Substrate-Dependent Study of Chain Orientation and Order in Alkylphosphonic Acid Self-Assembled Monolayers for ALD Blocking

Bobb-Semple, Dara; Zeng, Li; Cordova, Isvar; Bergsman, David S.; Nordlund, Dennis; Bent, Stacey F.

doi:10.1021/acs.langmuir.0c01974

Title: Substrate-Dependent Study of Chain Orientation and Order in Alkylphosphonic Acid Self-Assembled Monolayers for ALD Blocking

Journal Article · Tue Oct 20 00:00:00 EDT 2020 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.0c01974· OSTI ID:1769359

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^[3]; Nordlund, Dennis ^[4];

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Stanford Univ., CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

For years, many efforts in area selective atomic layer deposition (AS-ALD) have focused on trying to achieve high-quality self-assembled monolayers (SAMs), which have been shown by a number of studies to be effective for blocking deposition. In this work, we show that in some cases where a densely packed SAM is not formed, significant ALD inhibition may still be realized. The formation of octadecylphosphonic acid (ODPA) SAMs was evaluated on four metal substrates: Cu, Co, W, and Ru. The molecular orientation, chain packing, and relative surface coverage were evaluated using near-edge X-ray absorption fine structure (NEXAFS), Fourier transform infrared (FTIR) spectroscopy, and electrochemical impedance spectroscopy (EIS). ODPA SAMs formed on Co, Cu, and W showed strong angular dependence of the NEXAFS signal whereas ODPA on Ru did not, suggesting a disordered layer was formed on Ru. Additionally, EIS and FTIR spectroscopy confirmed that Co and Cu form densely packed, “crystal-like” SAMs whereas Ru and W form less dense monolayers, a surprising result since W-ODPA was previously shown to inhibit the ALD of ZnO and Al₂O₃ best among all the substrates. This work suggests that multiple factors play a role in SAM-based AS-ALD, not just the SAM quality. Therefore, metrological averaging techniques (e.g., WCA and FTIR spectroscopy) commonly used for evaluating SAMs to predict their suitability for ALD inhibition should be supplemented by more atomically sensitive methods. Finally, it highlights important considerations for describing the mechanism of SAM-based selective ALD.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-76SF00515; ECCS-1542152

OSTI ID:: 1769359

Journal Information:: Langmuir, Vol. 36, Issue 43; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
NEXAFS Spectroscopy Stöhr, Joachim Springer Series in Surface Sciences https://doi.org/10.1007/978-3-662-02853-7	book	January 1992
On the potential of tungsten as next-generation semiconductor interconnects Choi, Dooho; Barmak, Katayun Electronic Materials Letters, Vol. 13, Issue 5 https://doi.org/10.1007/s13391-017-1610-5	journal	September 2017
Stability of Phosphonic Acid Self-Assembled Monolayers on Amorphous and Single-Crystalline Aluminum Oxide Surfaces in Aqueous Solution Thissen, Peter; Valtiner, Markus; Grundmeier, Guido Langmuir, Vol. 26, Issue 1 https://doi.org/10.1021/la900935s	journal	January 2010
Active MnO _x Electrocatalysts Prepared by Atomic Layer Deposition for Oxygen Evolution and Oxygen Reduction Reactions Pickrahn, Katie L.; Park, Sang Wook; Gorlin, Yelena Advanced Energy Materials, Vol. 2, Issue 10 https://doi.org/10.1002/aenm.201200230	journal	June 2012
Area-Selective ALD with Soft Lithographic Methods: Using Self-Assembled Monolayers to Direct Film Deposition Jiang, Xirong; Bent, Stacey F. The Journal of Physical Chemistry C, Vol. 113, Issue 41 https://doi.org/10.1021/jp905317n	journal	September 2009
CuCO ₃ by XPS Vasquez, R. P. Surface Science Spectra, Vol. 5, Issue 4 https://doi.org/10.1116/1.1247884	journal	October 1998
Tuning the Work Function of Polar Zinc Oxide Surfaces using Modified Phosphonic Acid Self‐Assembled Monolayers Lange, Ilja; Reiter, Sina; Pätzel, Michael Advanced Functional Materials, Vol. 24, Issue 44 https://doi.org/10.1002/adfm.201401493	journal	September 2014
Assignment of NEXAFS Resonances in Alkanethiols and Their Implication on the Determination of Molecular Orientation of Aliphatic SAMs Völkner, Johannes; Klues, Michael; Witte, Gregor The Journal of Physical Chemistry C, Vol. 122, Issue 29 https://doi.org/10.1021/acs.jpcc.8b04342	journal	July 2018
Spontaneously organized molecular assemblies. 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared spectroscopy, and electrochemistry Porter, Marc D.; Bright, Thomas B.; Allara, David L. Journal of the American Chemical Society, Vol. 109, Issue 12 https://doi.org/10.1021/ja00246a011	journal	June 1987
Role of SAM Chain Length in Enhancing the Sensitivity of Nanopillar Modified Electrodes for Glucose Detection Anandan, Venkataramani; Gangadharan, Rajan; Zhang, Guigen Sensors, Vol. 9, Issue 3 https://doi.org/10.3390/s90301295	journal	February 2009
Characterization of Cu surface cleaning by hydrogen plasma Baklanov, M. R.; Shamiryan, D. G.; Tökei, Zs. Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 19, Issue 4 https://doi.org/10.1116/1.1387084	journal	January 2001
Formation and Ripening of Self-Assembled Multilayers from the Vapor-Phase Deposition of Dodecanethiol on Copper Oxide Bergsman, David S.; Liu, Tzu-Ling; Closser, Richard G. Chemistry of Materials, Vol. 30, Issue 16 https://doi.org/10.1021/acs.chemmater.8b02150	journal	July 2018
Real-Time Observation of Atomic Layer Deposition Inhibition: Metal Oxide Growth on Self-Assembled Alkanethiols Avila, Jason R.; DeMarco, Erica J.; Emery, Jonathan D. ACS Applied Materials & Interfaces, Vol. 6, Issue 15 https://doi.org/10.1021/am503008j	journal	July 2014
A New Resist for Area Selective Atomic and Molecular Layer Deposition on Metal–Dielectric Patterns Hashemi, Fatemeh Sadat Minaye; Prasittichai, Chaiya; Bent, Stacey F. The Journal of Physical Chemistry C, Vol. 118, Issue 20 https://doi.org/10.1021/jp502669f	journal	May 2014
Area-Selective Deposition: Fundamentals, Applications, and Future Outlook Parsons, Gregory N.; Clark, Robert D. Chemistry of Materials, Vol. 32, Issue 12 https://doi.org/10.1021/acs.chemmater.0c00722	journal	May 2020
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
Insulating Properties of Self-Assembled Monolayers Monitored by Impedance Spectroscopy Boubour, Emmanuelle; Lennox, R. Bruce Langmuir, Vol. 16, Issue 9 https://doi.org/10.1021/la991328c	journal	May 2000
Vapor-deposited octadecanethiol masking layer on copper to enable area selective Hf ₃ N ₄ atomic layer deposition on dielectrics studied by in situ spectroscopic ellipsometry Lecordier, Laurent; Herregods, Sebastiaan; Armini, Silvia Journal of Vacuum Science & Technology A, Vol. 36, Issue 3 https://doi.org/10.1116/1.5025688	journal	May 2018
Area-Selective Atomic Layer Deposition of Platinum on YSZ Substrates Using Microcontact Printed SAMs Jiang, Xirong; Bent, Stacey F. Journal of The Electrochemical Society, Vol. 154, Issue 12 https://doi.org/10.1149/1.2789301	journal	January 2007
Selective Deposition of Dielectrics: Limits and Advantages of Alkanethiol Blocking Agents on Metal–Dielectric Patterns Minaye Hashemi, Fatemeh Sadat; Birchansky, Bradlee R.; Bent, Stacey F. ACS Applied Materials & Interfaces, Vol. 8, Issue 48 https://doi.org/10.1021/acsami.6b09960	journal	November 2016
Self-Assembled Monolayer Formation on Copper: A Real Time Electrochemical Impedance Study Dilimon, V. S.; Fonder, G.; Delhalle, J. The Journal of Physical Chemistry C, Vol. 115, Issue 37 https://doi.org/10.1021/jp203652y	journal	August 2011
Carbon K -edge spectra of carbonate minerals Brandes, Jay A.; Wirick, Sue; Jacobsen, Chris Journal of Synchrotron Radiation, Vol. 17, Issue 5 https://doi.org/10.1107/S0909049510020029	journal	July 2010
Trends in the Carbonyl Core (C 1S, O 1S) → π* _C=O Transition in the Near-Edge X-ray Absorption Fine Structure Spectra of Organic Molecules Urquhart, S. G.; Ade, H. The Journal of Physical Chemistry B, Vol. 106, Issue 34 https://doi.org/10.1021/jp0255379	journal	August 2002
Impedance Spectroscopy of Self-Assembled Monolayers on Au(111): Sodium Ferrocyanide Charge Transfer at Modified Electrodes Janek, Richard P.; Fawcett, W. Ronald; Ulman, Abraham Langmuir, Vol. 14, Issue 11 https://doi.org/10.1021/la970980+	journal	May 1998
The orientation of Langmuir–Blodgett monolayers using NEXAFS Outka, D. A.; Stöhr, J.; Rabe, J. P. The Journal of Chemical Physics, Vol. 88, Issue 6 https://doi.org/10.1063/1.453862	journal	March 1988
Effect of substrate composition on atomic layer deposition using self-assembled monolayers as blocking layers Zhang, Wenyu; Engstrom, James R. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 34, Issue 1 https://doi.org/10.1116/1.4931722	journal	January 2016
Surface Modification of Titanium with Phosphonic Acid To Improve Bone Bonding: Characterization by XPS and ToF-SIMS Viornery, Carine; Chevolot, Yann; Léonard, Didier Langmuir, Vol. 18, Issue 7 https://doi.org/10.1021/la010908i	journal	April 2002
Semiconductor self-assembled monolayers as selective contacts for efficient PiN perovskite solar cells Yalcin, E.; Can, M.; Rodriguez-Seco, C. Energy & Environmental Science, Vol. 12, Issue 1 https://doi.org/10.1039/C8EE01831F	journal	January 2019
Self-assembled monolayer resist for atomic layer deposition of HfO2 and ZrO2 high-κ gate dielectrics Chen, Rong; Kim, Hyoungsub; McIntyre, Paul C. Applied Physics Letters, Vol. 84, Issue 20 https://doi.org/10.1063/1.1751211	journal	May 2004
Influence of indium–tin oxide surface structure on the ordering and coverage of carboxylic acid and thiol monolayers Cerruti, Marta; Rhodes, Crissy; Losego, Mark Journal of Physics D: Applied Physics, Vol. 40, Issue 14 https://doi.org/10.1088/0022-3727/40/14/016	journal	June 2007
Modification of Electrode Surfaces by Self-Assembled Monolayers of Thiol-Terminated Oligo(Phenyleneethynylene)s Kaur, Inderpreet; Zhao, Xiaotao; Bryce, Martin R. ChemPhysChem, Vol. 14, Issue 2 https://doi.org/10.1002/cphc.201200744	journal	January 2013
Characterizing the Molecular Order of Phosphonic Acid Self-Assembled Monolayers on Indium Tin Oxide Surfaces Losego, Mark D.; Guske, Joshua T.; Efremenko, Alina Langmuir, Vol. 27, Issue 19 https://doi.org/10.1021/la201161q	journal	October 2011
Inhibiting Metal Oxide Atomic Layer Deposition: Beyond Zinc Oxide Sampson, Matthew D.; Emery, Jonathan D.; Pellin, Michael J. ACS Applied Materials & Interfaces, Vol. 9, Issue 39 https://doi.org/10.1021/acsami.7b01410	journal	April 2017
Assembly of phosphonic acids on GaN and AlGaN Simpkins, B. S.; Hong, S.; Stine, R. Journal of Physics D: Applied Physics, Vol. 43, Issue 1 https://doi.org/10.1088/0022-3727/43/1/015303	journal	December 2009
Carbon K-shell excitation spectra of linear and branched alkanes Hitchcock, A. P.; Ishii, I. Journal of Electron Spectroscopy and Related Phenomena, Vol. 42, Issue 1 https://doi.org/10.1016/0368-2048(87)85002-8	journal	January 1987
Study of Insulating Properties of Alkanethiol Self-Assembled Monolayers Formed Under Prolonged Incubation Using Electrochemical Impedance Spectroscopy Agonafer, Damena D.; Chainani, Edward; Oruc, Muhammed E. Journal of Nanotechnology in Engineering and Medicine, Vol. 3, Issue 3 https://doi.org/10.1115/1.4007698	journal	August 2012
Nanoscale detection of organic signatures in carbonate microbialites Benzerara, K.; Menguy, N.; Lopez-Garcia, P. Proceedings of the National Academy of Sciences, Vol. 103, Issue 25 https://doi.org/10.1073/pnas.0603255103	journal	June 2006
Investigation of Self-Assembled Monolayer Resists for Hafnium Dioxide Atomic Layer Deposition Chen, Rong; Kim, Hyoungsub; McIntyre, Paul C. Chemistry of Materials, Vol. 17, Issue 3 https://doi.org/10.1021/cm0486666	journal	February 2005
Fifteen Nanometer Resolved Patterns in Selective Area Atomic Layer Deposition—Defectivity Reduction by Monolayer Design Wojtecki, Rudy; Mettry, Magi; Fine Nathel, Noah F. ACS Applied Materials & Interfaces, Vol. 10, Issue 44 https://doi.org/10.1021/acsami.8b13896	journal	October 2018
Self-Assembled Monolayers of Alkaneselenolates on (111) Gold and Silver Shaporenko, A.; Ulman, A.; Terfort, A. The Journal of Physical Chemistry B, Vol. 109, Issue 9 https://doi.org/10.1021/jp045052f	journal	March 2005
Area-Selective Atomic Layer Deposition Assisted by Self-Assembled Monolayers: A Comparison of Cu, Co, W, and Ru Bobb-Semple, Dara; Nardi, Katie Lynn; Draeger, Nerissa Chemistry of Materials, Vol. 31, Issue 5 https://doi.org/10.1021/acs.chemmater.8b04926	journal	February 2019
Characterization of phosphonic acid binding to zinc oxide Hotchkiss, Peter J.; Malicki, Michał; Giordano, Anthony J. Journal of Materials Chemistry, Vol. 21, Issue 9 https://doi.org/10.1039/c0jm02829k	journal	January 2011
Scanning Electrochemical Microscopy. 59. Effect of Defects and Structure on Electron Transfer through Self-Assembled Monolayers Kiani, Abolfazl; Alpuche-Aviles, Mario A.; Eggers, Paul K. Langmuir, Vol. 24, Issue 6 https://doi.org/10.1021/la702811t	journal	March 2008
Adsorption of Phosphonic Acid at the TiO ₂ Anatase (101) and Rutile (110) Surfaces Luschtinetz, Regina; Frenzel, Johannes; Milek, Theodor The Journal of Physical Chemistry C, Vol. 113, Issue 14 https://doi.org/10.1021/jp8110343	journal	March 2009
Atomic Layer Deposition of Ruthenium with TiN Interface for Sub-10 nm Advanced Interconnects beyond Copper Wen, Liang Gong; Roussel, Philippe; Pedreira, Olalla Varela ACS Applied Materials & Interfaces, Vol. 8, Issue 39 https://doi.org/10.1021/acsami.6b07181	journal	September 2016
Reaction Mechanism of Area-Selective Atomic Layer Deposition for Al ₂ O ₃ Nanopatterns Seo, Seunggi; Yeo, Byung Chul; Han, Sang Soo ACS Applied Materials & Interfaces, Vol. 9, Issue 47 https://doi.org/10.1021/acsami.7b13365	journal	November 2017
Determination of molecular orientations on surfaces from the angular dependence of near-edge x-ray-absorption fine-structure spectra Stöhr, J.; Outka, D. A. Physical Review B, Vol. 36, Issue 15 https://doi.org/10.1103/PhysRevB.36.7891	journal	November 1987
Highly Stable Monolayer Resists for Atomic Layer Deposition on Germanium and Silicon Chen, Rong; Bent, Stacey F. Chemistry of Materials, Vol. 18, Issue 16 https://doi.org/10.1021/cm0607785	journal	August 2006
XPS and XAS investigation of condensed and adsorbed n-octane on a Cu(110) surface Weiss, K.; Öström, H.; Triguero, L. Journal of Electron Spectroscopy and Related Phenomena, Vol. 128, Issue 2-3 https://doi.org/10.1016/S0368-2048(02)00282-7	journal	February 2003
Bonding Self-Assembled, Compact Organophosphonate Monolayers to the Native Oxide Surface of Silicon Hanson, Eric L.; Schwartz, Jeffrey; Nickel, Bert Journal of the American Chemical Society, Vol. 125, Issue 51 https://doi.org/10.1021/ja035956z	journal	December 2003
Surface Barrier Properties of Self-Assembled Monolayers as Deduced by Sum Frequency Generation Spectroscopy and Electrochemistry Cai, Xiaojun; Baldelli, Steven The Journal of Physical Chemistry C, Vol. 115, Issue 39 https://doi.org/10.1021/jp202060n	journal	September 2011
Electrochemistry of redox-active self-assembled monolayers Eckermann, Amanda L.; Feld, Daniel J.; Shaw, Justine A. Coordination Chemistry Reviews, Vol. 254, Issue 15-16 https://doi.org/10.1016/j.ccr.2009.12.023	journal	August 2010
Phosphonic Acid Modification of Indium−Tin Oxide Electrodes: Combined XPS/UPS/Contact Angle Studies Paniagua, Sergio A.; Hotchkiss, Peter J.; Jones, Simon C. The Journal of Physical Chemistry C, Vol. 112, Issue 21 https://doi.org/10.1021/jp710893k	journal	April 2008
Selective Growth of Titanium Nitride on HfO ₂ across Nanolines and Nanopillars Chopra, Sonali N.; Zhang, Zizhuo; Kaihlanen, Chris Chemistry of Materials, Vol. 28, Issue 14 https://doi.org/10.1021/acs.chemmater.6b01036	journal	July 2016
Self-Correcting Process for High Quality Patterning by Atomic Layer Deposition Minaye Hashemi, Fatemeh Sadat; Prasittichai, Chaiya; Bent, Stacey F. ACS Nano, Vol. 9, Issue 9 https://doi.org/10.1021/acsnano.5b03125	journal	July 2015
The interactions of Co, Mn and water with calcite surfaces Blanchard, David L.; Baer, D. R. Surface Science, Vol. 276, Issue 1-3 https://doi.org/10.1016/0039-6028(92)90692-Y	journal	October 1992
Perspective: New process technologies required for future devices and scaling Clark, R.; Tapily, K.; Yu, K. -H. APL Materials, Vol. 6, Issue 5 https://doi.org/10.1063/1.5026805	journal	May 2018
The Removal of Copper Oxides by Ethyl Alcohol Monitored In Situ by Spectroscopic Ellipsometry Satta, Alessandra; Shamiryan, Denis; Baklanov, Mikhaı̈l R. Journal of The Electrochemical Society, Vol. 150, Issue 5 https://doi.org/10.1149/1.1564108	journal	January 2003
Monitoring and Mapping Imperfections in Silane-Based Self-Assembled Monolayers by Chemical Amplification Jalali, Hanifa; Gates, Byron D. Langmuir, Vol. 25, Issue 16 https://doi.org/10.1021/la900443c	journal	August 2009

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