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Computational study of X-doped hexagonal boron nitride (h-BN): structural and electronic properties (X = P, S, O, F, Cl)

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Abstract

Hexagonal boron nitride (h-BN), with insulating band gap (> 6 eV) 2D material, has attracted extensive attentions. To discover potential applications in optoelectronic devices, modulation in electrical conductivity (n or p type) plays a significant role. In this paper, the structural and electronic properties of energetically stable doped boron nitride monolayer via ab initio calculations have been reported. Our basic focus is on fine tuning of the band gap with replacement of a number of elements by varying the dopant site. Our results show the opportunity to induce a reduced band gap values with smaller concentration of dopants, and also show many interesting physical properties with better structural stabilities, in X-doped BN sheet (X = P, S, O, F, Cl).

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This study is based on computational data which has been computed from our own recourses with valid VASP code.

References

  1. Geim IVGAK (2013) Van der Waals heterostructures. Nature 499:419

    Article  CAS  PubMed  Google Scholar 

  2. Novoselov AKGKS, Jiang D, Schedin F, Booth TJ, Khotkevich VV, Morozov SV (2005) Two-dimensional atomic crystals. Proc Natl Acad Sci PNAS 102:10451

    Article  CAS  PubMed  Google Scholar 

  3. Slotman SYGJ, van Wijk MM, Zhao P-L, Fasolino A, Katsnelson MI (2015) Effect of structural relaxation on the electronic structure of graphene on hexagonal boron nitride. Phys Rev Lett 115:186801

    Article  CAS  PubMed  Google Scholar 

  4. Novoselov AHCNKS (2012) Two-dimensional crystals-based heterostructures: materials with tailored properties. Phys Scr T146:014006

    Article  Google Scholar 

  5. Britnell L, Ribeiro RM, Eckmann A, Jalil R, Belle BD, Mishchenko A, Kim Y-J, Gorbachev RV, Georgiou T, Morozov SV et al (2013) Strong light-matter interactions in heterostructures of atomically thin films. Science (80- ) 340:1311

    Article  CAS  Google Scholar 

  6. Britnell L, Gorbachev RV, Jalil R, Belle BD, Schedin F, Mishchenko A, Georgiou T, Katsnelson MI, Eaves L, Morozov SV et al (2012) Field-effect tunneling transistor based on vertical graphene heterostructures. Science (80- ) 335:947

    Article  CAS  Google Scholar 

  7. Rodriguez-Vega ERM, Fischer J, Das Sarma S (2014) Ground state of graphene heterostructures in the presence of random charged impurities. Phys Rev Lett 90:035406

    Google Scholar 

  8. Govindaraju N, Singh RN (2014) Chapter 8 - Synthesis and properties of boron nitride nanotubes. In: Nanotube superfiber materials: changing engineering design. Elsevier Inc., pp 243–265

  9. Ismach A, Chou H, Ferrer DA, Wu YP, McDonnell S, Floresca HC, Covacevich A, Pope C, Piner R, Kim MJ et al (2012) Toward the controlled synthesis of hexagonal boron nitride films. ACS Nano 6:6378

    Article  CAS  PubMed  Google Scholar 

  10. Kim KK et al (2012) Synthesis of monolayer hexagonal boron nitride on Cu foil using chemical vapor deposition. Nano Lett 12(1):161–166

    Article  PubMed  Google Scholar 

  11. Khan CEBAF, Down MP, Smith GC, Foster CW (2017) Surfactant-exfoliated 2D hexagonal boron nitride (2D-hBN): role of surfactant upon the electrochemical reduction of oxygen and capacitance applications. J Mater Chem A 5:4103

    Article  CAS  Google Scholar 

  12. Byun DLS, Kim JH, Song SH, Lee M, Park JJ, Lee G, Hong SH (2016) Ordered scalable heterostructure comprising boron nitride and graphene for high-performance flexible supercapacitors. Chem Mater 28:7750

    Article  CAS  Google Scholar 

  13. Xie J, Liao L, Gong YJ, Li YB, Shi FF, Pei A, Sun J, Zhang RF, Kong B, Subbaraman R et al (2017) Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode. Sci Adv 3:3170

    Article  Google Scholar 

  14. Maiti SOKUN, Lee WJ, Lee JM, Oh Y, Kim JY, Kim JE, Shim J, Han TH (2014) Chemically modified/doped carbon nanotubes & graphene for optimized nanostructures & nanodevices. Adv Mater 26:40

    Article  CAS  PubMed  Google Scholar 

  15. Ding Y m et al (2016) Improvement of n-type conductivity in hexagonal boron nitride monolayers by doping, strain and adsorption. RSC Adv 6(35):29190–29196

    Article  CAS  Google Scholar 

  16. Wei F, Wan Q, Lin S, Guo H (2020) Origin of confined catalysis in nanoscale reactors between two- dimensional covers and metal substrates: mechanical or electronic?

  17. Carlone P (2017) Physics of organic semiconductors, 2nd edn. In: Brütting W, Adachi C (eds) Materials and Manufacturing Processes, 1st edn, vol 32, pp 458–459

  18. Tarasov EMVA, Zhang S, Tsai MY, Campell PM, Graham S, Barlow S, Marder SR (2015) Controlled doping of large-area trilayer MoS2 with molecular reductants and oxidants. Adv Mater 27:117

    Article  Google Scholar 

  19. Zobelli CCA, Gloter A, Ewels CP, Seifert G (2007) Electron knock-on cross section of carbon and boron nitride nanotubes. Phys Rev B 75:245402

    Article  Google Scholar 

  20. Gao X, Wang S, Lin S (2016) Defective hexagonal boron nitride nanosheet on Ni ( 111 ) and Cu ( 111 ): stability , electronic structures , and potential applications. (111).

  21. Sen Lin HG, Ye X, Johnson RS (2013) First-principles investigations of metal (Cu, Ag, Au, Pt, Rh, Pd, Fe, Co, and Ir) doped hexagonal boron nitride nanosheets: stability and catalysis of CO oxidation. J Phys Chem C 117:17319

    Article  Google Scholar 

  22. Bhattacharya A, Bhattacharya S, Das GP (2012) Band gap engineering by functionalization of BN sheet. Phys Rev B Condens Matter Mater Phys 85(3):1–9

    Article  Google Scholar 

  23. Cho H-B, Tokoi Y, Tanaka S, Suematsu H, Suzuki T, Niihara K, Nakayama T (2011) Modification of BN nanosheets and their thermal conducting properties in nanocomposite film with polysiloxane according to the orientation of BN. Compos Sci Technol 71:1046–1052

    Article  CAS  Google Scholar 

  24. Hu J, Yue M, Zhang H, Yuan Z, Li X (2020) A boron nitride nanosheets composite membrane for a long-life zinc-based flow battery. Angew Chem Int Ed Engl 59:6715–6719

    Article  CAS  PubMed  Google Scholar 

  25. Li YCLH, Santos EJG, Xing T, Cappelluti E, Roldan R, Watanabe TTK (2014) Dielectric screening in atomically thin boron nitride nanosheets. Nano Lett 15:218–223

    Article  PubMed  Google Scholar 

  26. Kim D, Liu X, Yu B, Mateti S, O’Dell LA, Rong Q, Chen Y(I) (2020) Amine-functionalized boron nitride nanosheets: a new functional additive for robust, flexible ion gel electrolyte with high lithium-ion transference number. Adv Funct Mater 30:1910813

    Article  CAS  Google Scholar 

  27. Da Rocha Martins J, Chacham H (2011) Disorder and segregation in B-C-N graphene-type layers and nanotubes: Tuning the band gap. ACS Nano 5:385–393

  28. Tayyab M, Hussain A, Adil W, Nabi S, Asif Q u A (2020) Band-gap engineering of graphene by Al doping and adsorption of Be and Br on impurity: A computational study. Comput Condens Matter 23:e00463

  29. Ullah S et al (2015) Band-gap tuning of graphene by Be doping and Be, B co-doping: a DFT study. RSC Adv 5(69):55762–55773

    Article  CAS  Google Scholar 

  30. Tayyab M, Hussain A, Asif Q u A, Adil W (2020) Band-gap tuning of graphene by Mg doping and adsorption of Br and Be on impurity: A DFT study. Comput Condens Matter 23:e00469

  31. Hussain A, Ullah S, Farhan MA (2016) Fine tuning the band-gap of graphene by atomic and molecular doping: a density functional theory study. RSC Adv 6(61):55990–56003

    Article  CAS  Google Scholar 

  32. Ullah S, Hussain A, Sato F (2017) Rectangular and hexagonal doping of graphene with B, N, and O: a DFT study. RSC Adv 7(26):16064–16068

    Article  CAS  Google Scholar 

  33. Tang Q, Zhou Z, Chen Z (2011) Molecular charge transfer: A simple and effective route to engineer the band structures of BN nanosheets and nanoribbons. J Phys Chem C 115:18531–18537

  34. Xu J, Wan Q, Anpo M, Lin S (2020) Bandgap opening of graphdiyne monolayer via B, N-codoping for photocatalytic overall water splitting: design strategy from DFT studies. J Phys Chem C

  35. Jhi SH, Kwon YK (2004) Hydrogen adsorption on boron nitride nanotubes: a path to room-temperature hydrogen storage. Phys Rev B Condens Matter Mater Phys 69(24):1–4

    Article  Google Scholar 

  36. Feng C et al (2019) Enhancing optical absorption and charge transfer: synthesis of S-doped h-BN with tunable band structures for metal-free visible-light-driven photocatalysis. Appl Catal B Environ

  37. Zobelli A, Ewels CP, Gloter A, Seifert G (2007) Vacancy migration in hexagonal boron nitride. Phys Rev B 75(9):1–7

  38. Azevedo S, Kaschny JR, De Castilho CMC, De Brito Mota F (2009) Electronic structure of defects in a boron nitride monolayer. Eur Phys J B 67:507–512

  39. Ataca C, Ciraci S (2010) Functionalization of BN honeycomb structure by adsorption and substitution of foreign atoms. Phys Rev B 82:165402

    Article  Google Scholar 

  40. Kobashi K (2014) Shift of Fermi level by substitutional impurity-atom doping in diamond and cubic- and hexagonal-boron nitrides.

  41. Sun F et al (2018) P-Type conductivity of hexagonal boron nitride as a dielectrically tunable monolayer: modulation doping with magnesium. Nanoscale 10(9):4361–4369

    Article  CAS  PubMed  Google Scholar 

  42. Nose K, Oba H, Yoshida T (2006) Electric conductivity of boron nitride thin films enhanced by in situ doping of zinc. Appl Phys Lett 89(11):112124

    Article  Google Scholar 

  43. Asif Q u A, Hussain A, Rafique HM, Tayyab M (2020) Computational study of Be-doped hexagonal boron nitride (h-BN): structural and electronic properties. Comput Condens Matter 23:e00474

    Article  Google Scholar 

  44. Wan Q, Wei F, Ma Z, Anpo M, Lin S (2019) Novel porous boron nitride nanosheet with carbon doping: potential metal-free photocatalyst for visible-light-driven overall water splitting. Photocatalysis 1800174:1–11

  45. Kresse G, Hafner J (1994) Ab initio molecular-dynamics simulation of the liquid-metalamorphous-semiconductor transition in germanium. Phys Rev B 49:14251–14269

  46. Blöchl PE (1994) Projector augmented-wave method. Phys Rev B 50:17953

    Article  Google Scholar 

  47. Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865–3868

  48. Monkhorst HJ, Pack JD (1976) Special points for Brillouin-zone integrations. Phys Rev B 13:5188–5192

  49. Ullah S, Denis PA, Sato F (2018) Hydrogenation and fluorination of 2D boron phosphide and boron arsenide: a density functional theory investigation. ACS Omega 3(12):16416–16423

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  50. Topsakal M, Aktürk E, Ciraci S (2009) First-principles study of two- and one-dimensional honeycomb structures of boron nitride. Phys Rev B - Condens Matter Mater Phys 79:115442

  51. Zhou YG, Xiao-Dong J, Wang ZG, Xiao HY, Gao F, Zu XT (2010) Electronic and magnetic properties of metal-doped BN sheet: A first-principles study. Phys Chem Chem Phys 12:7588–7592

  52. Paszkowicz W, Pelka JB, Knapp M, Szyszko T, Podsiadlo S (2002) Lattice parameters and anisotropic thermal expansion of hexagonal boron nitride in the 10-297.5 K temperature range. Appl Phys A Mater Sci Process 75:431–435

  53. Kim D-H, Kim H-S, Song MW, Lee S, Lee SY (2017) Geometric and electronic structures of monolayer hexagonal boron nitride with multi-vacancy. Nano Converg 4:1–8

  54. Naqvi SR, Rao GS, Luo W, Ahuja R, Hussain T (2017) Hexagonal boron nitride (h-BN) sheets decorated with OLi, ONa, and Li2F molecules for enhanced energy storage. ChemPhysChem 18(5):513–518

    Article  CAS  PubMed  Google Scholar 

  55. Legesse M, Rashkeev SN, Saidaoui H, El F, Ahzi S, Alharbi FH (2020) Band gap tuning in aluminum doped two-dimensional hexagonal boron nitride. Mater Chem Phys 250(April):123176

    Article  CAS  Google Scholar 

  56. Berseneva N, Gulans A, Krasheninnikov AV, Nieminen RM (2013) Electronic structure of boron nitride sheets doped with carbon from first-principles calculations. Phys Rev B - Condens Matter Mater Phys 87:035404

  57. Park KT, Terakura K, Hamada N (1987) Band-structure calculations for boron nitrides with three different crystal structures. J Phys C Solid State Phys 20:1241

  58. Mapasha RE, Igumbor E, Chetty N (2016) A hybrid density functional study of silicon and phosphorus doped hexagonal boron nitride monolayer. J Phys Conf Ser 759(1):012042–1251

  59. Denis PA (2013) Concentration dependence of the band gaps of phosphorus and sulfur doped graphene. Comput Mater Sci 67:203–206

    Article  CAS  Google Scholar 

  60. De Andrade Silva L, Guerini SC, Lemos V, Filho JM (2006) Electronic and structural properties of oxygen-doped BN nanotubes. IEEE Trans Nanotechnol 5(5):517–521

    Article  Google Scholar 

  61. Lu Q, Zhao Q, Yang T, Zhai C, Wang D, Zhang M (2018) Preparation of boron nitride nanoparticles with oxygen doping and a study of their room-temperature ferromagnetism. ACS Appl Mater Interfaces 10(15):12947–12953

    Article  CAS  PubMed  Google Scholar 

  62. Lei W et al (2014) Oxygen-doped boron nitride nanosheets with excellent performance in hydrogen storage. Nano Energy 6:219–224

    Article  CAS  Google Scholar 

  63. Tang C et al (2005) Fluorination and electrical conductivity of BN nanotubes. J Am Chem Soc 127(18):6552–6553

    Article  CAS  PubMed  Google Scholar 

  64. Ahmad A u et al (2019) A novel mechano-chemical synthesis route for fluorination of hexagonal boron nitride nanosheets. Ceram Int 45(15):19173–19181

    Article  Google Scholar 

  65. Radhakrishnan S et al (2017) Fluorinated h-BN As a magnetic semiconductor. Sci Adv 3(7):1–9

    Article  Google Scholar 

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Acknowledgments

The authors would like to thank the substantial support given by PINSTECH, Computational resources by PIEAS, Islamabad, Pakistan, Government College University, Faisalabad, Punjab, Pakistan and University of the Punjab, Lahore, Punjab, Pakistan. Special thanks to Haris Akram Bhatti for fruitful discussions.

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Authors and Affiliations

  1. Department of Physics, University of the Punjab, Quaid i Azam Campus, Lahore, Pakistan

    Qurat ul Ain Asif & Hafiz Muhammad Rafique

  2. Department of Physics, Government College University, Allama Iqbal Road, Faisalabad, Pakistan

    Qurat ul Ain Asif

  3. TPD, Pakistan Institute of Nuclear Science and Technology (PINSTECH), P. O. Nilore, Islamabad, Pakistan

    Akhtar Hussain & Azeem Nabi

  4. Department of Physics and Applied Mathematics, Pakistan Institute of Engineering and Applied Sciences (PIEAS), P. O. Nilore, Islamabad, Pakistan

    Azeem Nabi

  5. Department of Physics, International Islamic University, Islamabad, Pakistan

    Muhammad Tayyab

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  1. Qurat ul Ain Asif
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Contributions

Qurat ul Ain Asif and Akhtar Hussain had original idea for the study and carried out the calculations. They are responsible for data analysis and preparation. Qurat ul Ain Asif drafted the manuscript, which was corrected/revised by all the co-authors except Azeem Nabi who participated while replying the comments. Azeem Nabi helped to reply the comments raised by the reviewers. Muhammad Tayyab helped in data preparation, revision of the manuscript, and rescaling of figures. Hafiz Muhammad Rafique performed the supervisory role.

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Correspondence to Qurat ul Ain Asif.

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This manuscript is based on our own calculated data. No plagiarism or any other moral/ethical value has been violated.

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I, Dr. Akhtar Hussain, agree the research conducted on the subject matter and has played co-supervisory role in carrying out the research and preparation of the manuscript.

I, Azeem Nabi, agree the research conducted on the subject matter and played role as a co-author in carrying out the research and preparation of the manuscript.

I, Muhammad Tayyab, agree the research conducted on the subject matter and played role as a co-author in carrying out the research and preparation of the manuscript.

I, Dr. Hafiz Muhammad Rafique, agree the research conducted on the subject matter and has played supervisory role in carrying out the research and preparation of the manuscript.

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I, Dr. Akhtar Hussain, agree to submit the manuscript to Journal of Molecular Modeling.

I, Azeem Nabi, agree to submit the manuscript to Journal of Molecular Modeling.

I, Muhammad Tayyab, agree to submit the manuscript to Journal of Molecular Modeling.

I, Dr. Hafiz Muhammad Rafique, agree to submit the manuscript to Journal of Molecular Modeling.

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The computational code/resources for this study have been provided by Dr. Akhtar Hussain.

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Asif, Q.u.A., Hussain, A., Nabi, A. et al. Computational study of X-doped hexagonal boron nitride (h-BN): structural and electronic properties (X = P, S, O, F, Cl). J Mol Model 27, 31 (2021). https://doi.org/10.1007/s00894-020-04659-z

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