Revealing the atomic-scale structures of dislocations in calcium fluoride single crystal

Senyang Li; Yongzhe Wang; Bo Zhang; Zhuowei Lu; Ke Yan; Shukuan Guo; Zhonghan Zhang; Dapang Jiang; Huamin Kou; Yi Zeng; Liangbi Su

doi:10.59717/j.xinn-mater.2025.100129

The Innovation Materials > 2025 Vol. 3 > No. 2 > 100129

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Revealing the atomic-scale structures of dislocations in calcium fluoride single crystal

1.
State Key Laboratory of Functional Crystals and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
2.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
3.
Wuhan University of Technology, Wuhan 430070, China

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Corresponding authors: suliangbi@mail.sic.ac.cn (S.L.); bozhang@mail.sic.ac.cn (Z.B.)
Received Date: January 03, 2025

Accepted Date: April 03, 2025

Published Online: April 10, 2025

The Innovation Materials 3(2), https://doi.org/10.59717/j.xinn-mater.2025.100129 | Cite this article

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PUBLIC SUMMARY
1. The atomic structure of dislocations were identified by utilizing a combination of characterization methods.
  
  The underlying mechanism responsible for dislocation formation is revealed.
  
  Strategies for suppressing the formation of dislocations are proposed.

ABSTRACT

ABSTRACT

Dislocations are ubiquitous in crystalline solids and play a critical role in both material properties and device performance. Due to the numerous variables influencing crystal growth, such as temperature, pressure, and impurity levels, the synthesis of high-quality crystals with minimal defects remains a challenging and enduring goal in crystal research. Calcium fluoride (CaF₂) which is widely used in optical devices typically contains dislocations on the order of 10^-5 cm^-2. The sensitivity of the weak CaF₂ lattice to electron beams makes at atomic-level imaging using traditional scanning transmission electron microscopy difficult. Here, we utilize a combination of characterization methods to analyze the microstructure of dislocations in CaF₂, and the existence of both stored statistical dislocations (SSDs) and geometrically necessary dislocations (GNDs) are identified. SSDs mainly consist of perfect dislocations with a small amount of Frank partial dislocations, while GNDs are predominantly composed of Frank partial dislocations and stacking faults. Based on the calculated formation energies of dislocations and fluorite vacancies, the formation mechanisms of SSDs and GNDs are proposed. The findings in the present study deepen our understanding of the dislocations in CaF₂ and offer insights into strategies to further reduce the defect concentration in CaF₂ crystals.
- CaF₂ single crystal /
- statistically stored dislocation /
- geometrically necessary dislocation /
- iDPC-STEM /
- high-resolution EBSD

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REFERENCES

[1]	Dominguez J. E., Fu L. and Pan X. Q. (2002). Effect of crystal defects on the electrical properties in epitaxial tin dioxide thin films. Appl. Phys. Lett. 81:5168. DOI:10.1063/1.1530745 View in Article CrossRef Google Scholar
[2]	Hwang J. Y., Kim J., Kim H. S., et al. (2018). Effect of dislocation arrays at grain boundaries on electronic transport properties of bismuth antimony telluride: Unified strategy for high thermoelectric performance. Adv. Energy Mater. 8:1800065. DOI:10.1002/aenm.201800065 View in Article CrossRef Google Scholar
[3]	Armstrong M. D., Lan K. W., Guo Y., et al. (2021). Dislocation-mediated conductivity in oxides: Progress, challenges, and opportunities. ACS nano 15:9211. DOI:10.1021/acsnano.1c01557 View in Article CrossRef Google Scholar
[4]	Pratt P. L., Roy C. and Evans A. G. (1966). The role of grain boundaries in the plastic deformation of calcium fluoride. Conference: The role of grain boundaries and surfaces in ceramics. DOI:10.1007/978-1-4899-6311-6_14. View in Article Google Scholar
[5]	Jena D. and Mishra U. K. (2002). Effect of scattering by strain fields surrounding edge dislocations on electron transport in two-dimensional electron gases. Appl. Phys. Lett. 80:64. DOI:10.1063/1.1429758 View in Article CrossRef Google Scholar
[6]	Zhou S., Zhao X., Du P., et al. (2022). Application of patterned sapphire substrate for III-nitride light-emitting diodes. Nanoscale. 14:4887. DOI:10.1039/D1NR08221C View in Article CrossRef Google Scholar
[7]	Moriya K. (1991). Light scattering from defects in crystals: scattering by dislocations. Philos. Mag. B 64:425. DOI:10.1080/13642819108215267 View in Article CrossRef Google Scholar
[8]	Tanikawa T., Ohnishi K., Kanoh M., et al. (2018). Three-dimensional imaging of threading dislocations in GaN crystals using two-photon excitation photoluminescence. Appl. Phys. Express. 11:031004. DOI:10.7567/APEX.11.031004 View in Article CrossRef Google Scholar
[9]	Ben J., Sun X., Jia Y., et al. (2019). Influence of dislocations on the refractive index of AlN by nanoscale strain field. Nanoscale Res. Lett. 14:1. DOI:10.1186/s11671-019-3018-7 View in Article CrossRef Google Scholar
[10]	Hoshikawa K., Huang X., Taishi T., et al. (1999). Dislocation-Free Czochralski Silicon Crystal Growth without the Dislocation-Elimination-Necking Process. J. Appl. Phys. (Japan). 38:L1369. DOI:10.1143/JJAP.38.L1369 View in Article CrossRef Google Scholar
[11]	Yang G., Liu X., Xu L., et al. (2022). Dislocations in 4H silicon carbide single crystals. J. Synth. Cryst. 51:1673. DOI:10.4028/www.scientifc.net/MSF.858.393 View in Article CrossRef Google Scholar
[12]	Manning I., Matsuda Y., Chung G., et al. (2020). Progress in bulk 4H SiC crystal growth for 150 mm wafer production. Conference: MSF. 1004:37. DOI:10.4028/www.scientific.net/MSF.1004.37 View in Article CrossRef Google Scholar
[13]	Wang G., Zhang M., Zuo H., et al. (2007). Dislocation analysis for large-sized sapphire single crystal grown by SAPMAC method. Chinese. J. Struct. Chem. 26:1332. DOI:10.14102/j.cnki.0254-5861.2007.11.023 View in Article CrossRef Google Scholar
[14]	Muzy J., Fivel M., Labor S., et al. (2023). Influence of growth process and crystal defects on sapphire brittleness. J. Cryst. Growth. 618:127327. DOI:10.1016/j.jcrysgro.2023.127327 View in Article CrossRef Google Scholar
[15]	Motzer C. and Reichling M. (2009). High resolution study of etch figures on CaF₂ (111). J. Appl. Phys. 105:064309. DOI:10.1063/1.3078774 View in Article CrossRef Google Scholar
[16]	Abrahams M. S. and Herkart P. G. (1965). Effects of growth parameters on dislocations in CaF₂. J. Appl. Phys. 36:274. DOI:10.1063/1.1713890 View in Article CrossRef Google Scholar
[17]	Bioud Y. A., Boucherif A., Myronov M., et al. (2019). Uprooting defects to enable high-performance III–V optoelectronic devices on silicon. Nat. Commun. 10:4322. DOI:10.1038/s41467-019-12353-9 View in Article CrossRef Google Scholar
[18]	Taylor P. J., Jesser W. A., Benson J. D., et al. (2001). Optoelectronic device performance on reduced threading dislocation density GaAs/Si. J. Appl. Phys. 89:4365. DOI:10.1063/1.1347000 View in Article CrossRef Google Scholar
[19]	Cherns D. (2000). The structure and optoelectronic properties of dislocations in GaN. J. Phys: Condens. Matter. 12:10205. DOI:10.1088/0953-8984/12/49/320 View in Article CrossRef Google Scholar
[20]	Fahey P. M., Mader S. R., Stiffler S. R., et al. (1992). Stress-induced dislocations in silicon integrated circuits. IBM J. Res. Dev. 36:158. DOI:10.1147/rd.362.0158 View in Article CrossRef Google Scholar
[21]	Kittler M. and Reiche M. (2009). Dislocations as active components in novel silicon devices. Adv. Eng. Mater. 11:249. DOI:10.1002/adem.200800283 View in Article CrossRef Google Scholar
[22]	Evans A. G. and Pratt P. L. (1969). Dislocations in the fluorite structure. Philos. Mag. 20:1213. DOI:10.1080/14786436908228207 View in Article CrossRef Google Scholar
[23]	Keig G. A. and Coble R. L. (1968). Mobility of edge dislocations in single-crystal calcium fluoride. J. Appl. Phys. 39:6090. DOI:10.1063/1.1656121 View in Article CrossRef Google Scholar
[24]	Katz R. N. and Coble R. L. (1974). Effect of neodymium on dislocation velocity in CaF2. J. Appl. Phys. 45:2382. DOI:10.1063/1.1663601 View in Article CrossRef Google Scholar
[25]	Sadrabadi P., Eisenlohr P., Wehrhan G., et al. (2009). Evolution of dislocation structure and deformation resistance in creep exemplified on single crystals of CaF₂. Mater. Sci. Eng. A. 510:46. DOI:10.1016/j.msea.2008.04.086 View in Article CrossRef Google Scholar
[26]	Motzer C. and Reichling M. (2010). Morphological classification and quantitative analysis of etch pits. J. Appl. Phys. 108:113523. DOI:10.1063/1.3510535 View in Article CrossRef Google Scholar
[27]	Kuhlmann-Wilsdorf D. (1989). Theory of plastic deformation:-properties of low energy dislocation structures. Mater. Sci. Eng. A 113:1. DOI:10.1016/0921-5093(89)90290-6 View in Article CrossRef Google Scholar
[28]	Tao N. R., Wang Z. B., Tong W. P., et al. (2002). An investigation of surface nanocrystallization mechanism in Fe induced by surface mechanical attrition treatment. Acta Mater. 50:4603. DOI:10.1016/S1359-6454(02)00310-5 View in Article CrossRef Google Scholar
[29]	Landau P., Shneck R., Makov G., et al. (2009). Evolution of dislocation patterns in fcc metals. Conference: IOP Conf. Ser. Mater. Sci. Eng. 3:012004. DOI:10.1088/1757-899X/3/1/012004 View in Article CrossRef Google Scholar
[30]	Wu X., Tao, N., Hong Y., et al. (2002). Microstructure and evolution of mechanically-induced ultrafine grain in surface layer of AL-alloy subjected to USSP. Acta Mater. 50:2075. DOI:10.1016/S1359-6454(02)00051-4 View in Article CrossRef Google Scholar
[31]	Tang C., Wan W., Huang L., et al. (2022). On the formation and multiplicity of Si [001] small angle symmetric Tilt grain boundaries: Atomistic simulation of directional growth. Cryst. Growth Des. 22:7491. DOI:10.1021/acs.cgd.2c01046 View in Article CrossRef Google Scholar
[32]	Rolland P., Dicks K. and Ravel-Chapuis R. (2002). EBSD spatial resolution in the SEM when analyzing small grains or deformed material. Microsc. Microanal. 8:670. DOI:10.1017/S1431927602106350 View in Article CrossRef Google Scholar
[33]	Lehto P. (2021). Adaptive domain misorientation approach for the EBSD measurement of deformation induced dislocation sub-structures. Ultramicroscopy. 222:113203. DOI:10.1016/j.ultramic.2021.113203 View in Article CrossRef Google Scholar
[34]	Sadrabadi P., Durst K., Göken M., et al. (2009). Quantification of dislocation structures at high resolution by atomic force microscopy of dislocation etch pits. Philos. Mag. Lett. 89:391. DOI:10.1080/09500830902984554 View in Article CrossRef Google Scholar
[35]	Wang Y., Brodusch N., Gauvin R., et al. (2022). Line-rotated remapping for high-resolution electron backscatter diffraction. Ultramicroscopy. 242:113623. DOI:10.1016/j.ultramic.2022.113623 View in Article CrossRef Google Scholar
[36]	Murr L. E. (1974). Transmission electron microscope study of crystal defects in natural fluorite. Phys. Status. Solidi. A 22:239. DOI:10.1002/pssa.2210220128 View in Article CrossRef Google Scholar
[37]	Chadderton L. T., Johnson E. and Wohlenberg T. (1976). Observations of a regular void array in natural fluorite irradiated with 100 keV electrons. Phys. Scr. 13:127. DOI:10.1088/0031-8949/13/2/012 View in Article CrossRef Google Scholar
[38]	Karlušić M., Ghica C., Negrea R. F., et al. (2017). On the threshold for ion track formation in CaF2. New J. Phys. 19:023023. DOI:10.1088/1367-2630/aa5914 View in Article CrossRef Google Scholar
[39]	Lazić I. and Bosch, E. G. (2017). Analytical review of direct STEM imaging techniques for thin samples. Adv. Imaging Electron Phys. 199:75. DOI:10.1016/bs.aiep.2017.01.006 View in Article CrossRef Google Scholar
[40]	Bosch E. G. and Lazić I. (2015). Analysis of HR-STEM theory for thin specimen. Ultramicroscopy. 156:59. DOI:10.1016/j.ultramic.2015.02.004 View in Article CrossRef Google Scholar
[41]	Krivanek O. L., Chisholm M. F., Nicolosi, V. et al. (2010). Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy. Nature. 464:571. DOI:10.1038/nature08879 View in Article CrossRef Google Scholar
[42]	Yücelen E. Lazić I. and Bosch E. G. T. (2018). Phase contrast scanning transmission electron microscopy imaging of light and heavy atoms at the limit of contrast and resolution. Sci. Rep. 8:2676. DOI:10.1038/s41598-018-20377-2 View in Article CrossRef Google Scholar
[43]	Ma Y., Cai D., Li Y., et al. (2016). The influence of straight pore blockage on the selectivity of methanol to aromatics in nanosized Zn/ZSM-5: An atomic Cs-corrected STEM analysis study. RSC Adv. 6:74797. DOI:10.1039/C6RA19073A View in Article CrossRef Google Scholar
[44]	Shen B., Chen X., Shen K., et al. (2020). Imaging the node-linker coordination in the bulk and local structures of metal-organic frameworks. Nat. Commun. 11:2692. DOI:10.1038/s41467-020-16531-y View in Article CrossRef Google Scholar
[45]	Shen B., Wang H., Xiong H., et al. (2022). Atomic imaging of zeolite-confined single molecules by electron microscopy. Nature. 607:703. DOI:10.1038/s41586-022-04876-x View in Article CrossRef Google Scholar
[46]	Bhattacharjee S., Chen C. and Ahn W. S. (2014). Chromium terephthalate metal–organic framework MIL-101: synthesis, functionalization, and applications for adsorption and catalysis. RSC Adv. 4:52500. DOI:10.1039/C4RA11259H View in Article CrossRef Google Scholar
[47]	Ma M., Zhang X., Chen X., et al. (2023). In situ imaging of the atomic phase transition dynamics in metal halide perovskites. Nat. Commun. 14:7142. DOI:10.1038/s41467-023-42999-5 View in Article CrossRef Google Scholar
[48]	Liu B., Chen X., Huang N., et al. (2023). Imaging the dynamic influence of functional groups on metal-organic frameworks. Nat. Commun. 14:4835. DOI:10.1038/s41467-023-40590-6 View in Article CrossRef Google Scholar
[49]	Zhang H., Li G., Zhang J., et al. (2023). Three-dimensional inhomogeneity of zeolite structure and composition revealed by electron ptychography. Science. 380:633. DOI:10.1126/science.adg3183 View in Article CrossRef Google Scholar
[50]	Hohenberg P. and Kohn W. (1964). Inhomogeneous Electron Gas. Phys. Rev. 136:B864. DOI:10.1103/PhysRev.136.B864 View in Article CrossRef Google Scholar
[51]	Kresse G. and Furthmüller J. (1996). Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B. 54:11169. DOI:10.1103/PhysRevB.54.11169 View in Article CrossRef Google Scholar
[52]	Kresse G. and Hafner J. (1993). Ab initio molecular dynamics for liquid metals. Phys. Rev. B. 47:558. DOI:10.1103/PhysRevB.47.558 View in Article CrossRef Google Scholar
[53]	Kresse G. and Hafner J. (1994). Ab initio molecular-dynamics simulation of the liquid-metal--amorphous-semiconductor transition in germanium. Phys. Rev. B 49:14251. DOI:10.1103/PhysRevB.49.14251. View in Article Google Scholar
[54]	Kresse G. and Furthmüller J. (1996). Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6:15. DOI:10.1016/0927-0256(96)00008-0 View in Article CrossRef Google Scholar
[55]	Blöchl P. E. (1994). Projector augmented-wave method. Phys. Rev. B 50:17953. DOI:10.1103/PhysRevB.50.17953 View in Article CrossRef Google Scholar
[56]	Perdew J. P., Burke K. and Wang Y. (1996). Generalized gradient approximation for the exchange-correlation hole of a many-electron system. Phys. Rev. B 54:16533. DOI:10.1103/PhysRevB.54.16533 View in Article CrossRef Google Scholar
[57]	Perdew J. P., Ruzsinszky A., Csonka G. I., et al. (2008). Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces. Phys. Rev. Lett. 100:136406. DOI:10.1103/PhysRevLett.100.136406 View in Article CrossRef Google Scholar
[58]	Monkhorst H. J. and Pack J. D. (1976). Special points for Brillouin-zone integrations. Phys. Rev. B. 13:5188. DOI:10.1103/PhysRevB.13.5188 View in Article CrossRef Google Scholar
[59]	Blumenau A. T., Heggie M. I., Fall C. J., et al. (2002). Dislocations in diamond: Core structures and energies. Phys. Rev. B. 65:205205. DOI:10.1103/PhysRevB.65.205205 View in Article CrossRef Google Scholar
[60]	Hÿtch M. J., Putaux J. L. and Pénisson J. M. (2003). Measurement of the displacement field of dislocations to 0.03 Å by electron microscopy. Nature. 423:270. DOI:10.1038/nature01638. View in Article Google Scholar
[61]	Pennycook and Stephen J. (2009). Transmission electron microscopy: A textbook for materials science, Second Edition. Willianms D. B. and Carter C. B. (Springer). DOI:10.1017/S1431927609991140. View in Article Google Scholar
[62]	Bishara H., Lee S., Brink T., et al. (2021). Understanding grain boundary electrical resistivity in Cu: the effect of boundary structure. ACS nano. 15:16607. DOI:10.1021/acsnano.1c06367 View in Article CrossRef Google Scholar
[63]	Recker K. and Leckebusch R. (1971). Zur Züchtung von CaF₂-UND CaF₂ (U)-einkristallen aus der dampfphase. J. Cryst. Growth. 9:274. DOI:10.1016/0022-0248(71)90242-9 View in Article CrossRef Google Scholar
[64]	Bollmann W. (1980). Incorporation of O₂^- and OH^- ions in CaF₂ crystals by reaction with the surrounding atmosphere. Phys. Status. Solidi. A 57:601. DOI:10.1002/pssa.2210570217 View in Article CrossRef Google Scholar
[65]	Cockayne B., Robertson D. S. and Straughan B. W. (1964). Calcium fluoride: slip and polygonization during crystal growth. Nature. 203:1376. DOI:10.1038/2031376a0 View in Article CrossRef Google Scholar
[66]	Zou J., Fauler A., Senchenkov A. S., et al. (2021). Characterization of structural defects in (Cd, Zn) Te crystals grown by the travelling heater method. Crystals 11:1402. DOI:10.3390/cryst11111402 View in Article CrossRef Google Scholar
[67]	Kishan Rao K. and Sirdeshmukh D. B. (1990). Indentation studies on alkaline earth fluoride crystals at elevated temperatures. Pramana. 34:151. DOI:10.1007/BF02847199 View in Article CrossRef Google Scholar

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Li S., Wang Y., Zhang B., et al. (2025). Revealing the atomic-scale structures of dislocations in calcium fluoride single crystal. The Innovation Materials 3:100129. https://doi.org/10.59717/j.xinn-mater.2025.100129

Li S., Wang Y., Zhang B., et al. (2025). Revealing the atomic-scale structures of dislocations in calcium fluoride single crystal. The Innovation Materials 3:100129. https://doi.org/10.59717/j.xinn-mater.2025.100129

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Revealing the atomic-scale structures of dislocations in calcium fluoride single crystal

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Revealing the atomic-scale structures of dislocations in calcium fluoride single crystal

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