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      Surface NMR using quantum sensors in diamond

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          Significance

          Many of the functions and applications of materials in catalysis, energy conversion, drug delivery, bioanalysis, and electronics are based on their interfacial properties and structures. The characterization of their molecular properties under ambient or chemically reactive conditions is a fundamental scientific challenge. Here, we develop a surface-sensitive magnetic resonance technique that combines the nanoscale-sensing capabilities of defects in diamond with a high precision and versatile protocol for diamond surface modification. We demonstrate the functionality of this method for probing the molecular properties and kinetics at surfaces and interfaces under ambient conditions.

          Abstract

          NMR is a noninvasive, molecular-level spectroscopic technique widely used for chemical characterization. However, it lacks the sensitivity to probe the small number of spins at surfaces and interfaces. Here, we use nitrogen vacancy (NV) centers in diamond as quantum sensors to optically detect NMR signals from chemically modified thin films. To demonstrate the method’s capabilities, aluminum oxide layers, common supports in catalysis and materials science, are prepared by atomic layer deposition and are subsequently functionalized by phosphonate chemistry to form self-assembled monolayers. The surface NV-NMR technique detects spatially resolved NMR signals from the monolayer, indicates chemical binding, and quantifies molecular coverage. In addition, it can monitor in real time the formation kinetics at the solid–liquid interface. With our approach, we show that NV quantum sensors are a surface-sensitive NMR tool with femtomole sensitivity for in situ analysis in catalysis, materials, and biological research.

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          Most cited references55

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          Surface chemistry of atomic layer deposition: A case study for the trimethylaluminum/water process

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            Quantum sensing

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              SRIM – The stopping and range of ions in matter (2010)

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                Author and article information

                Journal
                Proc Natl Acad Sci U S A
                Proc Natl Acad Sci U S A
                pnas
                PNAS
                Proceedings of the National Academy of Sciences of the United States of America
                National Academy of Sciences
                0027-8424
                1091-6490
                26 January 2022
                1 February 2022
                26 January 2022
                : 119
                : 5
                : e2111607119
                Affiliations
                [1] aDepartment of Chemistry, Technical University of Munich , Munich 85748, Germany;
                [2] bWalter Schottky Institute, Technical University of Munich , Garching 85748, Germany;
                [3] cPhysics Department, Technical University of Munich , Garching 85748, Germany
                Author notes
                1To whom correspondence may be addressed. Email: dominik.bucher@ 123456tum.de .

                Edited by D. D. Awschalom, Pritzker School of Molecular Engineering, The University of Chicago, Chicago, IL; received June 24, 2021; accepted December 10, 2021

                Author contributions: D.B.B. designed research; K.S.L. and R.R. performed research; A.H., M.W.H., R.D.A., J.D.B., and I.D.S. contributed new reagents/analytic tools; K.S.L., A.H., R.R., and D.B.B. analyzed data; and K.S.L., R.R., and D.B.B. wrote the paper.

                Author information
                https://orcid.org/0000-0001-8532-4503
                https://orcid.org/0000-0003-0419-4992
                https://orcid.org/0000-0001-7968-617X
                https://orcid.org/0000-0003-3767-8782
                https://orcid.org/0000-0001-5238-7487
                Article
                202111607
                10.1073/pnas.2111607119
                8812553
                35082146
                f196cf61-f181-47af-8c8d-63e00c215dc9
                Copyright © 2022 the Author(s). Published by PNAS.

                This article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND).

                History
                : 10 December 2021
                Page count
                Pages: 8
                Funding
                Funded by: Deutsche Forschungsgemeinschaft (DFG) 501100001659
                Award ID: 412351169
                Award Recipient : Kristina S. Liu Award Recipient : Markus W Heindl Award Recipient : Robin D Allert Award Recipient : Johannes D. Bartl Award Recipient : Ian D Sharp Award Recipient : Roberto Rizzato Award Recipient : Dominik B Bucher
                Funded by: Deutsche Forschungsgemeinschaft (DFG) 501100001659
                Award ID: 390776260
                Award Recipient : Kristina S. Liu Award Recipient : Markus W Heindl Award Recipient : Robin D Allert Award Recipient : Johannes D. Bartl Award Recipient : Ian D Sharp Award Recipient : Roberto Rizzato Award Recipient : Dominik B Bucher
                Funded by: Deutsche Forschungsgemeinschaft (DFG) 501100001659
                Award ID: RI 3319/1-1
                Award Recipient : Kristina S. Liu Award Recipient : Markus W Heindl Award Recipient : Robin D Allert Award Recipient : Johannes D. Bartl Award Recipient : Ian D Sharp Award Recipient : Roberto Rizzato Award Recipient : Dominik B Bucher
                Funded by: EC | H2020 | H2020 Priority Excellent Science | H2020 European Research Council (ERC) 100010663
                Award ID: 841556
                Award Recipient : Alex Henning
                Categories
                405
                Physical Sciences
                Applied Physical Sciences

                quantum sensing,surface analysis,spectroscopy,nv center in diamond,self-assembled monolayer

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