Shaping terahertz waves using anisotropic shear modes in a van der Waals mineral
Source abstract
Abstract
The interlayer interactions in van der Waals (vdW) materials are imprinted in their low-frequency rigid-layer phonon spectra. Investigating the symmetries of these phonon modes offers a pathway to generate optical anisotropy in the terahertz range. Here, we employ polarization-sensitive terahertz time-domain spectroscopy to study a sample of clinochlore, a naturally abundant, large bandgap vdW mineral. Our measurements revealed a pronounced anisotropic feature in the complex refractive index spectrum near 1.13 THz, consistent with shear modes predicted by our density-functional perturbation theory that accounts for impurities in the mineral. Polarimetry analysis revealed that this shear phonon anisotropy reshapes the polarization state of transmitted terahertz waves, inducing both Faraday rotation and ellipticity. Furthermore, we applied Jones formalism to interpret the phononic symmetries and describe our observations in terms of its polarization eigenstates. These results highlight the potential of exploring vdW minerals as central building blocks for vdW heterostructures with compelling technological applications.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Acoustic Wave Resonator Technologies · Photonic Crystals and Applications · Terahertz technology and applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (58)
Show source-provided references
1. Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).10.1126/science.1102896 ↗
2. Frisenda, R., Niu, Y., Gant, P., Muñoz, M. & Castellanos-Gomez, A. Naturally occurring van der waals materials. npj 2D Mater. Appl. 4, 38 (2020).10.1038/s41699-020-00172-2 ↗
3. Ajayan, P., Kim, P. & Banerjee, K. Two-dimensional van der waals materials. Phys. Today 69, 38–44 (2016).10.1063/PT.3.3297 ↗
4. Islam, M. A. et al. Exfoliation mechanisms of 2d materials and their applications. Appl. Phys. Rev. 9, 041301 (2022).10.1063/5.0090717 ↗
5. Geim, A. K. & Grigorieva, I. V. Van der waals heterostructures. Nature 499, 419–425 (2013).10.1038/nature12385 ↗
6. Liu, Y. et al. Van der waals heterostructures and devices. Nat. Rev. Mater. 1, 16042 (2016).10.1038/natrevmats.2016.42 ↗
7. Castellanos-Gomez, A. et al. Van der waals heterostructures. Nat. Rev. Methods Prim. 2, 58 (2022).10.1038/s43586-022-00139-1 ↗
8. Dasgupta, A., Yang, X. & Gao, J. Naturally occurring van der waals heterostructure lengenbachite with strong in-plane structural and optical anisotropy. npj 2D Mater. Appl. 5, 88 (2021).10.1038/s41699-021-00271-8 ↗
9. Tripathi, R. P. N., Gao, J. & Yang, X. Natural layered mercury antimony sulfosalt livingstonite with anisotropic optical properties. Opt. Express 30, 19611–19628 (2022).10.1364/OE.458576 ↗
10. Dasgupta, A., Yang, X. & Gao, J. Natural 2d layered mineral cannizzarite with anisotropic optical responses. Sci. Rep. 12, 10006 (2022).10.1038/s41598-022-14046-8 ↗
11. Dasgupta, A., Belakovskiy, D. I., Chaplygin, I. V., Gao, J. & Yang, X. Large in-plane vibrational and optical anisotropy in natural 2d heterostructure abramovite. Sci. Rep. 12, 16803 (2022).10.1038/s41598-022-21042-5 ↗
12. Bindi, L. et al. Misfit-generated structural and optical anisotropies of the natural mos2−PbS van der waals heterostructure merelaniite. Phys. Rev. Mater. 6, 115202 (2022).10.1103/PhysRevMaterials.6.115202 ↗
13. Slavich, A. S. et al. Exploring van der waals materials with high anisotropy: geometrical and optical approaches. Light Sci. Appl. 13, 68 (2024).10.1038/s41377-024-01407-3 ↗
14. de Oliveira, R. et al. High throughput investigation of an emergent and naturally abundant 2d material: clinochlore. Appl. Surf. Sci. 599, 153959 (2022).10.1016/j.apsusc.2022.153959 ↗
15. De Oliveira, R., Cadore, A. R., Freitas, R. O. & Barcelos, I. D. Review on infrared nanospectroscopy of natural 2d phyllosilicates. J. Opt. Soc. Am. A 40, C157 (2023).10.1364/JOSAA.482518 ↗
16. Spinnler, G. E., Self, P. G., Iijima, S. & Buseck, P. R. Stacking disorder in clinochlore chlorite. Am. Min. 69, 252–263 (1984).
17. Ulian, G., Moro, D. & Valdrè, G. Infrared and raman spectroscopic features of clinochlore mg6si4o10(oh)8: a density functional theory contribution. Appl. Clay Sci. 197, 105779 (2020).10.1016/j.clay.2020.105779 ↗
18. Zallen, R. & Slade, M. Rigid-layer modes in chalcogenide crystals. Phys. Rev. B 9, 1627–1637 (1974).10.1103/PhysRevB.9.1627 ↗
19. Longuinhos, R. & Ribeiro-Soares, J. Ultra-weak interlayer coupling in two-dimensional gallium selenide. Phys. Chem. Chem. Phys. 18, 25401–25408 (2016).10.1039/C6CP03806A ↗
20. Longuinhos Monteiro Lobato, R. et al. Thickness dependence of wavenumbers and optical-activity selection rule of zone-center phonons in two-dimensional gallium sulfide metal monochalcogenide. Phys. Chem. Chem. Phys. 26, 27260–27269 (2024).10.1039/D4CP02695K ↗
21. Longuinhos, R. et al. Raman spectrum of layered jacutingaite (pt2hgse3) crystals-experimental and theoretical study. J. Raman Spectrosc. 51, 357–365 (2020).10.1002/jrs.5764 ↗
22. Longuinhos, R., Vymazalová, A., Cabral, A. R. & Ribeiro-Soares, J. Raman spectrum of layered tilkerodeite (pd2hgse3) topological insulator: the palladium analogue of jacutingaite (pt2hgse3). J. Phys. Condens. Matter 33, 065401 (2021).10.1088/1361-648X/abc35a ↗
23. Longuinhos Monteiro Lobato, R. & Ribeiro-Soares, J. Mechanical properties of layered tilkerodeite (pd2hgse3) and jacutingaite (pt2hgse3) crystals: insights on the interlayer, intralayer interactions, and phonons. J. Appl. Phys. 130, 015105 (2021).10.1063/5.0053171 ↗
24. Longuinhos, R. et al. Raman and far-infrared synchrotron nanospectroscopy of layered crystalline talc: vibrational properties, interlayer coupling, and symmetry crossover. J. Phys. Chem. C. 127, 5876–5885 (2023).10.1021/acs.jpcc.3c00017 ↗
25. Gasanly, N. M. et al. Davydov splitting and rigid-layer modes in InS crystal. Solid State Commun. 42, 843–845 (1982).10.1016/0038-1098(82)90221-6 ↗
26. Nakashima, S., Daimon, M. & Mitsuishi, A. Rigid layer modes and van der waals interactions in cdi2-cdbr2 mixed layer compounds. J. Phys. Chem. Solids 40, 39–44 (1979).10.1016/0022-3697(79)90092-1 ↗
27. Ulian, G., Moro, D. & Valdrè, G. Simulated infrared and raman spectroscopy, complex dielectric function and refractive index dataset of monoclinic c2/m stoichiometric clinochlore mg6si4o10(oh)8 as obtained from density functional theory. Data Brief. 32, 106208 (2020).10.1016/j.dib.2020.106208 ↗
28. Koch, M., Mittleman, D. M., Ornik, J. & Castro-Camus, E. Terahertz time-domain spectroscopy. Nat. Rev. Methods Prim. 3, 48 (2023).10.1038/s43586-023-00232-z ↗
29. Kawahala, N. M. et al. Thickness-dependent terahertz permittivity of epitaxially grown pbte thin films. Coatings 13, 1855 (2023).10.3390/coatings13111855 ↗
30. Norris, T., Cheng, G., Choi, W. J., Jang, H.-J. & Kotov, N. A. Terahertz time-domain polarimetry for generalized anistropic and chiral materials. In Terahertz, RF, Millimeter, and Submillimeter-Wave Technology and Applications XII (eds Sadwick, L. P. & Yang, T.) (SPIE, 2019).10.1117/12.2516383 ↗
31. Menzel, C., Rockstuhl, C. & Lederer, F. Advanced jones calculus for the classification of periodic metamaterials. Phys. Rev. A 82, 053811 (2010).10.1103/PhysRevA.82.053811 ↗
32. de Oliveira, R. et al. Water nanochannels in ultrathin clinochlore phyllosilicate mineral with ice-like behavior. J. Phys. Chem. C. 128, 14388–14398 (2024).10.1021/acs.jpcc.4c02170 ↗
33. Deer, W. A., Howie, R. A. & Zussman, J. An Introduction to the Rock-Forming Minerals (Mineralogical Society of Great Britain and Ireland, 2013).10.1180/DHZ ↗
34. Moro, D., Ulian, G. & Valdrè, G. Nanoscale cross-correlated afm, kelvin probe, elastic modulus and quantum mechanics investigation of clay mineral surfaces: the case of chlorite. Appl. Clay Sci. 131, 175–181 (2016).10.1016/j.clay.2015.11.023 ↗
35. Gopal, N. O., Narasimhulu, K. V. & Lakshmana Rao, J. Optical absorption, epr, infrared and raman spectral studies of clinochlore mineral. J. Phys. Chem. Solids 65, 1887–1893 (2004).10.1016/j.jpcs.2004.07.003 ↗
36. See Supplemental Information for details on the experimental methods, coefficients extraction, fits and temperature dependence of the THz-TDS data, and details of the density functional perturbation theory calculations.
37. Morikawa, O. et al. Faraday ellipticity and faraday rotation of a doped-silicon wafer studied by terahertz time-domain spectroscopy. J. Appl. Phys. 100, 033105 (2006).10.1063/1.2219981 ↗
38. Neu, J. & Schmuttenmaer, C. A. Tutorial: an introduction to terahertz time domain spectroscopy (thz-tds). J. Appl. Phys. 124, 231101 (2018).10.1063/1.5047659 ↗
39. Fox, M. Optical properties of solids 2nd edn (Oxford Univ. Press, 2010).
40. Li, X. et al. Terahertz faraday and kerr rotation spectroscopy of bi1−xsbx films in high magnetic fields up to 30 tesla. Phys. Rev. B 100, 115145 (2019).10.1103/PhysRevB.100.115145 ↗
41. Han, D., Jeong, H., Song, Y., Ahn, J. S. & Ahn, J. Lattice vibrations of natural seraphinite gemstone probed by terahertz time-domain spectroscopy. IEEE Trans. Terahertz Sci. Technol. 5, 1021–1027 (2015).10.1109/TTHZ.2015.2464087 ↗
42. Cheng, B., Taylor, P., Folkes, P., Rong, C. & Armitage, N. Magnetoterahertz response and faraday rotation from massive dirac fermions in the topological crystalline insulator $${{\rm{pb}}}0.5{{\rm{sn}}}0.5{\rm{Te}}$$. Phys. Rev. Lett. 122, 097401 (2019).10.1103/PhysRevLett.122.097401 ↗
43. Hernandez, F. G. G. et al. Observation of interplay between phonon chirality and electronic band topology. Sci. Adv. 9, eadj4074 (2023).10.1126/sciadv.adj4074 ↗
44. Fowles, G. R. Introduction to Modern Optics 2nd edn (Dover Publications, 1989).
45. Armitage, N. P. Constraints on jones transmission matrices from time-reversal invariance and discrete spatial symmetries. Phys. Rev. B 90, 035135 (2014).10.1103/PhysRevB.90.035135 ↗
46. Vernon, R. J. & Huggins, B. D. Extension of the jones matrix formalism to reflection problems and magnetic materials. J. Opt. Soc. Am. 70, 1364–1370 (1980).10.1364/JOSA.70.001364 ↗
47. Voronin, K. V. et al. Chiral photonic super-crystals based on helical van der waals homostructures. Laser Photonics Rev. 18, 2301113 (2024).10.1002/lpor.202301113 ↗
48. Voronin, K. V. et al. Programmable carbon nanotube networks: controlling optical properties through orientation and interaction. Adv. Sci. 11, 2404694 (2024).10.1002/advs.202404694 ↗
49. Hohenberg, P. & Kohn, W. Inhomogeneous electron gas. Phys. Rev. 136, B864–B871 (1964).10.1103/PhysRev.136.B864 ↗
50. Kohn, W. & Sham, L. J. Self-consistent equations including exchange and correlation effects. Phys. Rev. 140, A1133–A1138 (1965).10.1103/PhysRev.140.A1133 ↗
51. Baroni, S., De Gironcoli, S., Dal Corso, A. & Giannozzi, P. Phonons and related crystal properties from density-functional perturbation theory. Rev. Mod. Phys. 73, 515–562 (2001).10.1103/RevModPhys.73.515 ↗
52. Giannozzi, P. et al. Quantum espresso: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).10.1088/0953-8984/21/39/395502 ↗
53. Giannozzi, P. et al. Advanced capabilities for materials modelling with quantum espresso. J. Phys. Condens. Matter 29, 465901 (2017).10.1088/1361-648X/aa8f79 ↗
54. Perdew, J. P. et al. Restoring the density-gradient expansion for exchange in solids and surfaces. Phys. Rev. Lett. 100, 136406 (2008).10.1103/PhysRevLett.100.136406 ↗
55. Van Setten, M. et al. The pseudodojo: training and grading a 85 element optimized norm-conserving pseudopotential table. Comput. Phys. Commun. 226, 39–54 (2018).10.1016/j.cpc.2018.01.012 ↗
56. Hamann, D. R. Optimized norm-conserving vanderbilt pseudopotentials. Phys. Rev. B 88, 085117 (2013).10.1103/PhysRevB.88.085117 ↗
57. Monkhorst, H. J. & Pack, J. D. Special points for brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).10.1103/PhysRevB.13.5188 ↗
58. Marzari, N., Vanderbilt, D., De Vita, A. & Payne, M. C. Thermal contraction and disordering of the al(110) surface. Phys. Rev. Lett. 82, 3296–3299 (1999).10.1103/PhysRevLett.82.3296 ↗