Controlling the Schottky Barrier at the Pt/TiO2 Interface by Intercalation of a Self-Assembled Monolayer with Oriented Dipole Moments

Ano, Taishi; Kishimoto, Fuminao; Tsubaki, Shuntaro; Lu, Yi-Hsien; Hohman, J. Nathan; Maitani, Masato M.; Salmeron, Miquel; Wada, Yuji

doi:10.1021/acs.jpcc.1c00993

Controlling the Schottky Barrier at the Pt/TiO₂ Interface by Intercalation of a Self-Assembled Monolayer with Oriented Dipole Moments

Journal Article · Sun Jun 20 00:00:00 EDT 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c00993· OSTI ID:1844529

^[1]; ^[2]; ^[1]; ^[3]; ^[4]; ^[1]; ^[3]; Wada, Yuji ^[1]

Tokyo Inst. of Technology (Japan)
Univ. of Tokyo (Japan)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of Connecticut, Storrs, CT (United States)

Interfacial Schottky barriers can impact the catalytic function of Pt on TiO₂. Since the electronic structure is characteristic of each material, it may be advantageous to tailor the interfacial Schottky barrier by the addition of adsorbed layers. Here, we show that the Schottky barrier in Pt/TiO₂ can be mitigated by the insertion of self-assembled monolayers (SAM) of carboranethiols that possess an oriented dipole moment. A Pt substrate with the SAM on which TiO₂ nanoparticles are deposited is used to that effect. Kelvin Probe Force Microscopy shows thatm-9-carboranethiolate SAM with perpendicular dipole moments decreases the potential difference between TiO₂ and Pt by ~0.3 eV due to the interfacial electric field of the SAM. Furthermore, our findings open new opportunities for tailoring interfacial electronic structures not only in the metal-semiconductor junction, but also the semiconductor heterojunctions.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1844529

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 25 Vol. 125; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (32)

Molecular Self-Assembled Monolayers and Multilayers for Organic and Unconventional Inorganic Thin-Film Transistor Applications DiBenedetto, Sara A.; Facchetti, Antonio; Ratner, Mark A. Advanced Materials, Vol. 21, Issue 14-15 https://doi.org/10.1002/adma.200803267	journal	April 2009
Tuning Band Alignment Using Interface Dipoles at the Pt/Anatase TiO ₂ Interface Tachikawa, Takashi; Minohara, Makoto; Hikita, Yasuyuki Advanced Materials, Vol. 27, Issue 45 https://doi.org/10.1002/adma.201503339	journal	October 2015
Schottky-barrier and conductivity gas sensors based upon Pd/SnO2 and Pt/TiO2 Schierbaum, K. D.; Kirner, U. K.; Geiger, J. F. Sensors and Actuators B: Chemical, Vol. 4, Issue 1-2 https://doi.org/10.1016/0925-4005(91)80181-I	journal	May 1991
Influence of co-existing alcohol on charge transfer of H2 evolution under visible light with dye-sensitized nanocrystalline TiO2 Maitani, Masato M.; Zhan, Conghong; Mochizuki, Dai Applied Catalysis B: Environmental, Vol. 140-141 https://doi.org/10.1016/j.apcatb.2013.04.044	journal	August 2013
Highly-sensitive H2 sensor operating at room temperature using Pt/TiO2 nanoscale Schottky contacts Kwon, Hyunah; Lee, Yuna; Hwang, Sunyong Sensors and Actuators B: Chemical, Vol. 241 https://doi.org/10.1016/j.snb.2016.11.022	journal	March 2017
Effect of Pt/TiO2 interface on room temperature hydrogen sensing performance of memristor type Pt/TiO2/Pt structure Haidry, Azhar Ali; Ebach-Stahl, Andrea; Saruhan, Bilge Sensors and Actuators B: Chemical, Vol. 253 https://doi.org/10.1016/j.snb.2017.06.159	journal	December 2017
Ultra-flat platinum surfaces from template-stripping of sputter deposited films Blackstock, Jason J.; Li, Zhiyong; Freeman, Mark R. Surface Science, Vol. 546, Issue 2-3 https://doi.org/10.1016/j.susc.2003.09.039	journal	December 2003
Role of Molecular Dipoles in Charge Transport across Large Area Molecular Junctions Delineated Using Isomorphic Self-Assembled Monolayers Chen, Jiahao; Gathiaka, Symon; Wang, Zhengjia The Journal of Physical Chemistry C, Vol. 121, Issue 43 https://doi.org/10.1021/acs.jpcc.7b07634	journal	October 2017
Construction of Highly Hierarchical Layered Structure Consisting of Titanate Nanosheets, Tungstate Nanosheets, Ru(bpy) ₃ ²⁺ , and Pt(terpy) for Vectorial Photoinduced Z-Scheme Electron Transfer Kishimoto, Fuminao; Mochizuki, Dai; Maitani, Masato M. ACS Applied Materials & Interfaces, Vol. 10, Issue 43 https://doi.org/10.1021/acsami.8b14749	journal	October 2018
Ethylene Hydrogenation over Pt/TiO ₂ : A Charge-Sensitive Reaction Gunasooriya, G. T. Kasun Kalhara; Seebauer, Edmund G.; Saeys, Mark ACS Catalysis, Vol. 7, Issue 3 https://doi.org/10.1021/acscatal.6b02906	journal	February 2017
Band Bending in Semiconductors: Chemical and Physical Consequences at Surfaces and Interfaces Zhang, Zhen; Yates, John T. Chemical Reviews, Vol. 112, Issue 10 https://doi.org/10.1021/cr3000626	journal	June 2012
Self-Assembled Monolayers on Pt(111): Molecular Packing Structure and Strain Effects Observed by Scanning Tunneling Microscopy Lee, Sangyeob; Park, Jung; Ragan, Regina Journal of the American Chemical Society, Vol. 128, Issue 17 https://doi.org/10.1021/ja058037c	journal	April 2006
Direct Control of Electron Transfer to the Surface-CO Bond on a Pt/TiO₂ Catalytic Diode Deshlahra, Prashant; Schneider, William F.; Bernstein, Gary H. Journal of the American Chemical Society, Vol. 133, Issue 41, p. 16459-16467 https://doi.org/10.1021/ja2020789	journal	October 2011
Interface Dipoles Arising from Self-Assembled Monolayers on Gold: UV−Photoemission Studies of Alkanethiols and Partially Fluorinated Alkanethiols Alloway, Dana M.; Hofmann, Michael; Smith, Darrin L. The Journal of Physical Chemistry B, Vol. 107, Issue 42 https://doi.org/10.1021/jp034665+	journal	September 2003
Fabrication of TiO ₂ −Pt Coaxial Nanotube Array Schottky Structures for Enhanced Photocatalytic Degradation of Phenol in Aqueous Solution Chen, Huan; Chen, Shuo; Quan, Xie The Journal of Physical Chemistry C, Vol. 112, Issue 25 https://doi.org/10.1021/jp8011393	journal	June 2008
Tuning the Electronic Structure of Titanium Oxide Support to Enhance the Electrochemical Activity of Platinum Nanoparticles Shi, Feifei; Baker, L. Robert; Hervier, Antoine Nano Letters, Vol. 13, Issue 9 https://doi.org/10.1021/nl402392u	journal	August 2013
Interface Control in Organic Electronics Using Mixed Monolayers of Carboranethiol Isomers Kim, Jaemyung; Rim, You Seung; Liu, Yongsheng Nano Letters, Vol. 14, Issue 5 https://doi.org/10.1021/nl501081q	journal	April 2014
Sensing the Charge State of Single Gold Nanoparticles via Work Function Measurements Zhang, Yingjie; Pluchery, Olivier; Caillard, Louis Nano Letters, Vol. 15, Issue 1 https://doi.org/10.1021/nl503782s	journal	December 2014
Charge Trapping States at the SiO ₂ –Oligothiophene Monolayer Interface in Field Effect Transistors Studied by Kelvin Probe Force Microscopy Zhang, Yingjie; Ziegler, Dominik; Salmeron, Miquel ACS Nano, Vol. 7, Issue 9 https://doi.org/10.1021/nn403750h	journal	August 2013
Self-Assembly of Carboranethiol Isomers on Au{111}: Intermolecular Interactions Determined by Molecular Dipole Orientations Hohman, J. Nathan; Zhang, Pengpeng; Morin, Elizabeth I. ACS Nano, Vol. 3, Issue 3 https://doi.org/10.1021/nn800673d	journal	February 2009
Nanoscale semiconductor/catalyst interfaces in photoelectrochemistry Laskowski, Forrest A. L.; Oener, Sebastian Z.; Nellist, Michael R. Nature Materials, Vol. 19, Issue 1 https://doi.org/10.1038/s41563-019-0488-z	journal	October 2019
Metallic nanoparticle contacts for high-yield, ambient-stable molecular-monolayer devices Puebla-Hellmann, Gabriel; Venkatesan, Koushik; Mayor, Marcel Nature, Vol. 559, Issue 7713 https://doi.org/10.1038/s41586-018-0275-z	journal	July 2018
Photocatalytic water splitting with a quantum efficiency of almost unity Takata, Tsuyoshi; Jiang, Junzhe; Sakata, Yoshihisa Nature, Vol. 581, Issue 7809 https://doi.org/10.1038/s41586-020-2278-9	journal	May 2020
Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity van Deelen, Tom W.; Hernández Mejía, Carlos; de Jong, Krijn P. Nature Catalysis, Vol. 2, Issue 11 https://doi.org/10.1038/s41929-019-0364-x	journal	November 2019
A simplified theoretical guideline for overall water splitting using photocatalyst particles Garcia-Esparza, Angel T.; Takanabe, Kazuhiro Journal of Materials Chemistry A, Vol. 4, Issue 8 https://doi.org/10.1039/C5TA06983A	journal	January 2016
Determination and perturbation of the electronic potentials of solid catalysts for innovative catalysis Qi, Xingyu; Shinagawa, Tatsuya; Kishimoto, Fuminao Chemical Science, Vol. 12, Issue 2 https://doi.org/10.1039/D0SC05148A	journal	January 2021
Vacuum Thermionic Work Functions of Polycrystalline Be, Ti, Cr, Fe, Ni, Cu, Pt, and Type 304 Stainless Steel Wilson, R. G. Journal of Applied Physics, Vol. 37, Issue 6 https://doi.org/10.1063/1.1708797	journal	May 1966
Enhanced field emission from hydrogenated TiO ₂ nanotube arrays Zhu, Wei-Dong; Wang, Cheng-Wei; Chen, Jian-Biao Nanotechnology, Vol. 23, Issue 45 https://doi.org/10.1088/0957-4484/23/45/455204	journal	October 2012
Photoelectric Work Functions of Transition, Rare-Earth, and Noble Metals Eastman, D. E. Physical Review B, Vol. 2, Issue 1 https://doi.org/10.1103/PhysRevB.2.1	journal	July 1970
Calculation of the dynamic response of Schottky barriers with a continuous distribution of gap states Cohen, J. David; Lang, David V. Physical Review B, Vol. 25, Issue 8 https://doi.org/10.1103/PhysRevB.25.5321	journal	April 1982
Photoelectron-spectroscopy study of the electronic structure of Au and Ag overlayers on Pt(100), Pt(111), and Pt(997) surfaces Salmerón, M.; Ferrer, S.; Jazzar, M. Physical Review B, Vol. 28, Issue 12 https://doi.org/10.1103/PhysRevB.28.6758	journal	December 1983
Controlling Schottky energy barriers in organic electronic devices using self-assembled monolayers Campbell, I. H.; Rubin, S.; Zawodzinski, T. A. Physical Review B, Vol. 54, Issue 20 https://doi.org/10.1103/PhysRevB.54.R14321	journal	November 1996

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Controlling the Schottky Barrier at the Pt/TiO2 Interface by Intercalation of a Self-Assembled Monolayer with Oriented Dipole Moments

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Controlling the Schottky Barrier at the Pt/TiO₂ Interface by Intercalation of a Self-Assembled Monolayer with Oriented Dipole Moments