{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,27]],"date-time":"2026-06-27T03:48:40Z","timestamp":1782532120532,"version":"3.54.5"},"reference-count":19,"publisher":"MDPI AG","issue":"20","license":[{"start":{"date-parts":[[2025,10,15]],"date-time":"2025-10-15T00:00:00Z","timestamp":1760486400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Nanomaterials"],"abstract":"<jats:p>We present a study based on first-principles calculations of the vibrational and spectroscopic properties of four types of layered boron nitride (BN) polymorphs: e-BN (AA), h-BN (AA\u2032), r-BN (ABC), and b-BN (AB). By using density functional perturbation theory with van der Waals corrections, we calculate phonon frequencies and Raman\/infrared (IR) activities at the \u0393 point and extract specific spectral fingerprints for each stack. In e-BN, we observe a sharp, isolated high-frequency E\u2032 mode at 1420.9cm\u22121 that is active in both Raman and IR. For h-BN, the characteristic Raman E2g line occurs at 1415.5cm\u22121. The out-of-plane IR-active A2u branch shows a mid-frequency TO\/LO pair at 673.5\/806.6cm\u22121, which closely matches experimental results. Rhombohedral r-BN has a strong, coincident Raman\/IR high-frequency feature (E) at 1418.5cm\u22121, along with a large IR LO partner at 1647.3cm\u22121, consistent with observed Raman and IR signatures. Bernal b-BN displays the most complicated pattern. It combines a robust mid-frequency A2\u2033 pair (TO\/LO at 697.9\/803.5cm\u22121) with multiple high-frequency E\u2032 modes (TO near 1416.9 and 1428.1cm\u22121, each with LO counterparts). These stack-dependent Raman and IR fingerprints match existing experimental data for h-BN and r-BN and provide clear predictions for e-BN and b-BN. The results offer a consistent framework for identifying and interpreting vibrational spectra in layered sp2 boron nitride and related materials.<\/jats:p>","DOI":"10.3390\/nano15201567","type":"journal-article","created":{"date-parts":[[2025,10,15]],"date-time":"2025-10-15T11:57:42Z","timestamp":1760529462000},"page":"1567","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Raman and Infrared Signatures of Layered Boron Nitride Polytypes: A First-Principles Study"],"prefix":"10.3390","volume":"15","author":[{"ORCID":"https:\/\/orcid.org\/0009-0006-1739-6007","authenticated-orcid":false,"given":"Priyanka","family":"Mishra","sequence":"first","affiliation":[{"name":"Faculty of Physics, University of Warsaw, Pasteura 5, PL-02093 Warsaw, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0518-844X","authenticated-orcid":false,"given":"Nevill","family":"Gonzalez Szwacki","sequence":"additional","affiliation":[{"name":"Faculty of Physics, University of Warsaw, Pasteura 5, PL-02093 Warsaw, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2025,10,15]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"2000058","DOI":"10.1002\/advs.202000058","article-title":"2D Material Optoelectronics for Information Functional Device Applications: Status and Challenges","volume":"7","author":"Tan","year":"2020","journal-title":"Adv. Sci."},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Gil, B., Desrat, W., Rousseau, A., Elias, C., Valvin, P., Moret, M., Li, J., Janzen, E., Edgar, J.H., and Cassabois, G. (2022). Polytypes of sp2-Bonded Boron Nitride. Crystals, 12.","DOI":"10.3390\/cryst12060782"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"21101","DOI":"10.1021\/acs.jpcc.2c06895","article-title":"Rhombohedral and Turbostratic Boron Nitride Polytypes Investigated by X-ray Absorption Spectroscopy","volume":"126","author":"Olovsson","year":"2022","journal-title":"J. Phys. Chem. C"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"104102","DOI":"10.1103\/PhysRevB.68.104102","article-title":"Structural and electronic properties ofh-BN","volume":"68","author":"Liu","year":"2003","journal-title":"Phys. Rev. B"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"021006","DOI":"10.1088\/2053-1583\/ab0e24","article-title":"Alternative stacking sequences in hexagonal boron nitride","volume":"6","author":"Gilbert","year":"2019","journal-title":"2D Mater."},{"key":"ref_6","first-page":"115","article-title":"Toward accurate modeling of structure and energetics of bulk hexagonal boron nitride","volume":"45","year":"2023","journal-title":"J. Comput. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"924","DOI":"10.1134\/1.1187516","article-title":"Normal lattice vibrations and the crystal structure of anisotropic modifications of boron nitride","volume":"32","author":"Ordin","year":"1998","journal-title":"Semiconductors"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"eaau5832","DOI":"10.1126\/sciadv.aau5832","article-title":"Polymorphism of bulk boron nitride","volume":"5","author":"Cazorla","year":"2019","journal-title":"Sci. Adv."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"6000","DOI":"10.1021\/acs.jpcc.1c10943","article-title":"Diffusion Monte Carlo Study on Relative Stabilities of Boron Nitride Polymorphs","volume":"126","author":"Nikaido","year":"2022","journal-title":"J. Phys. Chem. C"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"e25925","DOI":"10.1002\/qua.25925","article-title":"Exploring point defects in hexagonal boron-nitrogen monolayers","volume":"119","author":"Korona","year":"2019","journal-title":"Int. J. Quantum Chem."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"036104","DOI":"10.1103\/PhysRevLett.111.036104","article-title":"Stacking in Bulk and Bilayer Hexagonal Boron Nitride","volume":"111","author":"Constantinescu","year":"2013","journal-title":"Phys. Rev. Lett."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"72","DOI":"10.1038\/s41699-024-00511-7","article-title":"Revealing polytypism in 2D boron nitride with UV photoluminescence","volume":"8","author":"Korona","year":"2024","journal-title":"NPJ 2D Mater. Appl."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"9864","DOI":"10.1039\/D3NR00578J","article-title":"Growth temperature induced changes of luminescence in epitaxial BN: From colour centres to donor\u2013acceptor recombination","volume":"15","author":"Korona","year":"2023","journal-title":"Nanoscale"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"934","DOI":"10.1002\/jcc.21112","article-title":"Role and effective treatment of dispersive forces in materials: Polyethylene and graphite crystals as test cases","volume":"30","author":"Barone","year":"2009","journal-title":"J. Comput. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"297","DOI":"10.1016\/j.physb.2007.08.012","article-title":"First principles study of structural and electronic properties of different phases of boron nitride","volume":"400","author":"Ahmed","year":"2007","journal-title":"Phys. B Condens. Matter"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"39","DOI":"10.1016\/j.cpc.2018.01.012","article-title":"The PseudoDojo: Training and grading a 85 element optimized norm-conserving pseudopotential table","volume":"226","author":"Giantomassi","year":"2018","journal-title":"Comput. Phys. Commun."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"543","DOI":"10.1103\/PhysRev.146.543","article-title":"Normal Modes in Hexagonal Boron Nitride","volume":"146","author":"Geick","year":"1966","journal-title":"Phys. Rev."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"23031","DOI":"10.1364\/OE.26.023031","article-title":"Effect of growth temperature on the structural and optical properties of few-layer hexagonal boron nitride by molecular beam epitaxy","volume":"26","author":"Laleyan","year":"2018","journal-title":"Opt. Express"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"2756","DOI":"10.1021\/acsnano.1c09717","article-title":"Bernal Boron Nitride Crystals Identified by Deep-Ultraviolet Cryomicroscopy","volume":"16","author":"Rousseau","year":"2022","journal-title":"ACS Nano"}],"container-title":["Nanomaterials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2079-4991\/15\/20\/1567\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,15]],"date-time":"2025-10-15T12:28:45Z","timestamp":1760531325000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2079-4991\/15\/20\/1567"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,10,15]]},"references-count":19,"journal-issue":{"issue":"20","published-online":{"date-parts":[[2025,10]]}},"alternative-id":["nano15201567"],"URL":"https:\/\/doi.org\/10.3390\/nano15201567","relation":{},"ISSN":["2079-4991"],"issn-type":[{"value":"2079-4991","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,10,15]]}}}