Macroscopic Defects of Large Bi12GeO20 Crystals Grown Using Vertical Bridgman Method

doi:10.15541/jim20220642

Abstract

Abstract:

As a multifunctional opto-electro material, Bi₁₂GeO₂₀crystal shows high-speed photorefractive response in visible range, excellent piezoelectric, acousto-optic, magneto-optic, optical rotation, and electro-optic properties, etc. Presently, Czochralski (Cz) method, which is commonly used to grow Bi₁₂GeO₂₀ crystals, has several bottle-necks, such as high growth cost, irregular crystal boule shapes, low growth yield, poor optical quality in large crystals, and small effective crystal cross-sectional area. In this study, large Bi₁₂GeO₂₀ crystals were firstly grown by using modified vertical Bridgman method in platinum crucibles and air atmosphere. Morphology, distribution, and constitutes of main macroscopic defects in as-grown Bi₁₂GeO₂₀ crystals were investigated, and the formation process and causes of the main macroscopic defects during the crystal growth were studied. Dendrite and tubular inclusions are two types of main macroscopic defects existed in as-grown Bi₁₂GeO₂₀ crystals. The formation of dendrite inclusions is closely related to the platinum corrosion, while the formation of tubular inclusions is associated with precipitation of platinum, a mismatch in the stacking of growth units due to instability of the seeding interface, and instability temperature field. Technical approaches to eliminate or reduce these two types of macroscopic defects during the growth using vertical Bridgman method were proposed. High optical quality, large Bi₁₂GeO₂₀ crystals with sizes up to 55 mm×55 mm×80 mm and significantly improved optical transmittance were grown reproducibly by reducing control temperature, decreasing period of melt preserved at high temperature, and selecting seed crystals with better quality.

Key words: Bi₁₂GeO₂₀ crystal, vertical Bridgman method, macroscopic defect, crystal growth

CLC Number:

TQ174

QI Xuejun, ZHANG Jian, CHEN Lei, WANG Shaohan, LI Xiang, DU Yong, CHEN Junfeng. Macroscopic Defects of Large Bi₁₂GeO₂₀ Crystals Grown Using Vertical Bridgman Method[J]. Journal of Inorganic Materials, 2023, 38(3): 280-287.

Figures/Tables 10

Fig. 1 TG-DSC curves (a) and XRD patterns (b) of Bi12GeO20 crystal

Fig. 2 Macroscopic defects in as-grown Bi12GeO20 crystal ingots (a) As-grown Bi12GeO20 crystal ingots; (b, c) Dendritic inclusions; (d) Tubular scattering defects under the illumination of 532 nm laser light; (e) Tubular inclusions in polished crystals

Fig. 3 Dendritic inclusions in Bi12GeO20 crystal observed by optical microscope(100×)

Fig. 4 SEM images (a, c, e) and EDS spectra (b, d, f) of dendritic inclusions in Bi12GeO20 crystals

Table 1 SEM-EDS composition analysis results of dendritic inclusions in Bi12GeO20 crystal (in atomic)

Spectrum	Pt/%	Bi/%	Ge/%	O/%	Bi/Ge
1	6.85	39.57	3.15	50.43	12.56
2	100.0	0	0	0	-
3	88.20	2.08	0	9.72	-
Matrix	0	36.27	3.11	60.62	11.66

Fig. 5 Elemental mappings of the dendritic inclusions in Bi12GeO20 crystal at the microstructural level by scanning electron microscope (SEM) with energy dispersive X-ray spectrometry (EDS) (a, c) Mappings of Bi, Pt, O, Ge; (b, d) Respective mappings of Bi, Pt, O, Ge

Fig. 6 Typical photos for the leakage of Pt crucibles (a) and Pt deposition (b) in as-grown crystal boule

Fig. 7 Optical morphology of as-grown Bi12GeO20 crystal boule on the tail end

Fig. 8 Pictures of as-grown Bi12GeO20 crystal boules with cross-sections of ϕ35 mm (a), and 55 mm×55 mm (b)

Fig. 9 Transmittance spectra of Bi12GeO20 crystals grown before and after growth parameters optimization Light path: 1 mm

References 32

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Macroscopic Defects of Large Bi₁₂GeO₂₀ Crystals Grown Using Vertical Bridgman Method

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