Chemistry:Boron nitride nanosheet

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Two-layer BN nanosheet.
Atomic-resolution images of a BN nanosheet prepared by CVD.[1]

Boron nitride nanosheet is a two-dimensional crystalline form of the hexagonal boron nitride (h-BN), which has a thickness of one to few atomic layers. It is similar in geometry as well as physical and thermal properties to its all-carbon analog graphene, but has very different chemical and electronic properties – contrary to the black and highly conducting graphene, BN nanosheets are electrical insulators with a band gap of ~5.9 eV, and therefore appear white in color.[2]

Uniform monoatomic BN nanosheets can be deposited by catalytic decomposition of borazine at a temperature ~1100 °C in a chemical vapor deposition setup, over substrate areas up to about 10 cm2. Owing to their hexagonal atomic structure, small lattice mismatch with graphene (~2%), and high uniformity they are used as substrates for graphene-based devices.[2][3]

Structure

BN nanosheets consist of sp2-conjugated boron and nitrogen atoms that form a honeycomb structure.[4][5] They contain two different edges: armchair and zig-zag. The armchair edge consists of either boron or nitrogen atoms, while the zig-zag edge consists of alternating boron and nitrogen atoms. These 2D structures can stack on top of each other and are held by Van der Waals forces to form few-layer boron nitride nanosheets. In these structures, the boron atoms of one sheet are positioned on top or below the nitrogen atoms due to electron-deficient nature of boron and electron-rich nature of nitrogen.[5][6]

Synthesis

CVD

Chemical vapor deposition is the most common method to produce BN nanosheets because it is a well-established and highly controllable process that yields high-quality material over areas exceeding 10 cm2.[2][6] There is a wide range of boron and nitride precursors for CVD synthesis, such as borazine, and their selection depends on toxicity,[6] stability,[5][6] reactivity,[6] and the nature of the CVD method.[5][6][7]

Mechanical cleavage

A typical electron micrograph of BN nanosheets prepared by ball milling (scale bar 50 nm).[8]

Mechanical cleaving methods of boron nitride use shear forces to break the weak van der Waals interactions between the BN layers.[5] Cleaved nanosheets have low defect densities and retain the lateral size of the original substrate.[5][6] Inspired by its use in the isolation of graphene, micromechanical cleavage, also known as the Scotch-tape method, has been used to consistently isolate few-layer and monolayer boron nitride nanosheets by subsequent exfoliation of the starting material with adhesive tape.[5][6] The disadvantage of this technique is that it is not scalable for large-scale production.[5][6][7]

Boron nitride sheets can be also exfoliated by ball milling, where shear forces are applied on the face of bulk boron nitride by rolling balls.[9] This technique yields large quantities of low-quality material with poor control over its properties.[5][6]

Unzipping of boron nitride nanotubes

BN nanosheets can be synthesized by the unzipping boron nitride nanotubes via potassium intercalation or etching by plasma or an inert gas. Here the intercalation method has a relatively low yield as boron nitride is resistive to the effects of intercalants.[5][6] In situ unzipping of boron nitride nanotubes to nanoribbons was achieved by Li et al.[10]

Solvent exfoliation and sonication

Solvent exfoliation is often used in tandem with sonication to isolate large quantities of boron nitride nanosheets. Polar solvents such as isopropyl alcohol[6] and DMF[11] are more effective in exfoliating boron nitride layers than nonpolar solvents because these solvents possess a similar surface energy to the surface energy of boron nitride nanosheets. Combinations of different solvents also exfoliate boron nitride better than individual solvents.[5] Many solvents suitable for BN exfoliation are rather toxic and expensive, but they can be replaced by water and isopropyl alcohol without significantly sacrificing the yield.[5][6][11]

Chemical functionalization and sonication

Chemical functionalization of boron nitride involves attaching molecules onto the outer and inner layers of bulk boron nitride.[6] There are three types of BN functionalization: covalent, ionic and or non-covalent.[5] Layers are exfoliated by placing the functionalized BN into a solvent and allowing the solvation force between the attached groups and the solvent to break the van der Waal forces between BN layers.[7] This method is slightly different from solvent exfoliation, which relies on the similarities between the surface energies of the solvent and boron nitride layers.

Solid state reactions

Heating a mixture of boron and nitrogen precursors, such as boric acid and urea, can produce boron nitride nanosheets.[5][7] The number of layers in these nanosheets was controlled by temperature (ca. 900 ˚C) and the urea content.[7]

Properties and applications

Mechanical properties. Monolayer boron nitride has an average Young's modulus of 0.865 TPa and fracture strength of 70.5 GPa. In contrast to graphene, whose strength decreases dramatically with increased thickness, few-layer boron nitride sheets have a strength similar to that of monolayer boron nitride.[12]

Thermal conductivity. The thermal conductivity of atomically thin boron nitride is one of the highest among semiconductors and electrical insulators; it increases with reduced thickness due to less intra-layer coupling.

Thermal stability. The air stability of graphene shows a clear thickness dependence: monolayer graphene is reactive to oxygen at 250 °C, strongly doped at 300 °C, and etched at 450 °C; in contrast, bulk graphite is not oxidized until 800 °C.[13] Atomically thin boron nitride has much better oxidation resistance than graphene. Monolayer boron nitride is not oxidized till 700 °C and can sustain up to 850 °C in air; bilayer and trilayer boron nitride nanosheets have slightly higher oxidation starting temperatures.[14] The excellent thermal stability, high impermeability to gas and liquid, and electrical insulation make atomically thin boron nitride potential coating materials for preventing surface oxidation and corrosion of metals[15][16] and other two-dimensional (2D) materials, such as black phosphorus.[17]

Better surface adsorption. Atomically thin boron nitride has been found to have better surface adsorption capabilities than bulk hexagonal boron nitride.[18] According to theoretical and experimental studies, atomically thin boron nitride as an adsorbent experiences conformational changes upon surface adsorption of molecules, increasing adsorption energy and efficiency. The synergic effect of the atomic thickness, high flexibility, stronger surface adsorption capability, electrical insulation, impermeability, high thermal and chemical stability of BN nanosheets can increase the Raman sensitivity by up to two orders, and in the meantime attain long-term stability and extraordinary reusability not achievable by other materials.[19][20]

Dielectric properties. Atomically thin hexagonal boron nitride is an excellent dielectric substrate for graphene, molybdenum disulphide (MoS2), and many other 2D material-based electronic and photonic devices. As shown by electric force microscopy (EFM) studies, the electric field screening in atomically thin boron nitride shows a weak dependence on thickness, which is in line with the smooth decay of electric field inside few-layer boron nitride revealed by the first-principles calculations.[21]

Raman characteristics. Raman spectroscopy has been a useful tool to study a variety of 2D materials, and the Raman signature of high-quality atomically thin boron nitride was first reported by Gorbachev et al.[22] and Li et al.[14] However, the two reported Raman results of monolayer boron nitride did not agree with each other. Cai et al. conducted systematic experimental and theoretical studies of the intrinsic Raman spectrum of atomically thin boron nitride.[23] They reveal that, in absence of interaction with a substrate, atomically thin boron nitride has a G-band frequency similar to that of bulk hexagonal boron nitride, but strain induced by the substrate can cause Raman shifts. Nevertheless, the Raman intensity of G-band can be used to estimate layer thickness and sample quality.

BN nanosheets are electrical insulators and have a wide band gap of ~5.9 eV, which can be changed by the presence of Stone–Wales defects within the structure, by doping or functionalization, or by changing the number of layers.[4][6] Owing to their hexagonal atomic structure, small lattice mismatch with graphene (~2%), and high uniformity, BN nanosheets are used as substrates for graphene-based devices.[2][3] BN nanosheets are also excellent proton conductors. Their high proton transport rate, combined with the high electrical resistance, may lead to applications in fuel cells and water electrolysis.[24]

References

  1. ↑ Aldalbahi, Ali; Zhou, Andrew Feng; Feng, Peter (2015). "Variations in Crystalline Structures and Electrical Properties of Single Crystalline Boron Nitride Nanosheets". Scientific Reports 5: 16703. doi:10.1038/srep16703. PMID 26563901. Bibcode: 2015NatSR...516703A. 
  2. ↑ 2.0 2.1 2.2 2.3 Park, Ji-Hoon; Park, Jin Cheol; Yun, Seok Joon; Kim, Hyun; Luong, Dinh Hoa; Kim, Soo Min; Choi, Soo Ho; Yang, Woochul et al. (2014). "Large-Area Monolayer Hexagonal Boron Nitride on Pt Foil". ACS Nano 8 (8): 8520–8. doi:10.1021/nn503140y. PMID 25094030. 
  3. ↑ 3.0 3.1 Wu, Q; Park, J. H.; Park, S; Jung, S. J.; Suh, H; Park, N; Wongwiriyapan, W; Lee, S et al. (2015). "Single Crystalline Film of Hexagonal Boron Nitride Atomic Monolayer by Controlling Nucleation Seeds and Domains". Scientific Reports 5: 16159. doi:10.1038/srep16159. PMID 26537788. Bibcode: 2015NatSR...516159W. 
  4. ↑ 4.0 4.1 Li, Lu Hua; Chen, Ying (2016). "Atomically Thin Boron Nitride: Unique Properties and Applications". Advanced Functional Materials 26 (16): 2594–2608. doi:10.1002/adfm.201504606. 
  5. ↑ 5.00 5.01 5.02 5.03 5.04 5.05 5.06 5.07 5.08 5.09 5.10 5.11 5.12 5.13 Bhimanapati, G. R.; Glavin, N. R.; Robinson, J. A. (2016-01-01). Iacopi, Francesca; Boeckl, John J.; Jagadish, Chennupati. eds. Semiconductors and Semimetals. 2D Materials. 95. Elsevier. pp. 101–147. doi:10.1016/bs.semsem.2016.04.004. ISBN 978-0-12-804272-4. 
  6. ↑ 6.00 6.01 6.02 6.03 6.04 6.05 6.06 6.07 6.08 6.09 6.10 6.11 6.12 6.13 6.14 Lin, Yi; Connell, John W. (2012). "Advances in 2D boron nitride nanostructures: nanosheets, nanoribbons, nanomeshes, and hybrids with graphene". Nanoscale 4 (22): 6908–39. doi:10.1039/c2nr32201c. PMID 23023445. Bibcode: 2012Nanos...4.6908L. 
  7. ↑ 7.0 7.1 7.2 7.3 7.4 Wang, Zifeng; Tang, Zijie; Xue, Qi; Huang, Yan; Huang, Yang; Zhu, Minshen; Pei, Zengxia; Li, Hongfei et al. (2016). "Fabrication of Boron Nitride Nanosheets by Exfoliation". The Chemical Record 16 (3): 1204–1215. doi:10.1002/tcr.201500302. PMID 27062213. 
  8. ↑ Lei, Weiwei; Mochalin, Vadym N.; Liu, Dan; Qin, Si; Gogotsi, Yury; Chen, Ying (2015). "Boron nitride colloidal solutions, ultralight aerogels and freestanding membranes through one-step exfoliation and functionalization". Nature Communications 6: 8849. doi:10.1038/ncomms9849. PMID 26611437. Bibcode: 2015NatCo...6.8849L. 
  9. ↑ Li, Lu Hua; Chen, Ying; Behan, Gavin; Zhang, Hongzhou; Petravic, Mladen; Glushenkov, Alexey M. (2011). "Large-scale mechanical peeling of boron nitride nanosheets by low-energy ball milling". Journal of Materials Chemistry 21 (32): 11862. doi:10.1039/c1jm11192b. 
  10. ↑ Li, Ling; Li, Lu Hua; Chen, Ying; Dai, Xiujuan J.; Lamb, Peter R.; Cheng, Bing-Ming; Lin, Meng-Yeh; Liu, Xiaowei (2013). "High-Quality Boron Nitride Nanoribbons: Unzipping during Nanotube Synthesis". Angewandte Chemie 125 (15): 4306–4310. doi:10.1002/ange.201209597. Bibcode: 2013AngCh.125.4306L. 
  11. ↑ 11.0 11.1 Zhi, Chunyi; Bando, Yoshio; Tang, Chengchun; Kuwahara, Hiroaki; Golberg, Dimitri (2009). "Large-Scale Fabrication of Boron Nitride Nanosheets and Their Utilization in Polymeric Composites with Improved Thermal and Mechanical Properties". Advanced Materials 21 (28): 2889–2893. doi:10.1002/adma.200900323. Bibcode: 2009AdM....21.2889Z. 
  12. ↑ Falin, Aleksey; Cai, Qiran; Santos, Elton J.G.; Scullion, Declan; Qian, Dong; Zhang, Rui; Yang, Zhi; Huang, Shaoming et al. (2017). "Mechanical properties of atomically thin boron nitride and the role of interlayer interactions". Nature Communications 8: 15815. doi:10.1038/ncomms15815. PMID 28639613. Bibcode: 2017NatCo...815815F. 
  13. ↑ Liu, Li; Ryu, Sunmin; Tomasik, Michelle R.; Stolyarova, Elena; Jung, Naeyoung; Hybertsen, Mark S.; Steigerwald, Michael L.; Brus, Louis E. et al. (2008). "Graphene Oxidation: Thickness-Dependent Etching and Strong Chemical Doping". Nano Letters 8 (7): 1965–1970. doi:10.1021/nl0808684. PMID 18563942. Bibcode: 2008NanoL...8.1965L. 
  14. ↑ 14.0 14.1 Li, Lu Hua; Cervenka, Jiri; Watanabe, Kenji; Taniguchi, Takashi; Chen, Ying (2014). "Strong Oxidation Resistance of Atomically Thin Boron Nitride Nanosheets". ACS Nano 8 (2): 1457–1462. doi:10.1021/nn500059s. PMID 24400990. 
  15. ↑ Li, Lu Hua; Xing, Tan; Chen, Ying; Jones, Rob (2014). "Nanosheets: Boron Nitride Nanosheets for Metal Protection (Adv. Mater. Interfaces 8/2014)". Advanced Materials Interfaces 1 (8): n/a. doi:10.1002/admi.201470047. 
  16. ↑ Liu, Zheng; Gong, Yongji; Zhou, Wu; Ma, Lulu; Yu, Jingjiang; Idrobo, Juan Carlos; Jung, Jeil; MacDonald, Allan H. et al. (2013). "Ultrathin high-temperature oxidation-resistant coatings of hexagonal boron nitride". Nature Communications 4 (1): 2541. doi:10.1038/ncomms3541. PMID 24092019. Bibcode: 2013NatCo...4.2541L. 
  17. ↑ Chen, Xiaolong; Wu, Yingying; Wu, Zefei; Han, Yu; Xu, Shuigang; Wang, Lin; Ye, Weiguang; Han, Tianyi et al. (2015). "High-quality sandwiched black phosphorus heterostructure and its quantum oscillations". Nature Communications 6 (1): 7315. doi:10.1038/ncomms8315. PMID 26099721. Bibcode: 2015NatCo...6.7315C. 
  18. ↑ Cai, Qiran; Du, Aijun; Gao, Guoping; Mateti, Srikanth; Cowie, Bruce C. C.; Qian, Dong; Zhang, Shuang; Lu, Yuerui et al. (2016). "Molecule-Induced Conformational Change in Boron Nitride Nanosheets with Enhanced Surface Adsorption". Advanced Functional Materials 26 (45): 8202–8210. doi:10.1002/adfm.201603160. 
  19. ↑ Cai, Qiran; Mateti, Srikanth; Yang, Wenrong; Jones, Rob; Watanabe, Kenji; Taniguchi, Takashi; Huang, Shaoming; Chen, Ying et al. (2016). "Inside Back Cover: Boron Nitride Nanosheets Improve Sensitivity and Reusability of Surface-Enhanced Raman Spectroscopy (Angew. Chem. Int. Ed. 29/2016)". Angewandte Chemie International Edition 55 (29): 8457. doi:10.1002/anie.201604295. 
  20. ↑ Cai, Qiran; Mateti, Srikanth; Watanabe, Kenji; Taniguchi, Takashi; Huang, Shaoming; Chen, Ying; Li, Lu Hua (2016). "Boron Nitride Nanosheet-Veiled Gold Nanoparticles for Surface-Enhanced Raman Scattering". ACS Applied Materials & Interfaces 8 (24): 15630–15636. doi:10.1021/acsami.6b04320. PMID 27254250. 
  21. ↑ Li, Lu Hua; Santos, Elton J. G.; Xing, Tan; Cappelluti, Emmanuele; Roldán, Rafael; Chen, Ying; Watanabe, Kenji; Taniguchi, Takashi (2015). "Dielectric Screening in Atomically Thin Boron Nitride Nanosheets". Nano Letters 15 (1): 218–223. doi:10.1021/nl503411a. PMID 25457561. Bibcode: 2015NanoL..15..218L. 
  22. ↑ Gorbachev, Roman V.; Riaz, Ibtsam; Nair, Rahul R.; Jalil, Rashid; Britnell, Liam; Belle, Branson D.; Hill, Ernie W.; Novoselov, Kostya S. et al. (2011). "Hunting for Monolayer Boron Nitride: Optical and Raman Signatures". Small 7 (4): 465–468. doi:10.1002/smll.201001628. PMID 21360804. 
  23. ↑ Cai, Qiran; Scullion, Declan; Falin, Aleksey; Watanabe, Kenji; Taniguchi, Takashi; Chen, Ying; Santos, Elton J. G.; Li, Lu Hua (2017). "Raman signature and phonon dispersion of atomically thin boron nitride". Nanoscale 9 (9): 3059–3067. doi:10.1039/c6nr09312d. PMID 28191567. https://pure.qub.ac.uk/portal/en/publications/raman-signature-and-phonon-dispersion-of-atomically-thin-boron-nitride(5f58d958-22ab-450f-97fb-cd7c0f25f5b4).html. 
  24. ↑ Hu, S. (2014). "Proton transport through one-atom-thick crystals". Nature 516 (7530): 227–230. doi:10.1038/nature14015. PMID 25470058. Bibcode: 2014Natur.516..227H. 



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