Structure of n-alkyltrichlorosilane mono layers on Si(100)/SiO2

Ocko, B.; Will, J.; Magerl, A.

doi:10.1021/acs.langmuir.5b03091

Title: Structure of n-alkyltrichlorosilane mono layers on Si(100)/SiO₂

Journal Article · Mon Oct 05 00:00:00 EDT 2015 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.5b03091· OSTI ID:1240699

Ocko, B. ^[1]; Will, J. ^[2]; Magerl, A. ^[2]

Brookhaven National Lab. (BNL), Upton, NY (United States)
Friedrich-Alexander-Univ Erlangen-Nurnberg, Erlangen (Germany)

The structure of n-alkyltrichlorosilane self-assembled monolayers (SAMs) of alkyl chain lengths n = 12, 14, 18, and 22 formed on the amorphous native oxide of silicon (100) has been investigated via angstrom-resolution surface X-ray scattering techniques, with particular focus on the proliferation of lateral order along the molecules’ long axis. Grazing incidence diffraction shows that the monolayer is composed of hexagonally packed crystalline-like domains for n = 14, 18, and 22 with a lateral size of about 60 Å. However, Bragg rod analysis shows that ~12 of the CH₂ units are not included in the crystalline-like domains. We assign this, and the limited lateral crystallites’ size, to strain induced by the size mismatch between the optimal chain–chain and headgroup–headgroup spacings. Lastly, analysis of X-ray reflectivity profiles for n = 12, 14, and 22 shows that the density profile used to successfully model n = 18 provides an excellent fit where the analysis-derived parameters provide complementary structural information to the grazing incidence results.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC00112704

OSTI ID:: 1240699

Report Number(s):: BNL-111848-2016-JA; R&D Project: PO034; KC0203010

Journal Information:: Langmuir, Vol. 31, Issue 43; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 25 works

Citation information provided by
Web of Science

References (57)

Organized monolayers by adsorption. 1. Formation and structure of oleophobic mixed monolayers on solid surfaces Sagiv, Jacob Journal of the American Chemical Society, Vol. 102, Issue 1 https://doi.org/10.1021/ja00521a016	journal	January 1980
Formation of monolayer films by the spontaneous assembly of organic thiols from solution onto gold Bain, Colin D.; Troughton, E. Barry; Tao, Yu Tai Journal of the American Chemical Society, Vol. 111, Issue 1, p. 321-335 https://doi.org/10.1021/ja00183a049	journal	January 1989
Engineering Silicon Oxide Surfaces Using Self-Assembled Monolayers Onclin, Steffen; Ravoo, Bart Jan; Reinhoudt, David N. Angewandte Chemie International Edition, Vol. 44, Issue 39 https://doi.org/10.1002/anie.200500633	journal	October 2005
Structure and growth of self-assembling monolayers Schreiber, Frank Progress in Surface Science, Vol. 65, Issue 5-8 https://doi.org/10.1016/S0079-6816(00)00024-1	journal	November 2000
Formation and Structure of Self-Assembled Monolayers Ulman, Abraham Chemical Reviews, Vol. 96, Issue 4, p. 1533-1554 https://doi.org/10.1021/cr9502357	journal	January 1996
Self-assembled monolayers for liquid crystal alignment: simple preparation on glass using alkyltrialkoxysilanes Walba, David M.; Liberko, Charles A.; Korblova, Eva Liquid Crystals, Vol. 31, Issue 4 https://doi.org/10.1080/02678290410001666075	journal	April 2004
The Potential of Molecular Self-Assembled Monolayers in Organic Electronic Devices Halik, Marcus; Hirsch, Andreas Advanced Materials, Vol. 23, Issue 22-23 https://doi.org/10.1002/adma.201100337	journal	April 2011
Highly oriented crystals at the buried interface in polythiophene thin-film transistors Joseph Kline, R.; McGehee, Michael D.; Toney, Michael F. Nature Materials, Vol. 5, Issue 3 https://doi.org/10.1038/nmat1590	journal	February 2006
Biosensing with plasmonic nanosensors Anker, Jeffrey N.; Hall, W. Paige; Lyandres, Olga Nature Materials, Vol. 7, Issue 6 https://doi.org/10.1038/nmat2162	journal	June 2008
The application of alkanethiol self-assembled monolayers to enzyme electrodes Gooding, J. Justin; Hibbert, D. Brynn TrAC Trends in Analytical Chemistry, Vol. 18, Issue 8 https://doi.org/10.1016/S0165-9936(99)00133-8	journal	August 1999
Thin Films of (3-Aminopropyl)triethoxysilane on Aluminum Oxide and Gold Substrates Kurth, Dirk G.; Bein, Thomas Langmuir, Vol. 11, Issue 8 https://doi.org/10.1021/la00008a035	journal	August 1995
Chain Length Dependence of the Frictional Properties of Alkylsilane Molecules Self-Assembled on Mica Studied by Atomic Force Microscopy Xiao, Xudong; Hu, Jun; Charych, Deborah H. Langmuir, Vol. 12, Issue 2 https://doi.org/10.1021/la950771u	journal	January 1996
M ECHANISMS AND K INETICS OF S ELF -A SSEMBLED M ONOLAYER F ORMATION Schwartz, Daniel K. Annual Review of Physical Chemistry, Vol. 52, Issue 1 https://doi.org/10.1146/annurev.physchem.52.1.107	journal	October 2001
Covalent Surface Modification of Oxide Surfaces Pujari, Sidharam P.; Scheres, Luc; Marcelis, Antonius T. M. Angewandte Chemie International Edition, Vol. 53, Issue 25 https://doi.org/10.1002/anie.201306709	journal	May 2014
X‐ray grazing incidence diffraction from alkylsiloxane monolayers on silicon wafers Tidswell, I. M.; Rabedeau, T. A.; Pershan, P. S. The Journal of Chemical Physics, Vol. 95, Issue 4 https://doi.org/10.1063/1.460886	journal	August 1991
Formation of an organized monolayer by solution adsorption of octadecyltrichlorosilane on gold: electrochemical properties and structural characterization Finklea, H. O.; Robinson, L. R.; Blackburn, A. Langmuir, Vol. 2, Issue 2 https://doi.org/10.1021/la00068a022	journal	March 1986
Silanation of silica surfaces. A new method of constructing pure or mixed monolayers Silberzan, P.; Leger, L.; Ausserre, D. Langmuir, Vol. 7, Issue 8 https://doi.org/10.1021/la00056a017	journal	August 1991
An infrared study of the reaction of octadecyltrichlorosilane with silica Tripp, C. P.; Hair, M. L. Langmuir, Vol. 8, Issue 4 https://doi.org/10.1021/la00040a018	journal	April 1992
Direct Observation of the Surface Bonds between Self-Assembled Monolayers of Octadecyltrichlorosilane and Silica Surfaces: A Low-Frequency IR Study at the Solid/Liquid Interface Tripp, C. P.; Hair, M. L. Langmuir, Vol. 11, Issue 4 https://doi.org/10.1021/la00004a029	journal	April 1995
Transition Temperatures for n -Alkyltrichlorosilane Monolayers Rye, R. R. Langmuir, Vol. 13, Issue 9 https://doi.org/10.1021/la960934u	journal	April 1997
Thoughts on the Structure of Alkylsilane Monolayers Stevens, Mark J. Langmuir, Vol. 15, Issue 8 https://doi.org/10.1021/la981064e	journal	April 1999
Multiple Transmission-Reflection IR Spectroscopy Shows that Surface Hydroxyls Play Only a Minor Role in Alkylsilane Monolayer Formation on Silica Naik, Vikrant V.; Crobu, Maura; Venkataraman, Nagaiyanallur V. The Journal of Physical Chemistry Letters, Vol. 4, Issue 16 https://doi.org/10.1021/jz401440d	journal	July 2013
Heads or Tails: Which Is More Important in Molecular Self-Assembly? Bent, Stacey F. ACS Nano, Vol. 1, Issue 1 https://doi.org/10.1021/nn700118k	journal	August 2007
X-ray specular reflection studies of silicon coated by organic monolayers (alkylsiloxanes) Tidswell, I. M.; Ocko, B. M.; Pershan, P. S. Physical Review B, Vol. 41, Issue 2 https://doi.org/10.1103/PhysRevB.41.1111	journal	January 1990
Hydrogen-bonded multilayers of self-assembling silanes: structure elucidation by combined Fourier transform infra-red spectroscopy and X-ray scattering techniques Maoz, Rivka; Sagiv, Jacob; Degenhardt, Detlef Supramolecular Science, Vol. 2, Issue 1 https://doi.org/10.1016/0968-5677(96)85635-5	journal	January 1995
Postassembly Chemical Modification of a Highly Ordered Organosilane Multilayer: New Insights into the Structure, Bonding, and Dynamics of Self-Assembling Silane Monolayers Wen, Ke; Maoz, Rivka; Cohen, Hagai ACS Nano, Vol. 2, Issue 3 https://doi.org/10.1021/nn800011t	journal	March 2008
Pseudorotational Epitaxy of Self-Assembled Octadecyltrichlorosilane Monolayers on Sapphire (0001) Steinrück, H. -G.; Magerl, A.; Deutsch, M. Physical Review Letters, Vol. 113, Issue 15 https://doi.org/10.1103/PhysRevLett.113.156101	journal	October 2014
Nanoscale Structure of Si/SiO ₂ /Organics Interfaces Steinrück, Hans-Georg; Schiener, Andreas; Schindler, Torben ACS Nano, Vol. 8, Issue 12 https://doi.org/10.1021/nn5056223	journal	November 2014
Self‐assembled silane monolayers: an efficient step‐by‐step recipe for high‐quality, low energy surfaces Lessel, M.; Bäumchen, O.; Klos, M. Surface and Interface Analysis, Vol. 47, Issue 5 https://doi.org/10.1002/sia.5729	journal	March 2015
Liquid Surfaces and Interfaces: Synchrotron X-ray Methods Pershan, Peter S.; Schlossman, Mark https://doi.org/10.1017/CBO9781139045872	book	September 2012
Principles and applications of grazing incidence X-ray and neutron scattering from ordered molecular monolayers at the air-water interface Als-Nielsen, Jens; Jacquemain, Didier; Kjaer, Kristian Physics Reports, Vol. 246, Issue 5 https://doi.org/10.1016/0370-1573(94)90046-9	journal	October 1994
Surface freezing in chain molecules: Normal alkanes Ocko, B. M.; Wu, X. Z.; Sirota, E. B. Physical Review E, Vol. 55, Issue 3 https://doi.org/10.1103/PhysRevE.55.3164	journal	March 1997
What x rays can tell us about the interfacial profile of water near hydrophobic surfaces Uysal, Ahmet; Chu, Miaoqi; Stripe, Benjamin Physical Review B, Vol. 88, Issue 3 https://doi.org/10.1103/PhysRevB.88.035431	journal	July 2013
Design and Characterization of Crystalline Thin Film Architectures at the Air−Liquid Interface: Simplicity to Complexity Kuzmenko, Ivan; Rapaport, Hanna; Kjaer, Kristian Chemical Reviews, Vol. 101, Issue 6 https://doi.org/10.1021/cr990038y	journal	June 2001
Rotator phases of the normal alkanes: An x‐ray scattering study Sirota, E. B.; King, H. E.; Singer, D. M. The Journal of Chemical Physics, Vol. 98, Issue 7 https://doi.org/10.1063/1.464874	journal	April 1993
Water and ice in contact with octadecyl-trichlorosilane functionalized surfaces: A high resolution x-ray reflectivity study Mezger, Markus; Schöder, Sebastian; Reichert, Harald The Journal of Chemical Physics, Vol. 128, Issue 24 https://doi.org/10.1063/1.2931574	journal	June 2008
In situ and interrupted-growth studies of the self-assembly of octadecyltrichlorosilane monolayers Richter, A. G.; Yu, C. -J.; Datta, A. Physical Review E, Vol. 61, Issue 1 https://doi.org/10.1103/PhysRevE.61.607	journal	January 2000
How Water Meets a Hydrophobic Surface Poynor, Adelé; Hong, Liang; Robinson, Ian K. Physical Review Letters, Vol. 97, Issue 26 https://doi.org/10.1103/PhysRevLett.97.266101	journal	December 2006
Order and Melting in Self-Assembled Alkanol Monolayers on Amorphous SiO ₂ Haddad, Julia; Steinrück, Hans-Georg; Hlaing, Htay The Journal of Physical Chemistry C, Vol. 119, Issue 31 https://doi.org/10.1021/acs.jpcc.5b03554	journal	July 2015
Unifying Interfacial Self-Assembly and Surface Freezing Ocko, B. M.; Hlaing, H.; Jepsen, P. N. Physical Review Letters, Vol. 106, Issue 13 https://doi.org/10.1103/PhysRevLett.106.137801	journal	March 2011
Crystalline Phases of Alkyl-Thiol Monolayers on Liquid Mercury Ocko, B. M.; Kraack, H.; Pershan, P. S. Physical Review Letters, Vol. 94, Issue 1 https://doi.org/10.1103/PhysRevLett.94.017802	journal	January 2005
Surface Freezing in Hydrated Alcohol Melts Gang, O.; Ocko, B. M.; Wu, X. Z. Physical Review Letters, Vol. 80, Issue 6 https://doi.org/10.1103/PhysRevLett.80.1264	journal	February 1998
Molecular Aggregation State of n -Octadecyltrichlorosilane Monolayers Prepared by the Langmuir and Chemisorption Methods Kojio, Ken; Takahara, Atsushi; Omote, Kazuhiko Langmuir, Vol. 16, Issue 8 https://doi.org/10.1021/la9909042	journal	April 2000
Positional order and thermal expansion of surface crystalline N -alkane monolayers Ocko, B. M.; Sirota, E. B.; Deutsch, M. Physical Review E, Vol. 63, Issue 3 https://doi.org/10.1103/PhysRevE.63.032602	journal	February 2001
The Structure and Phase Diagram of Langmuir Films of Alcohols on Mercury Kraack, H.; Ocko, B. M.; Pershan, P. S. Langmuir, Vol. 20, Issue 13 https://doi.org/10.1021/la0497954	journal	June 2004
Effect of Leaving Group on the Structures of Alkylsilane SAMs Naik, Vikrant V.; Städler, Roman; Spencer, Nicholas D. Langmuir, Vol. 30, Issue 49 https://doi.org/10.1021/la503739j	journal	December 2014
A Near Edge X-ray Absorption Fine Structure Spectroscopy and X-ray Photoelectron Spectroscopy Study of the Film Properties of Self-Assembled Monolayers of Organosilanes on Oxidized Si(100) Bierbaum, K.; Kinzler, M.; Woell, Ch. Langmuir, Vol. 11, Issue 2 https://doi.org/10.1021/la00002a025	journal	February 1995
Real-Time Grazing Incidence X-ray Diffraction Studies of Polymerizing n -Octadecyltrimethoxysilane Langmuir Monolayers at the Air/Water Interface Carino, Stephen R.; Tostmann, Holger; Underhill, Royale S. Journal of the American Chemical Society, Vol. 123, Issue 4 https://doi.org/10.1021/ja0057777	journal	January 2001
Influence of Headgroup Cross-Linking on Chain Packing in Langmuir Monolayers of n -Alkyltrialkoxysilanes Fontaine, P.; Goldmann, M.; Rondelez, F. Langmuir, Vol. 15, Issue 4 https://doi.org/10.1021/la9809933	journal	February 1999
X-ray grazing incidence studies of the 2D crystallization of monolayers of 1-alcohols at the air-water interface Legrand, J. F.; Renault, A.; Konovalov, O. Thin Solid Films, Vol. 248, Issue 1 https://doi.org/10.1016/0040-6090(94)90218-6	journal	August 1994
Structure of octadecanol monolayers: An x-ray diffraction study Brezesinski, G.; Kaganer, V. M.; Möhwald, H. The Journal of Chemical Physics, Vol. 109, Issue 5 https://doi.org/10.1063/1.476777	journal	August 1998
A Grazing-Incidence X-ray Diffraction Study of Octadecanol Monolayers at High Surface Pressures Steitz, R.; Peng, J. B.; Peterson, I. R. Langmuir, Vol. 14, Issue 25 https://doi.org/10.1021/la980163p	journal	November 1998
Evidence for a Unique Chain Organization in Long Chain Silane Monolayers Deposited on Two Widely Different Solid Substrates Allara, David L.; Parikh, Atul N.; Rondelez, Francis Langmuir, Vol. 11, Issue 7 https://doi.org/10.1021/la00007a007	journal	July 1995
Statistical model of short alcohol monolayers: Chain conformations and melting transition Rieu, J. P.; Vallade, M. The Journal of Chemical Physics, Vol. 104, Issue 19 https://doi.org/10.1063/1.471478	journal	May 1996
The morphology of integrated self-assembled monolayers and their impact on devices – A computational and experimental approach Novak, Michael; Jäger, Christof M.; Rumpel, Armin Organic Electronics, Vol. 11, Issue 8 https://doi.org/10.1016/j.orgel.2010.05.009	journal	August 2010
Partial Crystallinity in Alkyl Side Chain Polymers Dictates Surface Freezing Prasad, Shishir; Jiang, Zhang; Sinha, Sunil K. Physical Review Letters, Vol. 101, Issue 6 https://doi.org/10.1103/PhysRevLett.101.065505	journal	August 2008
A molecular simulation study of an organosilane self-assembled monolayer/SiO2 substrate interface Yamamoto, Hideaki; Watanabe, Takanobu; Ohdomari, Iwao The Journal of Chemical Physics, Vol. 128, Issue 16 https://doi.org/10.1063/1.2895052	journal	April 2008

Cited By (4)

Flexible sample cell for real-time GISAXS, GIWAXS and XRR: design and construction Berlinghof, M.; Bär, C.; Haas, D. Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2018-03803	text	January 2018
Mixed Organic Ligand Shells: Controlling the Nanoparticle Surface Morphology toward Tuning the Optoelectronic Properties Henkel, Christian; Wittmann, Judith E.; Träg, Johannes Small, Vol. 16, Issue 2 https://doi.org/10.1002/smll.201903729	journal	November 2019
Flexible sample cell for real-time GISAXS, GIWAXS and XRR: design and construction Berlinghof, M.; Bär, C.; Haas, D. Journal of Synchrotron Radiation, Vol. 25, Issue 6 https://doi.org/10.1107/s1600577518013218	journal	October 2018
Synchrotron Scattering Methods for Nanomaterials and Soft Matter Research Narayanan, Theyencheri; Konovalov, Oleg Materials, Vol. 13, Issue 3 https://doi.org/10.3390/ma13030752	journal	February 2020

Similar Records

Asphaltene Adsorption onto Self-Assembled Monolayers of Alkyltrichlorosilanes of Varying Chain Length

Journal Article · Thu Jan 01 00:00:00 EST 2009 · ACS Applied Materials & Interfaces · OSTI ID:1240699

Turgman-Cohen, S; Fischer, D; Kilpatrick, P; +1 more

A chemical modification of alkanethiol self-assembled monolayers with alkyltrichlorosilanes for the protection of copper against corrosion

Journal Article · Mon Aug 01 00:00:00 EDT 1994 · Journal of the Electrochemical Society; (United States) · OSTI ID:1240699

Itoh, Miki; Nishihara, Hiroshi; Aramaki, Kunitsugu

The protection ability of 11-mercapto-1-undecanol self-assembled monolayer modified with alkyltrichlorosilanes against corrosion of copper

Journal Article · Thu Jun 01 00:00:00 EDT 1995 · Journal of the Electrochemical Society · OSTI ID:1240699

Itoh, Miki; Nishihara, Hiroshi; Aramaki, Kunitsugu

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY

Title: Structure of n-alkyltrichlorosilane mono layers on Si(100)/SiO2

Citation Formats

References (57)

Cited By (4)

Similar Records

Related Subjects

Title: Structure of n-alkyltrichlorosilane mono layers on Si(100)/SiO₂