铜箔上生长的六角氮化硼薄膜的扫描隧道显微镜研究

徐丹; 殷俊; 孙昊桦; 王观勇; 钱冬; 管丹丹; 李耀义; 郭万林; 刘灿华; 贾金锋

doi:10.7498/aps.65.116801

摘要

利用扫描隧道显微镜研究了采用化学气相沉积法在铜箔表面生长出的高质量的六角氮化硼薄膜. 大范围的扫描隧道显微镜图像显示出该薄膜具有原子级平整的表面, 而扫描隧道谱则显示, 扫描隧道显微镜图像反映出的是该薄膜样品的隧穿势垒空间分布. 极低偏压的扫描隧道显微镜图像呈现了氮化硼薄膜表面的六角蜂窝周期性原子排列, 而高偏压的扫描隧道显微镜图像则呈现出无序和有序排列区域共存的电子调制图案. 该调制图案并非源于氮化硼薄膜和铜箔衬底的面内晶格失配, 而极有可能来源于两者界面处的氢、硼和/或氮原子在铜箔表面的吸附所导致的隧穿势垒的局域空间分布.

关键词:

Abstract

Analogous to graphite, hexagonal boron nitride (h-BN) has a layered structure composed of boron and nitrogen atoms that are alternatively bond to each other in a honeycomb array. As the layers are held together by weak van der Waals forces, h-BN thin films can be grown on surfaces of various metal crystals in a layer-by-layer manner, which is again similar to graphene sheets and thus attracts a lot of research interests. In this work, scanning tunneling microscope and spectroscope (STM and STS) were applied to the study of an h-BN thin film with a thickness of about 10 nm grown on Cu foil by means of chemical vapor deposition. X-ray diffraction from the Cu foil shows only one strong peak of Cu(200) in the angle range of 40-60, indicating that the Cu foil is mainly Cu(100). After sufficient annealing in an UHV chamber, the h-BN film sample is transferred to a cooling stage (77 K) for STM/STS measurement. Its high quality is confirmed by a large-scale STM scan that shows an atomically flat topography. A series of dI/dV data taken within varied energy windows all exhibit similar U shapes but with different bottom widths that monotonously decrease with the sweeping energy window. The dI/dV curve taken in the energy window of [-1 V, +1 V] even shows no energy gap in spite that h-BN film is insulating with a quite large energy gap of around 6 eV, as observed in a large-energy-window dI/dV curve (from -5 V to +5 V). These results indicate that the STM images reflect the spatial distribution of tunneling barriers between Cu(100) substrate and STM tip, rather than the local density of states of the h-BN surface. At high sample biases (from 4 V to 1 V), STM images exhibit an electronic modulation pattern with short range order. The modulation pattern displays a substructure in low-bias STM images (less than 100 mV), which finally turns to the (11) lattice of h-BN surface when the sample bias is extremely lowered to 3 mV. It is found that the electronic modulation pattern cannot be fully reproduced by superimposing hexagonal BN lattice on tetragonal Cu(100) lattice, no matter what their relative in-plane crystal orientation is. This implies that the electronic modulation pattern in the STM images is not a Mori pattern due to lattice mismatch. We speculate that it may originate from spatial distribution of tunneling barrier induced by adsorption of H, B and/or N atoms on the Cu(100) surface in the CVD growth process.

Keywords:

作者及机构信息

1.
上海交通大学物理与天文系, 人工结构及量子调控教育部重点实验室, 上海 200240;

2.
南京航空航天大学航空宇航学院, 机械结构力学及控制国家重点实验室, 纳智能材料器件教育部重点实验室, 南京 210016;

3.
人工微结构科学与技术协同创新中心, 南京 210093

通信作者: 刘灿华, canhualiu@sjtu.edu.cn;jfjia@sjtu.edu.cn ; 贾金锋, canhualiu@sjtu.edu.cn;jfjia@sjtu.edu.cn

基金项目: 国家重点基础研究发展计划(批准号: 2013CB921902, 2012CB927401, 2013CB932604, 2012CB933403)、国家自然科学基金(批准号: 11521404, 11134008, 11574201, 11574202, 11504230, 51472117, 51535005)、上海市科委科技基金(批准号: 15JC1402300, 14PJ1404600) 和江苏省自然科学基金(批准号: BK20130781)资助的课题.

Authors and contacts

1.
Key Laboratory of Artificial Structures and Quantum Control, Department of Physics and Astronomy, Shanghai Jiao Tong University, Shanghai 200240, China;

2.
State Key Laboratory of Mechanics and Control of Mechanical Structures, Key Laboratory for Intelligent Nano Materials and Devices of the Ministry of Education Institute of Nanoscience, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China;

3.
Collaborative Innovation Center of Advanced Microstructures, Nanjing 210093, China

Corresponding author: Liu Can-Hua, canhualiu@sjtu.edu.cn;jfjia@sjtu.edu.cn ; Jia Jin-Feng, canhualiu@sjtu.edu.cn;jfjia@sjtu.edu.cn

Funds: Project supported by the National Basic Research Program of China (Grant Nos. 2013CB921902, 2012CB927401, 2013CB932604, 2012CB933403), the National Natural Science Foundation of China (Grant Nos. 11521404, 11134008, 11574201, 11574202, 11504230, 51472117, 51535005, 51472117, 51535005), Shanghai Committee of Science and Technology, China (Grant Nos. 15JC1402300, 14PJ1404600), and Jiangsu Province Natural Science Foundation, China (Grant No. BK20130781).

参考文献

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[47]	Kidambi P R, Blume R, Kling J, Wagner J B, Baehtz C, Weatherup R S, Schloegl R, Bayer B C, Hofmann S 2014 Chem. Mater. 26 6380

施引文献

[1]	Novoselov K S, Geim A K, Morozov S V, Jiang D, Katsnelson M I, Grigorieva I V, Dubonos S V, Firsov A A 2005 Nature 438 197
[2]	Zhang Y, Tan Y W, Stormer H L, Kim P 2005 Nature 438 201
[3]	Geim A K, Novoselov K S 2007 Nature Mater. 6 183
[4]	Lee C, Wei X, Kysar J W, Hone J 2008 Science 321 385
[5]	Castro Neto A H, Guinea F, Peres N M R, Novoselov K S, Geim A K 2009 Rev. Mod. Phys. 81 109
[6]	Gao Y, Zhang Y, Chen P, Li Y, Liu M, Gao T, Ma D, Chen Y, Cheng Z, Qiu X, Duan W, Liu Z 2013 Nano Lett. 13 3439
[7]	Geim A K, Grigorieva I V 2013 Nature 499 419
[8]	Gilje S, Han S, Wang M, Wang K L, Kaner R B 2007 Nano Lett. 7 3394
[9]	Oostinga J B, Heersche H B, Liu X, Morpurgo A F, Vandersypen L M K 2007 Nature Mater. 7 151
[10]	Blake P, Brimicombe P D, Nair R R, Booth T J, Jiang D, Schedin F, Ponomarenko L A, Morozov S V, Gleeson H F, Hill E W, Geim A K, Novoselov K S 2008 Nano Lett. 8 1704
[11]	Xia F, Mueller T, Lin Y M, Valdes-Garcia A, Avouris P 2009 Nature Nanotech. 4 839
[12]	Dean C R, Young A F, Meric I, Lee C, Wang L, Sorgenfrei S, Watanabe K, Taniguchi T, Kim P, Shepard K L, Hone J 2010 Nature Nanotech. 5 722
[13]	Lu X B, Zhang G Y 2015 Acta Phys. Sin. 64 077305 (in Chinese) [卢晓波, 张广宇 2015 64 077305]
[14]	Liu M X, Zhang Y F, Liu Z F 2015 Acta Phys. Sin. 64 078101 (in Chinese) [刘梦溪, 张艳锋, 刘忠范 2015 64 078101]
[15]	Zhang K, Zhang H, Cheng X 2016 Chin. Phys. B 25 037104
[16]	Li G F, Hu J, Lv H, Cui Z, Hou X, Liu S, Du Y 2016 Chin. Phys. B 25 027304
[17]	Jin C, Lin F, Suenaga K, Iijima S 2009 Phys. Rev. Lett. 102 195505
[18]	Alem N, Erni R, Kisielowski C, Rossell M D, Gannett W, Zettl A 2009 Phys. Rev. B 80 155425
[19]	Shi Y, Hamsen C, Jia X, Kim K K, Reina A, Hofmann M, Hsu A L, Zhang K, Li H, Juang Z Y, Dresselhaus M S, Li L J, Kong J 2010 Nano Lett. 10 4134
[20]	Song L, Ci L, Lu H, Sorokin P B, Jin C, Ni J, Kvashnin A G, Kvashnin D G, Lou J, Yakobson B I, Ajayan P M 2010 Nano Lett. 10 3209
[21]	Kim K K, Hsu A, Jia X, Kim S M, Shi Y, Hofmann M, Nezich D, Rodriguez-Nieva J F, Dresselhaus M, Palacios T, Kong J 2012 Nano Lett. 12 161
[22]	Yin J, Yu J, Li X, Li J, Zhou J, Zhang Z, Guo W 2015 Small 11 4497
[23]	Li X, Yin J, Zhou J, Guo W 2014 Nanotechnology 25 105701
[24]	Radisavljevic B, Radenovic A, Brivio J, Giacometti V, Kis A 2011 Nature Nanotech. 6 147
[25]	Ross J S, Wu S, Yu H, Ghimire N J, Jones A M, Aivazian G, Yan J Q, Mandrus D G, Xiao D, Yao W, Xu X D 2013 Nat. Commun. 4 1474
[26]	Ma Y D, Dai Y, Guo M, Niu C W, Lu J B, Huang B B 2011 Phys. Chem. Chem. Phys. 13 15546
[27]	Georgiou T, Jalil R, Belle B D, Britnell L, Gorbachev R V, Morozov S V, Kim Y J, Gholinia A, Haigh S J, Makarovsky O, Eaves L, Ponomarenko L A, Geim A K, Novoselov K S, Mishchenko A 2013 Nature Nanotech. 8 100
[28]	Chiritescu C, Cahill D G, Nguyen N, Johnson D, Bodapati A, Keblinski P, Zschack P 2007 Science 135 351
[29]	Fang H, Chuang S, Chang T C, Takei K, Takahashi T, Javey A 2012 Nano Lett. 12 3788
[30]	Watanabe K, Taniguchi T, Kanda H 2004 Nature Mater. 3 404
[31]	Kim K K, Hsu A, Jia X, Kim S M, Shi Y, Dresselhaus M, Palacios T, Kong J 2012 ACS Nano 6 8583
[32]	Kubota Y, Watanabe K, Tsuda O, Taniguchi T 2007 Science 317 932
[33]	Laskowski R, Blaha P, Gallauner T, Schwarz K 2007 Phys. Rev. Lett. 98 106802
[34]	Brugger T, Gnther S, Wang B, Hugo Dil J, Bocquet M L, Osterwalder J, Wintterlin J, Greber T 2009 Phys. Rev. B 79 045407
[35]	Sutter P, Lahiri J, Albrecht P, Sutter E 2011 ACS Nano 5 7303
[36]	Nagashima A, Tejima N, Gamou Y, Kawai T, Oshima C 1995 Phys. Rev. B 51 4606
[37]	Rokuta E, Hasegawa Y, Suzuki K, Gamou Y, Oshima C, Nagashima A 1997 Phys. Rev. Lett. 79 4609
[38]	Auwrter W, Suter H U, Sachdev H, Greber T 2004 Chem. Mater. 16 343
[39]	Schulz F, Drost R, Hmlinen S K, Demonchaux T, Seitsonen A P, Liljeroth P 2014 Phys. Rev. B 89 235429
[40]	Mller F, Stwe K, Sachdev H 2005 Chem. Mater. 17 3464
[41]	Morscher M, Corso M, Greber T, Osterwalder J 2006 Surf. Sci. 600 3280
[42]	Corso M, Greber T, Osterwalder J 2005 Surf. Sci. 577 L78
[43]	Preobrajenski A B, Vinogradov A S, Ng M L, Ćavar E, Westerstrm R, Mikkelsen A, Lundgren E, Mrtensson N 2007 Phys. Rev. B 75 245412
[44]	Joshi S, Ecija D, Koitz R, Iannuzzi M, Seitsonen A P, Hutter J, Sachdev H, Vijayaraghavan S, Bischoff F, Seufert K, Barth J V, Auwrter W 2012 Nano Lett. 12 5821
[45]	Tay R Y, Griep M H, Mallick G, Tsang S H, Singh R S, Tumlin T, Teo E H, Karna S P 2014 Nano Lett. 14 839
[46]	Kim G, Jang A R, Jeong H Y, Lee Z, Kang D J, Shin H S 2013 Nano Lett. 13 1834
[47]	Kidambi P R, Blume R, Kling J, Wagner J B, Baehtz C, Weatherup R S, Schloegl R, Bayer B C, Hofmann S 2014 Chem. Mater. 26 6380

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