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Atom Probe Study of 1-Octadecanethiol Self-Assembled Monolayers on Platinum (111) and (200) Surfaces

Published online by Cambridge University Press:  07 September 2021

Helena Solodenko Open the ORCID record for Helena Solodenko [Opens in a new window] ,
Patrick Stender Open the ORCID record for Patrick Stender [Opens in a new window]  and
Guido Schmitz
Helena Solodenko*
Affiliation:
Institute for Materials Science, Chair of Materials Physics, University of Stuttgart, Heisenbergstr. 3, 70569 Stuttgart, Germany
Patrick Stender
Affiliation:
Institute for Materials Science, Chair of Materials Physics, University of Stuttgart, Heisenbergstr. 3, 70569 Stuttgart, Germany
Guido Schmitz
Affiliation:
Institute for Materials Science, Chair of Materials Physics, University of Stuttgart, Heisenbergstr. 3, 70569 Stuttgart, Germany
*
*Corresponding author: Helena Solodenko, E-mail: [email protected]
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Abstract

Atom probe tomography measurements of self-assembled monolayers of 1-octadecanethiol on platinum tips were performed and their fragmentation behavior under the influence of different laser powers was investigated. The carbon backbone evaporates in the form of small hydrocarbon fragments consisting of one to four carbon atoms, while sulfur evaporates exclusively as single ions. The carbon molecules evaporate at very low fields of 5.9 V/nm, while S requires a considerably higher evaporation field of 23.4 V/nm. With increasing laser power, a weak, but noticeable trend toward larger fragment sizes is observed. No hydrocarbon fragments containing S are detected, indicating that a strong S–Pt bond has formed. The observed surface coverage of S fits well with literature values and is higher for (111)-oriented samples than for (200).

Keywords

coveragefragmentationlaser dependencethiolate
Type
Applications in Biology
Information
Microscopy and Microanalysis , Volume 28 , Issue 4 , August 2022 , pp. 1300 - 1309
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Copyright
Copyright © The Author(s), 2021. Published by Cambridge University Press on behalf of the Microscopy Society of America

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References

Acharya, R, Peng, B, Chan, PKL, Schmitz, G & Klauk, H (2019). Achieving ultralow turn-on voltages in organic thin-film transistors: Investigating fluoroalkylphosphonic acid self-assembled monolayer hybrid dielectrics. ACS Appl Mater Interfaces 11, 27104–27111.CrossRefGoogle ScholarPubMed
Alagta, A, Felhösi, I, Bertoti, I & Kálmán, E (2008). Corrosion protection properties of hydroxamic acid self-assembled monolayer on carbon steel. Corros Sci 50, 1644–1649.CrossRefGoogle Scholar
Appa Rao, BV, Yakub Iqbal, M & Sreedhar, B (2009). Self-assembled monolayer of 2-(octadecylthio)benzothiazole for corrosion protection of copper. Corros Sci 51, 1441–1452.CrossRefGoogle Scholar
Bas, P, Bostel, A, Deconihout, B & Blavette, D (1995). A general protocol for the reconstruction of 3D atom probe data. Appl Surf Sci 87–88, 298–304.CrossRefGoogle Scholar
Beebe, JM, Engelkes, VB, Miller, LL & Frisbie, CD (2002). Contact resistance in metal-molecule-metal junctions based on aliphatic SAMs: Effects of surface linker and metal work function. J Am Chem Soc 124, 11268–11269.CrossRefGoogle ScholarPubMed
Blobner, F, Abufager, PN, Han, R, Bauer, J, Duncan, DA, Maurer, RJ, Reuter, K, Feulner, P & Allegretti, F (2015). Thiolate-bonded self-assembled monolayers on Ni(111): Bonding strength, structure, and stability. J Phys Chem C 119, 15455–15468.CrossRefGoogle Scholar
Cairney, JM, McCarroll, I, Chen, Y-S, Eder, K, Sato, T, Liu, Z, Rosenthal, A & Wepf, R (2019). Correlative UHV-cryo transfer suite: Connecting atom probe, SEM-FIB, transmission electron microscopy via an environmentally-controlled glovebox. Microsc Microanal 25, 2494–2495.CrossRefGoogle Scholar
Casalini, S, Bortolotti, CA, Leonardi, F & Biscarini, F (2017). Self-assembled monolayers in organic electronics. Chem Soc Rev 46, 40–71.CrossRefGoogle ScholarPubMed
Chen, Y-S, Griffith, MJ & Cairney, JM (2021). Cryo atom probe: Freezing atoms in place for 3D mapping. Nano Today 37, 101107.CrossRefGoogle Scholar
Colorado, R & Lee, TR (2003). Wettabilities of self-assembled monolayers on gold generated from progressively fluorinated alkanethiols. Langmuir 19, 3288–3296.CrossRefGoogle Scholar
Dietrich, CA, Schuldt, R, Born, D, Solodenko, H, Schmitz, G & Kästner, J (2020). Evaporation and fragmentation of organic molecules in strong electric fields simulated with DFT. J Phys Chem A 124, 8633–8642.CrossRefGoogle ScholarPubMed
Eder, K, Felfer, PJ, Gault, B, Ceguerra, AV, La Fontaine, A, Masters, AF, Maschmeyer, T & Cairney, JM (2017). A new approach to understand the adsorption of thiophene on different surfaces: An atom probe investigation of self-assembled monolayers. Langmuir 33, 9573–9581.CrossRefGoogle ScholarPubMed
El-Zoka, AA, Kim, S-H, Deville, S, Newman, RC, Stephenson, LT & Gault, B (2020). Enabling near-atomic-scale analysis of frozen water. Sci Adv 6, eabd6324.CrossRefGoogle ScholarPubMed
Floridia Addato, MA, Rubert, AA, Benítez, GA, Fonticelli, MH, Carrasco, J, Carro, P & Salvarezza, RC (2011). Alkanethiol adsorption on platinum: Chain length effects on the quality of self-assembled monolayers. J Phys Chem C 115, 17788–17798.CrossRefGoogle Scholar
Gault, B, Danoix, F, Hoummada, K, Mangelinck, D & Leitner, H (2012 a). Impact of directional walk on atom probe microanalysis. Ultramicroscopy 113, 182–191.CrossRefGoogle Scholar
Gault, B, Moody, MP, Cairney, JM & Ringer, SP (2012 b). Atom Probe Microscopy. New York, NY: Springer New York; Springer e-books; Imprint; Springer.CrossRefGoogle Scholar
Gault, B, Yang, W, Ratinac, KR, Zheng, R, Braet, F & Ringer, SP (2010). Atom probe microscopy of self-assembled monolayers: Preliminary results. Langmuir 26, 5291–5294.CrossRefGoogle ScholarPubMed
Gerstl, S & Wepf, R (2015). Methods in creating, transferring, & measuring cryogenic samples for APT. Microsc Microanal 21, 517–518.CrossRefGoogle Scholar
Gerstl, SS, Tacke, S, Chen, Y-S, Wagner, J & Wepf, R (2017). Enabling atom probe analyses of new materials classes with vacuum-cryo-transfer capabilities. Microsc Microanal 23, 612–613.CrossRefGoogle Scholar
Houston, JE & Kim, HI (2002). Adhesion, friction, and mechanical properties of functionalized alkanethiol self-assembled monolayers. Acc Chem Res 35, 547–553.CrossRefGoogle ScholarPubMed
Jedaa, A, Burkhardt, M, Zschieschang, U, Klauk, H, Habich, D, Schmid, G & Halik, M (2009). The impact of self-assembled monolayer thickness in hybrid gate dielectrics for organic thin-film transistors. Org Electron 10, 1442–1447.CrossRefGoogle Scholar
Jeske, T & Schmitz, G (2001). Nanoscale analysis of the early interreaction stages in Al/Ni. Scr Mater 45, 555–560.CrossRefGoogle Scholar
Kelly, TF, Nishikawa, O, Panitz, JA & Prosa, TJ (2009). Prospects for nanobiology with atom-probe tomography. MRS Bull 34, 744–750.CrossRefGoogle Scholar
Kingham, DR (1982). The post-ionization of field evaporated ions: A theoretical explanation of multiple charge states. Surf Sci 116, 273–301.CrossRefGoogle Scholar
Leggett, GJ (2003). Friction force microscopy of self-assembled monolayers: Probing molecular organisation at the nanometre scale. Anal Chim Acta 479, 17–38.CrossRefGoogle Scholar
Li, Z, Chang, S-C & Williams, RS (2003). Self-assembly of alkanethiol molecules onto platinum and platinum oxide surfaces. Langmuir 19, 6744–6749.CrossRefGoogle Scholar
Love, JC, Estroff, LA, Kriebel, JK, Nuzzo, RG & Whitesides, GM (2005). Self-assembled monolayers of thiolates on metals as a form of nanotechnology. Chem Rev 105, 1103–1169.CrossRefGoogle ScholarPubMed
Meng, K, Schwarz, TM, Weikum, EM, Stender, P & Schmitz, G (2021). Frozen n-tetradecane investigated by cryo-atom probe tomography. J Microsc Microanal. doi:10.1017/S143192762101254X.Google Scholar
Miller, MK (2000). Atom Probe Tomography: Analysis at the Atomic Level. Boston, MA: Springer US.CrossRefGoogle Scholar
Miller, MK & Forbes, RG (2014). The local electrode atom probe. In Atom-Probe Tomography. Boston, MA: Springer.CrossRefGoogle Scholar
Nam, AJ (1995). Benign making of sharp tips for STM and FIM: Pt, Ir, Au, Pd, and Rh. J Vac Sci Technol B 13, 1556.CrossRefGoogle Scholar
Nickerson, BS, Karahka, M & Kreuzer, HJ (2015). Disintegration and field evaporation of thiolate polymers in high electric fields. Ultramicroscopy 159(Pt 2), 173–177.CrossRefGoogle ScholarPubMed
Nishikawa, O, Taniguchi, M & Saito, Y (2008). Study of characteristic fragmentation of nanocarbon by the scanning atom probe. J Vac Sci Technol A 26, 1074–1078.CrossRefGoogle Scholar
Perea, DE, Liu, J, Bartrand, J, Dicken, Q, Thevuthasan, ST, Browning, ND & Evans, JE (2016). Atom probe tomographic mapping directly reveals the atomic distribution of phosphorus in resin embedded ferritin. Sci Rep 6, 22321.CrossRefGoogle ScholarPubMed
Petrovykh, DY, Kimura-Suda, H, Opdahl, A, Richter, LJ, Tarlov, MJ & Whitman, LJ (2006). Alkanethiols on platinum: Multicomponent self-assembled monolayers. Langmuir 22, 2578–2587.CrossRefGoogle ScholarPubMed
Prosa, TJ, Keeney, SK & Kelly, TF (2010). Atom probe tomography analysis of poly(3-alkylthiophene)s. J Microsc 237, 155–167.CrossRefGoogle ScholarPubMed
Prosa, TJ, Kostrna, SLP & Kelly, TF (2006). Laser atom probe tomography: Application to polymers. In 19th International Vacuum Nanoelectronics, pp. 533–534.CrossRefGoogle Scholar
Proudian, AP, Jaskot, MB, Diercks, DR, Gorman, BP & Zimmerman, JD (2019). Atom probe tomography of molecular organic materials: Sub-dalton nanometer-scale quantification. Chem Mater 31, 2241–2247.CrossRefGoogle Scholar
Rechmann, J, Krzywiecki, M & Erbe, A (2019). Carbon-sulfur bond cleavage during adsorption of octadecane thiol to copper in ethanol. Langmuir 35, 6888–6897.CrossRefGoogle Scholar
Sauvage, X, Vurpillot, F & Lefebvre-Ulrikson, W (2016). Atom Probe Tomography: Put Theory into Practice. Cambride, MA, USA: Academic Press.Google Scholar
Saxey, DW (2011). Correlated ion analysis and the interpretation of atom probe mass spectra. Ultramicroscopy 111, 473–479.CrossRefGoogle ScholarPubMed
Schlesiger, R, Oberdorfer, C, Würz, R, Greiwe, G, Stender, P, Artmeier, M, Pelka, P, Spaleck, F & Schmitz, G (2010). Design of a laser-assisted tomographic atom probe at Münster University. Rev Sci Instrum 81, 43703.CrossRefGoogle ScholarPubMed
Schwartz, DK (2001). Mechanisms and kinetics of self-assembled monolayer formation. Annu Rev Phys Chem 52, 107–137.CrossRefGoogle ScholarPubMed
Schwarz, TM, Weikum, EM, Meng, K, Hadjixenophontos, E, Dietrich, CA, Kästner, J, Stender, P & Schmitz, G (2020). Field evaporation and atom probe tomography of pure water tips. Sci Rep 10, 20271.CrossRefGoogle ScholarPubMed
Stender, P & Balla, I (2018). Inspico - High resolution analysis. Available at: https://inspico.eu/ (accessed March 25, 2021).Google Scholar
Stender, P, Gault, B, Schwarz, TM, Woods, EV, Kim, S-H, Ott, J, Stephenson, LT, Schmitz, G, Freysoldt, C, Kästner, J & El-Zoka, AA (2021). Status and direction of atom probe analysis of frozen liquids. Microsc Microanal (submitted). arXiv:2102.01954.Google Scholar
Stender, P, Oberdorfer, C, Artmeier, M, Pelka, P, Spaleck, F & Schmitz, G (2007). New tomographic atom probe at University of Muenster, Germany. Ultramicroscopy 107, 726–733.CrossRefGoogle ScholarPubMed
Stoffers, A, Oberdorfer, C & Schmitz, G (2012). Controlled field evaporation of fluorinated self-assembled monolayers. Langmuir 28, 56–59.CrossRefGoogle ScholarPubMed
Taniguchi, M, Nishikawa, O & Ikai, A (2012). Atomic level analysis of biomolecules by a scanning atom probe. Surf Interface Anal 44, 721–723.CrossRefGoogle Scholar
Tsong, TT (2005). Atom-Probe Field Ion Microscopy: Field Ion Emission, and Surfaces and Interfaces at Atomic Resolution. Cambridge: Cambridge University Press.Google Scholar
Ulman, A (1996). Formation and structure of self-assembled monolayers. Chem Rev 96, 1533–1554.CrossRefGoogle ScholarPubMed
Vericat, C, Vela, ME, Corthey, G, Pensa, E, Cortés, E, Fonticelli, MH, Ibañez, F, Benitez, GE, Carro, P & Salvarezza, RC (2014). Self-assembled monolayers of thiolates on metals: A review article on sulfur-metal chemistry and surface structures. RSC Adv 4, 27730–27754.CrossRefGoogle Scholar
Whitesides, GM & Laibinis, PE (1990). Wet chemical approaches to the characterization of organic surfaces: Self-assembled monolayers, wetting, and the physical-organic chemistry of the solid-liquid interface. Langmuir 6, 87–96.CrossRefGoogle Scholar
Zhang, Y & Hillier, AC (2010). Three-dimensional atom probe tomography of oxide, anion, and alkanethiolate coatings on gold. Anal Chem 82, 6139–6147.CrossRefGoogle ScholarPubMed
Zschieschang, U & Klauk, H (2015). Low-voltage organic transistors with steep subthreshold slope fabricated on commercially available paper. Org Electron 25, 340–344.CrossRefGoogle Scholar