numerical simulation of heat and mass transfer during Czochralski silicon crystal growth under the application of crystal-crucible counter- and iso-rotations［J］. Journal of Crystal Growth， 2019， 507： 50-57.
23	LI X L， LIU Y L， WANG B， et al. Global heat loss and thermal stress analysis in Czochralski crystal growth［J］. Crystal Research and Technology， 2014， 49（6）： 376-382.
24	冯银红，沈桂英，赵有文，等. 无位错Te-GaSb（100）单晶抛光衬底的晶格完整性［J］. 人工晶体学报， 2022， 51（6）： 1003-1011.
	FENG Y H， SHEN G Y， ZHAO Y W， et al. Lattice perfection of dislocation-free （100） Te-GaSb single crystal polished substrate［J］. Journal of Synthetic Crystals， 2022， 51（6）： 1003-1011 （in Chinese）.
25	SHEN G Y， ZHAO Y W， LIU J M， et al. Oxidation related particles on GaSb （100） substrate surfaces［J］. Journal of Crystal Growth， 2022， 581： 126499.
26	GRAY N W， PRAX A， JOHNSON D， et al. Rapid development of high-volume manufacturing methods for epi-ready GaSb wafers up to 6″ diameter for IR imaging applications［C］// SPIE Defense+Security. Proc SPIE 9819， Infrared Technology and Applications XLII， Baltimore， MD， USA. 2016， 9819： 274-284.
27	MARTINEZ R， TYBJERG M， FLINT P， et al. A study of the preparation of epitaxy-ready polished surfaces of （100） gallium antimonide substrates demonstrating ultra-low surface defects for MBE growth［C］// Infrared Technology and Applications XLII. Baltimore， Maryland， USA. SPIE， 2016： 298-309.
28	FURLONG M J， MARTINEZ B， TYBJERG M， et al. Growth and characterization of ≥6″ epitaxy-ready GaSb substrates for use in large area infrared imaging applications［C］// Infrared Technology and Applications XLI. Baltimore， Maryland， USA. SPIE， 2015： 182-189.
29	MARTINEZ R， AMIRHAGHI S， SMITH B， et al. Large diameter ‘ultra-flat’ epitaxy ready GaSb substrates： requirements for MBE grown advanced infrared detectors［C］// Infrared Technology and Applications XXXVIII. Baltimore， Maryland. SPIE， 2012： 8353.

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