Intercalation induced quasi-freestanding layer in TiSe2

Yilmaz, Turgut; Ng, Yi Sheng; Rajapitamahuni, Anil; Kundu, Asish; Wang, Hui-Qiong; Zheng, Jin-Cheng; Vescovo, Elio

doi:10.1103/jvm3-l8d2

Intercalation induced quasi-freestanding layer in TiSe₂

Journal Article · Fri Aug 08 04:00:00 EDT 2025 · Physical Review B

DOI:https://doi.org/10.1103/jvm3-l8d2· OSTI ID:2589358

^[1]; ^[2]; Rajapitamahuni, Anil ^[3]; Kundu, Asish ^[3]; ^[4]; ^[4]; ^[3]

Xiamen Univ. Malaysia, Sepeng (Malaysia); Univ. of Connecticut, Storrs, CT (United States)
Xiamen Univ. Malaysia, Sepeng (Malaysia)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Xiamen Univ. (China); Xiamen Univ. Malaysia, Sepeng (Malaysia)

Angle-resolved photoemission spectroscopy is employed to study the electronic structure of bulk TiSe₂ before and after doping with potassium impurities. A splitting in the conduction band into two branches is observed after room-temperature deposition. The splitting energy increases to approximately 130 meV when the sample is cooled to 40 K. One branch exhibits a nondispersive two-dimensional feature, while the other shows the characteristics of three-dimensional bulk band dispersion. Core-level spectroscopy suggests that the K impurities predominantly occupy the intercalated sites within the van der Waals gap. Furthermore, the results indicate the formation of a quasi-freestanding TiSe₂ layer. Additionally, doping completely suppresses the periodic lattice distortion in the surface region. These findings are further supported by density functional theory calculations, which compare the band structure of monolayer and bulk TiSe₂ with experimental data. Thus, the dimensional and intrinsic electronic properties of 1⁢𝑇−TiSe₂ can be controlled through the intercalation procedure used in this work.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); Xiamen University Malaysia

Grant/Contract Number:: SC0012704

OSTI ID:: 2589358

Report Number(s):: BNL--228953-2025-JAAM

Journal Information:: Physical Review B, Journal Name: Physical Review B Journal Issue: 8 Vol. 112; ISSN 2469-9950; ISSN 2469-9969

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (52)

K⁺ Induced Phase Transformation of Layered Titanium Disulfide Boosts Ultrafast Potassium‐Ion Storage Zhang, Xiao; Zhu, Hezhen; He, Qiu Advanced Functional Materials, Vol. 32, Issue 39 https://doi.org/10.1002/adfm.202205330	journal	July 2022
Controlling the Charge Density Wave Transition in Monolayer TiSe ₂ : Substrate and Doping Effects Kolekar, Sadhu; Bonilla, Manuel; Diaz, Horacio Coy Advanced Quantum Technologies, Vol. 1, Issue 3 https://doi.org/10.1002/qute.201800070	journal	October 2018
Concerning the semimetallic characters of TiS2 and TiSe2 Wilson, John A. Solid State Communications, Vol. 22, Issue 9 https://doi.org/10.1016/0038-1098(77)90133-8	journal	June 1977
Atomic subshell photoionization cross sections and asymmetry parameters: 1 ⩽ Z ⩽ 103 Yeh, J. J.; Lindau, I. Atomic Data and Nuclear Data Tables, Vol. 32, Issue 1 https://doi.org/10.1016/0092-640X(85)90016-6	journal	January 1985
Exchange reaction between intercalated Na and K studied by synchrotron radiation Starnberg, H. I.; Brauer, H. E.; Hughes, H. P. Surface Science, Vol. 377-379 https://doi.org/10.1016/S0039-6028(96)01513-0	journal	April 1997
Molybdenum chalcogenides based anode materials for alkali metal ions batteries: Beyond lithium ion batteries Zhou, Yanli; Han, Qi; Liu, Yan Energy Storage Materials, Vol. 50 https://doi.org/10.1016/j.ensm.2022.05.031	journal	September 2022
Recent development of two-dimensional transition metal dichalcogenides and their applications Choi, Wonbong; Choudhary, Nitin; Han, Gang Hee Materials Today, Vol. 20, Issue 3 https://doi.org/10.1016/j.mattod.2016.10.002	journal	April 2017
Photoemission study on electronic structure of TiSe2 Negishi, S.; Negishi, H.; Shimada, K. Physica B: Condensed Matter, Vol. 383, Issue 1 https://doi.org/10.1016/j.physb.2006.03.088	journal	August 2006
Electronic structure study of Cu-doped 1T-TiSe2 by angle-resolved photoemission spectroscopy Jeong, Jinwon; Jeong, Jinhwan; Noh, Han-Jin Physica C: Superconductivity and its Applications, Vol. 470 https://doi.org/10.1016/j.physc.2009.11.123	journal	December 2010
Unveiling the charge density wave inhomogeneity and pseudogap state in 1 T -TiSe 2 Zhang, Kai-Wen; Yang, Chao-Long; Lei, Bin Science Bulletin, Vol. 63, Issue 7 https://doi.org/10.1016/j.scib.2018.02.018	journal	April 2018
Electronic Structure of a Quasi-Freestanding MoS ₂ Monolayer Eknapakul, T.; King, P. D. C.; Asakawa, M. Nano Letters, Vol. 14, Issue 3 https://doi.org/10.1021/nl4042824	journal	February 2014
2D transition metal dichalcogenides Manzeli, Sajedeh; Ovchinnikov, Dmitry; Pasquier, Diego Nature Reviews Materials, Vol. 2, Issue 8 https://doi.org/10.1038/natrevmats.2017.33	journal	June 2017
Monolayer atomic crystal molecular superlattices Wang, Chen; He, Qiyuan; Halim, Udayabagya Nature, Vol. 555, Issue 7695 https://doi.org/10.1038/nature25774	journal	March 2018
Tuning thermal conductivity in molybdenum disulfide by electrochemical intercalation Zhu, Gaohua; Liu, Jun; Zheng, Qiye Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13211	journal	October 2016
Charge density wave transition in single-layer titanium diselenide Chen, P.; Chan, Y. -H.; Fang, X. -Y. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9943	journal	November 2015
Phase-engineered low-resistance contacts for ultrathin MoS₂ transistors Kappera, Rajesh; Voiry, Damien; Yalcin, Sibel Ebru Nature Materials, Vol. 13, Issue 12, p. 1128-1134 https://doi.org/10.1038/nmat4080	journal	August 2014
Electrical switching in a magnetically intercalated transition metal dichalcogenide Nair, Nityan L.; Maniv, Eran; John, Caolan Nature Materials, Vol. 19, Issue 2 https://doi.org/10.1038/s41563-019-0518-x	journal	November 2019
Spatially controlled doping of two-dimensional SnS2 through intercalation for electronics Gong, Yongji; Yuan, Hongtao; Wu, Chun-Lan Nature Nanotechnology, Vol. 13, Issue 4 https://doi.org/10.1038/s41565-018-0069-3	journal	February 2018
Engineering covalently bonded 2D layered materials by self-intercalation Zhao, Xiaoxu; Song, Peng; Wang, Chengcai Nature, Vol. 581, Issue 7807 https://doi.org/10.1038/s41586-020-2241-9	journal	May 2020
Intercalation in two-dimensional transition metal chalcogenides Jung, Yeonwoong; Zhou, Yu; Cha, Judy J. Inorganic Chemistry Frontiers, Vol. 3, Issue 4 https://doi.org/10.1039/C5QI00242G	journal	January 2016
Two-dimensional transition metal dichalcogenides as promising anodes for potassium ion batteries from first-principles prediction Zhang, Zixiang; Yang, Mingye; Zhao, Ni Physical Chemistry Chemical Physics, Vol. 21, Issue 42 https://doi.org/10.1039/C9CP03948A	journal	January 2019
Transition metal dichalcogenides for alkali metal ion batteries: engineering strategies at the atomic level Chen, Biao; Chao, Dongliang; Liu, Enzuo Energy & Environmental Science, Vol. 13, Issue 4 https://doi.org/10.1039/C9EE03549D	journal	January 2020
Intercalation and exfoliation chemistries of transition metal dichalcogenides Zhang, Qingyong; Mei, Liang; Cao, Xiehong Journal of Materials Chemistry A, Vol. 8, Issue 31 https://doi.org/10.1039/D0TA03727C	journal	January 2020
Metallic 1T phase source/drain electrodes for field effect transistors from chemical vapor deposited MoS ₂ Kappera, Rajesh; Voiry, Damien; Yalcin, Sibel Ebru APL Materials, Vol. 2, Issue 9 https://doi.org/10.1063/1.4896077	journal	September 2014
Charge-density waves and superlattices in the metallic layered transition metal dichalcogenides Wilson, J. A.; Di Salvo, F. J.; Mahajan, S. Advances in Physics, Vol. 24, Issue 2 https://doi.org/10.1080/00018737500101391	journal	March 1975
Electronic properties of intercalation complexes of the transition metal dichalcogenides Friend, R. H.; Yoffe, A. D. Advances in Physics, Vol. 36, Issue 1 https://doi.org/10.1080/00018738700101951	journal	January 1987
The Electron Spectro-Microscopy (ESM) Beamline at NSLS-II Rajapitamahuni, A.; Yilmaz, T.; Kaznatcheev, K. Synchrotron Radiation News, Vol. 37, Issue 4 https://doi.org/10.1080/08940886.2024.2391254	journal	July 2024
Structural distortion in TiSe ₂ and related materials-a possible Jahn-Teller effect? Hughes, H. P. Journal of Physics C: Solid State Physics, Vol. 10, Issue 11 https://doi.org/10.1088/0022-3719/10/11/009	journal	June 1977
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502 https://doi.org/10.1088/0953-8984/21/39/395502	journal	September 2009
On the origin of charge-density waves in select layered transition-metal dichalcogenides Rossnagel, K. Journal of Physics: Condensed Matter, Vol. 23, Issue 21 https://doi.org/10.1088/0953-8984/23/21/213001	journal	May 2011
Advanced capabilities for materials modelling with Quantum ESPRESSO Giannozzi, P.; Andreussi, O.; Brumme, T. Journal of Physics: Condensed Matter, Vol. 29, Issue 46 https://doi.org/10.1088/1361-648X/aa8f79	journal	October 2017
Suppression and emergence of charge-density waves at the surfaces of layered 1 T -TiSe ₂ and 1 T -TaS ₂ by in situ Rb deposition Rossnagel, K. New Journal of Physics, Vol. 12, Issue 12 https://doi.org/10.1088/1367-2630/12/12/125018	journal	December 2010
Probing the exciton condensate phase in 1 T -TiSe ₂ with photoemission Monney, C.; Schwier, E. F.; Garnier, M. G. New Journal of Physics, Vol. 12, Issue 12 https://doi.org/10.1088/1367-2630/12/12/125019	journal	December 2010
Ground-State Energy of a Many-Fermion System. II Luttinger, J. M.; Ward, J. C. Physical Review, Vol. 118, Issue 5 https://doi.org/10.1103/PhysRev.118.1417	journal	June 1960
Electronic structure of TiSe 2 from a quasi-self-consistent G 0 W 0 approach Hellgren, Maria; Baguet, Lucas; Calandra, Matteo Physical Review B, Vol. 103, Issue 7 https://doi.org/10.1103/PhysRevB.103.075101	journal	February 2021
Quasi-freestanding graphene on SiC(0001) via cobalt intercalation of zero-layer graphene Rybkina, A. A.; Filnov, S. O.; Tarasov, A. V. Physical Review B, Vol. 104, Issue 15 https://doi.org/10.1103/PhysRevB.104.155423	journal	October 2021
Gapless surface electronic structure of 1T−TiSe2 in the distorted phase Yilmaz, Turgut; Vescovo, Elio Physical Review B, Vol. 108, Issue 15 https://doi.org/10.1103/PhysRevB.108.155105	journal	October 2023
Dichotomy of metallic electron density and charge density wave in 1T−TiSe2 Jeong, Dongjoon; Kim, Jimin; Jin, Kyung-Hwan Physical Review B, Vol. 109, Issue 12 https://doi.org/10.1103/PhysRevB.109.125117	journal	March 2024
Electronic properties and superlattice formation in the semimetal TiSe 2 Di Salvo, F. J.; Moncton, D. E.; Waszczak, J. V. Physical Review B, Vol. 14, Issue 10 https://doi.org/10.1103/PhysRevB.14.4321	journal	November 1976
Experimental band structure of 1T - TiSe 2 in the normal and charge-density-wave phases Stoffel, N. G.; Kevan, S. D.; Smith, N. V. Physical Review B, Vol. 31, Issue 12 https://doi.org/10.1103/PhysRevB.31.8049	journal	June 1985
Bulk and surface electronic structure of 1 T − TiS 2 and 1 T − TiSe 2 Fang, C. M.; de Groot, R. A.; Haas, C. Physical Review B, Vol. 56, Issue 8 https://doi.org/10.1103/PhysRevB.56.4455	journal	August 1997
Electronic structure of pure and alkali-metal-intercalatedVSe2 Brauer, H. E.; Starnberg, H. I.; Holleboom, L. J. Physical Review B, Vol. 58, Issue 15 https://doi.org/10.1103/PhysRevB.58.10031	journal	October 1998
Photoemission of bands above the Fermi level: The excitonic insulator phase transition in 1 T − TiSe 2 Pillo, Th.; Hayoz, J.; Berger, H. Physical Review B, Vol. 61, Issue 23 https://doi.org/10.1103/PhysRevB.61.16213	journal	June 2000
Exciton-phonon-driven charge density wave in TiSe 2 van Wezel, Jasper; Nahai-Williamson, Paul; Saxena, Siddarth S. Physical Review B, Vol. 81, Issue 16 https://doi.org/10.1103/PhysRevB.81.165109	journal	April 2010
Extracting E versus k ⃗ effective band structure from supercell calculations on alloys and impurities Popescu, Voicu; Zunger, Alex Physical Review B, Vol. 85, Issue 8 https://doi.org/10.1103/PhysRevB.85.085201	journal	February 2012
Electronic and vibrational properties of TiSe 2 in the charge-density-wave phase from first principles Bianco, Raffaello; Calandra, Matteo; Mauri, Francesco Physical Review B, Vol. 92, Issue 9 https://doi.org/10.1103/PhysRevB.92.094107	journal	September 2015
1 T − TiSe 2 : Semimetal or Semiconductor? Rasch, Julia C. E.; Stemmler, Torsten; Müller, Beate Physical Review Letters, Vol. 101, Issue 23 https://doi.org/10.1103/PhysRevLett.101.237602	journal	December 2008
Charge Transfer Effects in Naturally Occurring van der Waals Heterostructures ( PbSe ) 1.16 ( TiSe 2 ) m ( m = 1 , 2) Yao, Q.; Shen, D. W.; Wen, C. H. P. Physical Review Letters, Vol. 120, Issue 10 https://doi.org/10.1103/PhysRevLett.120.106401	journal	March 2018
Carrier-Density Control of the Quantum-Confined 1T−TiSe2 Charge Density Wave Jaouen, T.; Pulkkinen, A.; Rumo, M. Physical Review Letters, Vol. 130, Issue 22 https://doi.org/10.1103/PhysRevLett.130.226401	journal	May 2023
Charge Density Wave, Superconductivity, and Anomalous Metallic Behavior in 2D Transition Metal Dichalcogenides Castro Neto, A. H. Physical Review Letters, Vol. 86, Issue 19 https://doi.org/10.1103/PhysRevLett.86.4382	journal	May 2001
Evidence for an Excitonic Insulator Phase in 1 T − TiSe 2 Cercellier, H.; Monney, C.; Clerc, F. Physical Review Letters, Vol. 99, Issue 14 https://doi.org/10.1103/PhysRevLett.99.146403	journal	October 2007
Dimensionality reduction and band quantization induced by potassium intercalation in 1 T − HfTe 2 Nakata, Y.; Sugawara, K.; Chainani, A. Physical Review Materials, Vol. 3, Issue 7 https://doi.org/10.1103/PhysRevMaterials.3.071001	journal	July 2019

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Intercalation induced quasi-freestanding layer in TiSe2

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