铜氧化层及其上制备锑纳米结构的STM研究

铜氧化层及其上制备锑纳米结构的STM研究

钟  毓，黄  敏，于迎辉^*

(1. 中国科学院精密测量科学与技术创新研究院，波谱与原子分子物理国家重点实验室，湖北武汉430071；2．中国科学院大学，北京100039；3. 湖北大学物理与电子科学学院，湖北武汉430062)

摘  要  利用高分辨扫描隧道显微镜(STM)研究了Cu(111)和Cu(110)的氧化层及其上形成的锑纳米结构。Cu(111)表面氧化形成褶皱起伏的(√13R46°× √93R22°)结构，在其表面沉积锑原子，出现由长程有序的氧化层结构到无序再到长程有序锑结构的转变。通过原子分辨的STM研究发现，长程有序的锑结构可表征为(√7 × √7)R19°或(√7 × √7)R41°。Cu(110)表面氧化形成(2 × 1)和c(6 × 2)结构，结合密度泛函理论计算，给出了二者的几何模型。在其表面沉积锑原子，形成高低起伏的(6 × 6)和少量平整的c(2 × 2) 锑结构。在铜单晶表面沉积锑原子并氧化的情况下并未观察到上述各纳米结构。

关键词 氧化层；锑纳米结构；扫描隧道显微镜

中图分类号：TB383；TG115  文献标识码：Adoi:10.3969/j.issn.1000-6281.2021.04.005

STM studies of copper oxide layers and fabricated antimony nanostructures

ZHONG Yu^1，2，HUANG Min³，YU Ying-hui³*

(1. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan Hubei 430071；

2. University of Chinese Academy of Sciences, Beijing 10004；3. Faculty of Physics and Electronic Sciences, Hubei University, Wuhan Hubei 430062, China)

Abstract  The oxide layers of Cu(111) and Cu(110) as well as the fabricated antimony nanostructures are systemically studied by high-resolution scanning tunneling microscope (STM). The oxidation of Cu(111) surface forms a corrugated row-like oxide structure with a (√13R46°× √93R22°) unit celland six inequivalent orientations. Initially the antimony deposition leads to structural transformation from long-range order to disorder. Subsequently, a well-ordered antimony structure forms with uniform atomic heights and is assigned to (√7 × √7)R19°or (√7 × √7)R41°phase as characterized by atomically-resolved STM. For Cu(110), the oxidation forms the (2 × 1) and c(6 × 2) structures at different oxygen-exposure and annealing conditions. Combined with density functional theory calculations, the models of both structures are addressed. Antimony deposition on the oxide layer of Cu(110) gives rise to formation of wrinkled (6 × 6) and flat c(2 × 2) structures. The wrinkled (6 × 6) structure consists of protruded and dipped Sb atoms. Contrastly, the oxidation of deposited antimony on pristine copper surfaces forms disordered structures.

Keywords   oxide layer；antimony nanostructure；scanning tunneling microscope

 “全文下载请到同方知网，万方数据库或重庆维普等数据库中下载！”

[1] BANSZERUS L, SCHMITZ M, ENGELS S, et al. Ultrahigh-mobility graphene devices from chemical vapor deposition on reusable copper [J]. Science Advances, 2015, 1: e1500222.

[2] DENG J, XIA B, MA X, et al. Epitaxial growth of ultraflat stanene with topological band inversion[J]. Nature Materials, 2018, 17(12): 1081–1086.

[3] XIAO H Y, ZU X T, HE X, et al. Sb adsorption on Cu(1 1 0), (1 0 0), and (1 1 1) surfaces[J]. Chemical Physics, 2006, 325(2/3): 519–524.

[4] 佘利敏，于迎辉，卢双赞，等. Sb /Cu(111) 表面上酞氰钴分子的吸附取向与自组装结构研究[J]. 电子显微学报，2013，32(3):219-223.

[5] DENK M, DENK R, HOHAGE M, et al. Effect of postgrowth oxygen exposure on the magnetic properties of Ni on the Cu-CuO stripe phase[J]. Physical Review B, 2012, 85(1): 014423.

[6] ERNST K H, LUDVIKSSON A, ZHANG R, et al. Growth model for metal films on oxide surfaces: Cu on ZnO(0001)-O[J]. Physical Review B, 1993, 47(20): 13782–13796.

[7] DIEBOLD U, PAN J M, MADEY T E. Growth mode of ultrathin copper overlayers on TiO2(110)[J]. Physical Review B, 1993, 47(7): 3868–3876.

[8] FORTUNATO E, BARQUINHA P, MARTINS R. Oxide semiconductor thin-film transistors: a review of recent advances[J]. Advanced Materials, 2012, 24(22): 2945–2986.

[9] YU X, MARKS T J, FACCHETTI A. Metal oxides for optoelectronic applications[J]. Nature Materials, 2016, 15(4): 383–396.

[10] HEREMANS J, THRUSH C M, LIN Y M, et al. Transport properties of antimony nanowires[J]. Physical Review B, 2001, 63(8): 854061–854068.

[11] ZHANG M, WANG Z, XI G, et al. Large-scale synthesis of antimony nanobelt bundles[J]. Journal of Crystal Growth, 2004, 268(1/2): 215–221.

[12] HU H, MO M, YANG B, et al. A rational complexing-reduction route to antimony nanotubes[J]. New Journal of Chemistry, 2003, 27(8): 1161–1163.

[13] ZHANG S, YAN Z, LI Y, et al. Atomically thin arsenene and antimonene: semimetal-semiconductor and indirect-direct band-gap transitions[J]. Angewandte Chemie - International Edition, 2015, 54(10): 3112–3115.

[14] NIU T, ZHOU W, ZHOU D, et al. Modulating epitaxial atomic structure of antimonene through interface design[J]. Advanced Materials, 2019, 31(29): 1902606.

[15] ZHU S Y, SHAO Y, WANG E, et al. Evidence of topological edge states in buckled antimonene monolayers[J]. Nano Letters, 2019, 19(9): 6323–6329.

[16] WANG X, SONG J, QU J. Antimonene: From experimental preparation to practical application[J]. Angewandte Chemie - International Edition, 2019, 58(6): 1574–1584.

[17] KRESSE G, HAFNER J. Ab initio molecular dynamics for liquid metals[J]. Physical Review B, 1993, 47: 558.

[18] KRESSE G, FURTHMÜLLER J.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[J].  Physical Review B, 1996, 54: 11169.

[19] PERDEW J P, BURKE K, ERNZERHOF M. Generalized gradient approximation made simple[J]. Physical Review Letters, 1996, 77: 3865.

[20] KRESSE G, JOUBERT D. From ultrasoft pseudopotentials to the projector augmented-wave method[J]. Physical Review B, 1999, 59: 1758.

[21] WIAME F, MAURICE V, MARCUS P. Initial stages of oxidation of Cu(1 1 1)[J]. Surface Science, 2007, 601(5): 1193–1204.

[22] JENSEN F, BESENBACHER F, LAEGSGAARD E, et al. Oxidation of Cu(111): two new oxygen induced reconstructions[J]. Surface Science Letters, 1991, 259(111): L774–L780.

[23] MATSUMOTO T, BENNETT R A, STONE P, et al. Scanning tunneling microscopy studies of oxygen adsorption on Cu (111) [J]. Surface Science, 2001, 471(1/2/3): 225–245.

[24] YANG F, CHOI Y, LIU P, et al. Autocatalytic reductibon of a Cu₂O/Cu(111) surface by CO: STM, XPS, and DFT studies[J]. Journal of Physical Chemistry C, 2010, 114(40): 17042–17050.

[25] THERRIEN A J, ZHANG R, LUCCI F R, et al. Structurally accurate model for the “29” -structure of Cu_xO/Cu(111): a DFT and STM study[J]. Journal of Physical Chemistry C, 2016, 120(20): 10879–10886.

[26] AN W, XU F, STACCHIOLA D, et al. Potassium-induced effect on the structure and chemical activity of the Cu_xO/Cu(111) (x ≤ 2) surface: a combined scanning tunneling microscopy and density functional theory study[J]. ChemCatChem, 2015, 7(23): 3865–3872.

[27] DORENBOS G, BREEMAN M, BOERMA D O. Low-energy ion-scattering study of the oxygen-induced reconstructed p(2 × 1) and c(6 × 2) surfaces of Cu(110)[J]. Physical Review B, 1993, 47: 1580–1588.

[28] COULMAN D J, WINTTERLIN J, BEHM R J, et al. Novel mechanism for the formation of chemisorption phases: the (2 × 1 )O-Cu(110) “added-row” reconstruction[J]. Physical Review Letters, 1990, 64(15): 1761–1764.

[29] POUTHIER V, RAMSEYER C, GIRARDET C, et al.Characterization of the reconstruction by means of molecular adsorption [J]. Physical Review B, 1998, 58(15): 9998–10002.

[30] CABRERA-SANFELIX P, LIN C, ARNAU A, et al. Hybridization between Cu-O chain and Cu(110) surface states in the O(2 × 1)/Cu(110) surface from first principles[J]. Journal of Physics Condensed Matter, 2013, 25: 135003.

[31] DUAN X, WARSCHKOW O, SOON A, et al. Density functional study of oxygen on Cu(100) and Cu(110) surfaces[J]. Physical Review B, 2010, 81(7): 075430.

[32] LIU Q, LI L, CAI N, et al.  Oxygen chemisorption-induced surface phase transitions on Cu(110)[J]. Surface Science, 2014, 627: 75–84.