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Control of Surface and Edge Oxidation on Phosphorene
Kuntz, Kaci L.; Wells, Rebekah A.; Hu, Jun; Yang, Teng; Dong, Baojuan; Guo, Huaihong; Woomer, Adam H.; Druffel, Daniel L.; Alabanza, Anginelle; Tomanek, David; Warren, Scott C.; Warren, SC (reprint author), Univ North Carolina Chapel Hill, Dept Chem, Chapel Hill, NC 27599 USA.; Warren, SC (reprint author), Univ North Carolina Chapel Hill, Dept Appl Phys Sci, Chapel Hill, NC 27599 USA.
2017-03-15
Source PublicationACS APPLIED MATERIALS & INTERFACES
ISSN1944-8244
Volume9Issue:10Pages:9126-9135
AbstractPhosphorene is emerging as an important two-dimensional semiconductor, but controlling the surface chemistry of phosphorene remains a significant challenge. Here, we show that controlled oxidation of phosphorene determines the composition and spatial distribution of the resulting oxide. We used X-ray photoemission spectroscopy to measure the binding energy shifts that accompany oxidation. We interpreted these spectra by calculating the binding energy shift for 24 likely bonding configurations, including phosphorus oxides and hydroxides located on the basal surface or edges of flakes. After brief exposure to high-purity oxygen or high-purity water vapor at room temperature, we observed phosphorus in the +1 and +2 oxidation states; longer exposures led to a large population of phosphorus in the +3 oxidation state. To provide insight into the spatial distribution of the oxide, transmission electron microscopy was performed at several stages during the oxidation. We found crucial differences between oxygen and water oxidants: while pure oxygen produced an oxide layer on the van der Waals surface, water oxidized the material at pre-existing defects such as edges or steps. We propose a mechanism based on the thermodynamics of electron transfer to interpret these observations. This work opens a route to functionalize the basal surface or edges of two-dimensional (2D) black phosphorus through site-selective chemical reactions and presents the opportunity to explore the synthesis of 2D phosphorene oxide by oxidation.; Phosphorene is emerging as an important two-dimensional semiconductor, but controlling the surface chemistry of phosphorene remains a significant challenge. Here, we show that controlled oxidation of phosphorene determines the composition and spatial distribution of the resulting oxide. We used X-ray photoemission spectroscopy to measure the binding energy shifts that accompany oxidation. We interpreted these spectra by calculating the binding energy shift for 24 likely bonding configurations, including phosphorus oxides and hydroxides located on the basal surface or edges of flakes. After brief exposure to high-purity oxygen or high-purity water vapor at room temperature, we observed phosphorus in the +1 and +2 oxidation states; longer exposures led to a large population of phosphorus in the +3 oxidation state. To provide insight into the spatial distribution of the oxide, transmission electron microscopy was performed at several stages during the oxidation. We found crucial differences between oxygen and water oxidants: while pure oxygen produced an oxide layer on the van der Waals surface, water oxidized the material at pre-existing defects such as edges or steps. We propose a mechanism based on the thermodynamics of electron transfer to interpret these observations. This work opens a route to functionalize the basal surface or edges of two-dimensional (2D) black phosphorus through site-selective chemical reactions and presents the opportunity to explore the synthesis of 2D phosphorene oxide by oxidation.
description.department[kuntz, kaci l. ; wells, rebekah a. ; hu, jun ; woomer, adam h. ; druffel, daniel l. ; alabanza, anginelle ; warren, scott c.] univ north carolina chapel hill, dept chem, chapel hill, nc 27599 usa ; [yang, teng ; dong, baojuan] chinese acad sci, shenyang natl lab mat sci, inst met res, shenyang 110016, peoples r china ; [guo, huaihong] liaoning shihua univ, coll sci, fushun 113001, peoples r china ; [tomanek, david] michigan state univ, dept phys & astron, e lansing, mi 48824 usa ; [warren, scott c.] univ north carolina chapel hill, dept appl phys sci, chapel hill, nc 27599 usa
Keyword2d Materials Black Phosphorus Phosphorene Oxidation Surface Functionalization Edge Functionalization Dft Binding Energy Shift
Subject AreaNanoscience & Nanotechnology ; Materials Science, Multidisciplinary
Funding OrganizationUNC Chapel Hill startup funds; ACS Petroleum Research Fund [55497-DNI3]; NSFC [51331006, U1537204]; NSF/AFOSR EFRI 2-DARE Grant [EFMA-1433459]; Liaoning Province Doctor Startup Fund [201601325]; Liaoning Shihua University Grant [2016XJJ-044]; National Science Foundation as part of the National Nanotechnology Coordinated Infrastructure, NNCI [ECCS-1542015]; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0001011]
Indexed BySCI
Language英语
Document Type期刊论文
Identifierhttp://ir.imr.ac.cn/handle/321006/78232
Collection中国科学院金属研究所
Corresponding AuthorWarren, SC (reprint author), Univ North Carolina Chapel Hill, Dept Chem, Chapel Hill, NC 27599 USA.; Warren, SC (reprint author), Univ North Carolina Chapel Hill, Dept Appl Phys Sci, Chapel Hill, NC 27599 USA.
Recommended Citation
GB/T 7714
Kuntz, Kaci L.,Wells, Rebekah A.,Hu, Jun,et al. Control of Surface and Edge Oxidation on Phosphorene[J]. ACS APPLIED MATERIALS & INTERFACES,2017,9(10):9126-9135.
APA Kuntz, Kaci L..,Wells, Rebekah A..,Hu, Jun.,Yang, Teng.,Dong, Baojuan.,...&Warren, SC .(2017).Control of Surface and Edge Oxidation on Phosphorene.ACS APPLIED MATERIALS & INTERFACES,9(10),9126-9135.
MLA Kuntz, Kaci L.,et al."Control of Surface and Edge Oxidation on Phosphorene".ACS APPLIED MATERIALS & INTERFACES 9.10(2017):9126-9135.
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