Rationalizing energy level alignment by characterizing Lewis acid/base and ionic interactions at printable semiconductor/ionic liquid interfaces

Du Hill, Linze; De Keersmaecker, Michel; Colbert, Adam E.; Hill, Joshua W.; Placencia, Diogenes; Boercker, Janice E.; Armstrong, Neal R.; Ratcliff, Erin L.

doi:10.1039/d1mh01306h

Rationalizing energy level alignment by characterizing Lewis acid/base and ionic interactions at printable semiconductor/ionic liquid interfaces

Journal Article · Mon Nov 29 00:00:00 UTC 2021 · Materials Horizons

DOI:https://doi.org/10.1039/d1mh01306h· OSTI ID:1833838

Du Hill, Linze ^[1]; ^[2]; ^[3]; Hill, Joshua W. ^[2]; Placencia, Diogenes ^[3]; ^[3]; ^[2]; ^[2]

Univ. of Arizona, Tucson, AZ (United States); University of Arizona
Univ. of Arizona, Tucson, AZ (United States)
US Naval Research Lab., Washington, DC (United States)

Charge transfer and energy conversion processes at semiconductor/electrolyte interfaces are controlled by local electric field distributions, which can be especially challenging to measure. Furthermore, we leverage the low vapor pressure and vacuum compatibility of ionic liquid electrolytes to undertake a layer-by-layer, ultra-high vacuum deposition of a prototypical ionic liquid EMIM⁺ (1-ethyl-3-methylimidazolium) and TFSI^– (bis(trifluoromethylsulfonyl)-imide) on the surfaces of different electronic materials. We consider a case-by-case study between a standard metal (Au) and four printed electronic materials, where interfaces are characterized by a combination of X-ray and ultraviolet photoemission spectroscopies (XPS/UPS). For template-stripped gold surfaces, we observe through XPS a preferential orientation of the TFSI anion at the gold surface, enabling large electric fields (~10⁸ eV m^–1) within the first two monolayers detected by a large surface vacuum level shift (0.7 eV) in UPS.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Arizona, Tucson, AZ (United States)

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

Grant/Contract Number:: SC0020208

OSTI ID:: 1833838

Alternate ID(s):: OSTI ID: 1833894

Journal Information:: Materials Horizons, Journal Name: Materials Horizons Journal Issue: 1 Vol. 9; ISSN 2051-6347

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (63)

Energy Level Alignment and Interfacial Electronic Structures at Organic/Metal and Organic/Organic Interfaces Ishii, Hisao; Sugiyama, Kiyoshi; Ito, Eisuke Advanced Materials, Vol. 11, Issue 8, p. 605-625 https://doi.org/10.1002/(SICI)1521-4095(199906)11:8<605::AID-ADMA605>3.0.CO;2-Q	journal	June 1999
Electrochemical Surface Science Kolb, Dieter M. Angewandte Chemie International Edition, Vol. 40, Issue 7 https://doi.org/10.1002/1521-3773(20010401)40:7<1162::AID-ANIE1162>3.0.CO;2-F	journal	April 2001
Interface Engineering for Organic Electronics Ma, Hong; Yip, Hin-Lap; Huang, Fei Advanced Functional Materials, Vol. 20, Issue 9 https://doi.org/10.1002/adfm.200902236	journal	April 2010
Modification of the Gallium-Doped Zinc Oxide Surface with Self-Assembled Monolayers of Phosphonic Acids: A Joint Theoretical and Experimental Study Li, Hong; Ratcliff, Erin L.; Sigdel, Ajaya K. Advanced Functional Materials, Vol. 24, Issue 23 https://doi.org/10.1002/adfm.201303670	journal	February 2014
Chemically Controlled Reversible and Irreversible Extraction Barriers Via Stable Interface Modification of Zinc Oxide Electron Collection Layer in Polycarbazole-based Organic Solar Cells Cowan, Sarah R.; Schulz, Philip; Giordano, Anthony J. Advanced Functional Materials, Vol. 24, Issue 29 https://doi.org/10.1002/adfm.201400158	journal	April 2014
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
Electron Energetics at Surfaces and Interfaces: Concepts and Experiments Cahen, D.; Kahn, A. Advanced Materials, Vol. 15, Issue 4 https://doi.org/10.1002/adma.200390065	journal	February 2003
Investigating the Influence of Interfacial Contact Properties on Open Circuit Voltages in Organic Photovoltaic Performance: Work Function Versus Selectivity Ratcliff, Erin L.; Garcia, Andres; Paniagua, Sergio A. Advanced Energy Materials, Vol. 3, Issue 5 https://doi.org/10.1002/aenm.201200669	journal	February 2013
From Defects to Degradation: A Mechanistic Understanding of Degradation in Perovskite Solar Cell Devices and Modules Dunfield, Sean P.; Bliss, Lyle; Zhang, Fei Advanced Energy Materials, Vol. 10, Issue 26 https://doi.org/10.1002/aenm.201904054	journal	March 2020
Towards a Molecular Understanding of Cation-Anion Interactions-Probing the Electronic Structure of Imidazolium Ionic Liquids by NMR Spectroscopy, X-ray Photoelectron Spectroscopy and Theoretical Calculations Cremer, Till; Kolbeck, Claudia; Lovelock, Kevin R. J. Chemistry - A European Journal, Vol. 16, Issue 30 https://doi.org/10.1002/chem.201001032	journal	July 2010
Physical Vapor Deposition of [EMIM][Tf ₂ N]: A New Approach to the Modification of Surface Properties with Ultrathin Ionic Liquid Films Cremer, Till; Killian, Manuela; Gottfried, J. Michael ChemPhysChem, Vol. 9, Issue 15 https://doi.org/10.1002/cphc.200800300	journal	October 2008
Quantitative electron spectroscopy of surfaces: A standard data base for electron inelastic mean free paths in solids Seah, M. P.; Dench, W. A. Surface and Interface Analysis, Vol. 1, Issue 1 https://doi.org/10.1002/sia.740010103	journal	February 1979
Semicrystalline morphology in thin films of poly(3-hexylthiophene) Thurn-Albrecht, T.; Thomann, R.; Heinzel, T. Colloid & Polymer Science, Vol. 282, Issue 8, p. 932-938 https://doi.org/10.1007/s00396-004-1100-9	journal	June 2004
Electrochemical surface science: past, present and future Kolb, Dieter M. Journal of Solid State Electrochemistry, Vol. 15, Issue 7-8 https://doi.org/10.1007/s10008-011-1396-6	journal	May 2011
Microscopic investigations of semiconductor interfaces Margaritondo, G. Solid-State Electronics, Vol. 26, Issue 6 https://doi.org/10.1016/0038-1101(83)90165-X	journal	June 1983
Continuous work function monitoring for electrode emersion Rath, D. L.; Kolb, D. M. Surface Science, Vol. 109, Issue 3 https://doi.org/10.1016/0039-6028(81)90432-5	journal	September 1981
Continuous work function monitoring of the emersed double layer Hansen, Galen J.; Hansen, Wilford N. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 150, Issue 1-2 https://doi.org/10.1016/S0022-0728(83)80201-0	journal	July 1983
Elementary processes at semiconductor/electrolyte interfaces: perspectives and limits of electron spectroscopy Mayer, Th.; Lebedev, M.; Hunger, R. Applied Surface Science, Vol. 252, Issue 1 https://doi.org/10.1016/j.apsusc.2005.01.110	journal	September 2005
Molecular-level understanding of electric double layer in ionic liquids Yan, Jia-Wei; Tian, Zhong-Qun; Mao, Bing-Wei Current Opinion in Electrochemistry, Vol. 4, Issue 1 https://doi.org/10.1016/j.coelec.2017.09.008	journal	August 2017
In-situ STM and AFM Studies on Electrochemical Interfaces in imidazolium-based ionic liquids Liu, Shuai; Peng, Jin; Chen, Li Electrochimica Acta, Vol. 309 https://doi.org/10.1016/j.electacta.2019.04.066	journal	June 2019
Overcoming Redox Reactions at Perovskite-Nickel Oxide Interfaces to Boost Voltages in Perovskite Solar Cells Boyd, Caleb C.; Shallcross, R. Clayton; Moot, Taylor Joule, Vol. 4, Issue 8 https://doi.org/10.1016/j.joule.2020.06.004	journal	August 2020
The interplay between molecular structure and dielectric propertiesin ionic liquids: A comparative study Haddad, Boumediene; Kachroudi, Achraf; Turky, Gamal Journal of Molecular Liquids, Vol. 324 https://doi.org/10.1016/j.molliq.2020.114674	journal	February 2021
The role of hydrogen atoms in interactions involving imidazolium-based ionic liquids Kempter, V.; Kirchner, B. Journal of Molecular Structure, Vol. 972, Issue 1-3 https://doi.org/10.1016/j.molstruc.2010.02.003	journal	May 2010
Sputtered nickel oxide thin film for efficient hole transport layer in polymer–fullerene bulk-heterojunction organic solar cell Widjonarko, N. Edwin; Ratcliff, Erin L.; Perkins, Craig L. Thin Solid Films, Vol. 520, Issue 10 https://doi.org/10.1016/j.tsf.2011.10.059	journal	March 2012
Intersystem Subpopulation Charge Transfer and Conformational Relaxation Preceding in Situ Conductivity in Electrochemically Doped Poly(3-hexylthiophene) Electrodes Harris, Jonathan K.; Neelamraju, Bharati; Ratcliff, Erin L. Chemistry of Materials, Vol. 31, Issue 17 https://doi.org/10.1021/acs.chemmater.9b01298	journal	December 2018
Characterization of the Interface Structure of 1-Ethyl-2,3-alkylimidazolium Bis(trifluoromethylsulfonyl)imide on a Au(111) Surface with Molecular Dynamics Simulations Wang, Yue; Sun, Yifei; Dong, Yubin The Journal of Physical Chemistry B, Vol. 125, Issue 14 https://doi.org/10.1021/acs.jpcb.0c09994	journal	April 2021
Self-Assembled Monolayers with Embedded Dipole Moments for Work Function Engineering of Oxide Substrates Asyuda, Andika; Gärtner, Michael; Wan, Xianglong The Journal of Physical Chemistry C, Vol. 124, Issue 16 https://doi.org/10.1021/acs.jpcc.0c00482	journal	March 2020
Surface Modification of Indium–Tin Oxide with Functionalized Perylene Diimides: Characterization of Orientation, Electron-Transfer Kinetics and Electronic Structure Zheng, Yilong; Giordano, Anthony J.; Shallcross, R. Clayton The Journal of Physical Chemistry C, Vol. 120, Issue 36 https://doi.org/10.1021/acs.jpcc.6b06812	journal	September 2016
Quantifying the Extent of Contact Doping at the Interface between High Work Function Electrical Contacts and Poly(3-hexylthiophene) (P3HT) Shallcross, R. Clayton; Stubhan, Tobias; Ratcliff, Erin L. The Journal of Physical Chemistry Letters, Vol. 6, Issue 8 https://doi.org/10.1021/acs.jpclett.5b00444	journal	March 2015
Growth of Multilayers of Ionic Liquids on Au(111) Investigated by Atomic Force Microscopy in Ultrahigh Vacuum Meusel, Manuel; Lexow, Matthias; Gezmis, Afra Langmuir, Vol. 36, Issue 45 https://doi.org/10.1021/acs.langmuir.0c02596	journal	November 2020
Impact of Titanium Dioxide Surface Defects on the Interfacial Composition and Energetics of Evaporated Perovskite Active Layers Shallcross, R. Clayton; Olthof, Selina; Meerholz, Klaus ACS Applied Materials & Interfaces, Vol. 11, Issue 35 https://doi.org/10.1021/acsami.9b09935	journal	August 2019
Nanostructure of the Ionic Liquid–Graphite Stern Layer Elbourne, Aaron; McDonald, Samila; Voïchovsky, Kislon ACS Nano, Vol. 9, Issue 7 https://doi.org/10.1021/acsnano.5b02921	journal	June 2015
Ionic Liquid Vapors in Vacuum: Possibility to Derive Anodic Stabilities from DFT and UPS Kuusik, Ivar; Kook, Mati; Pärna, Rainer ACS Omega, Vol. 6, Issue 8 https://doi.org/10.1021/acsomega.0c05369	journal	February 2021
The Modification of Indium Tin Oxide with Phosphonic Acids: Mechanism of Binding, Tuning of Surface Properties, and Potential for Use in Organic Electronic Applications Hotchkiss, Peter J.; Jones, Simon C.; Paniagua, Sergio A. Accounts of Chemical Research, Vol. 45, Issue 3 https://doi.org/10.1021/ar200119g	journal	October 2011
Evidence for near-Surface NiOOH Species in Solution-Processed NiO _x Selective Interlayer Materials: Impact on Energetics and the Performance of Polymer Bulk Heterojunction Photovoltaics Ratcliff, Erin L.; Meyer, Jens; Steirer, K. Xerxes Chemistry of Materials, Vol. 23, Issue 22 https://doi.org/10.1021/cm202296p	journal	November 2011
Energetics of the semiconductor-electrolyte interface Turner, John A. Journal of Chemical Education, Vol. 60, Issue 4 https://doi.org/10.1021/ed060p327	journal	April 1983
Finding the Way to Solar Fuels with Dye-Sensitized Photoelectrosynthesis Cells Brennaman, M. Kyle; Dillon, Robert J.; Alibabaei, Leila Journal of the American Chemical Society, Vol. 138, Issue 40 https://doi.org/10.1021/jacs.6b06466	journal	September 2016
Molecular Dynamics Study of the Ionic Liquid 1- n -Butyl-3-methylimidazolium Hexafluorophosphate Morrow, Timothy I.; Maginn, Edward J. The Journal of Physical Chemistry B, Vol. 106, Issue 49 https://doi.org/10.1021/jp0267003	journal	December 2002
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
Interfacial Electrostatics of Self-Assembled Monolayers of Alkane Thiolates on Au(111): Work Function Modification and Molecular Level Alignments Rousseau, R.; De Renzi, V.; Mazzarello, R. The Journal of Physical Chemistry B, Vol. 110, Issue 22 https://doi.org/10.1021/jp061720g	journal	June 2006
Influence of Electrode Surface Composition and Energetics on Small-Molecule Organic Solar Cell Performance: Polar versus Nonpolar Donors on Indium Tin Oxide Contacts Gantz, Jeremy; Placencia, Diogenes; Giordano, Anthony The Journal of Physical Chemistry C, Vol. 117, Issue 3 https://doi.org/10.1021/jp307546v	journal	January 2013
A Density Functional Theory Study of the Reconstruction of Gold (111) Surfaces Torres, Edmanuel; DiLabio, Gino A. The Journal of Physical Chemistry C, Vol. 118, Issue 29 https://doi.org/10.1021/jp411368v	journal	July 2014
Glass−Liquid Transition, Crystallization, and Melting of a Room Temperature Ionic Liquid: Thin Films of 1-Ethyl-3-methylimidazolium Bis[trifluoromethanesulfonyl]imide Studied with TOF-SIMS Souda, Ryutaro The Journal of Physical Chemistry B, Vol. 112, Issue 48 https://doi.org/10.1021/jp805120m	journal	November 2008
Physical Chemistry of Semiconductor−Liquid Interfaces Nozik, Arthur J.; Memming, Rüdiger The Journal of Physical Chemistry, Vol. 100, Issue 31 https://doi.org/10.1021/jp953720e	journal	January 1996
Built-In Potential in Conjugated Polymer Diodes with Changing Anode Work Function: Interfacial States and Deviation from the Schottky–Mott Limit MacLeod, Bradley A.; Horwitz, Noah E.; Ratcliff, Erin L. The Journal of Physical Chemistry Letters, Vol. 3, Issue 9 https://doi.org/10.1021/jz300283h	journal	April 2012
Formation and in Situ Modification of Monolayers Chemisorbed on Ultraflat Template-Stripped Gold Surfaces Wagner, Peter; Hegner, Martin; Guentherodt, Hans-Joachim Langmuir, Vol. 11, Issue 10 https://doi.org/10.1021/la00010a043	journal	October 1995
Electronic Structure of the Surface of the Ionic Liquid [EMIM][Tf ₂ N] Studied by Metastable Impact Electron Spectroscopy (MIES), UPS, and XPS Höfft, O.; Bahr, S.; Himmerlich, M. Langmuir, Vol. 22, Issue 17 https://doi.org/10.1021/la060943v	journal	August 2006
Bias-Dependent Molecular-Level Structure of Electrical Double Layer in Ionic Liquid on Graphite Black, Jennifer M.; Walters, Deron; Labuda, Aleksander Nano Letters, Vol. 13, Issue 12, p. 5954-5960 https://doi.org/10.1021/nl4031083	journal	November 2013
Defects in perovskite-halides and their effects in solar cells Ball, James M.; Petrozza, Annamaria Nature Energy, Vol. 1, Issue 11 https://doi.org/10.1038/nenergy.2016.149	journal	October 2016
Insight into the Electrical Double Layer of an Ionic Liquid on Graphene Jurado, L. Andres; Espinosa-Marzal, Rosa M. Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-04576-x	journal	June 2017
Nickel oxide interlayer films from nickel formate–ethylenediamine precursor: influence of annealing on thin film properties and photovoltaic device performance Steirer, K. X.; Richards, R. E.; Sigdel, A. K. Journal of Materials Chemistry A, Vol. 3, Issue 20 https://doi.org/10.1039/C5TA01379H	journal	January 2015
On the thickness of the double layer in ionic liquids Ruzanov, Anton; Lembinen, Meeri; Jakovits, Pelle Physical Chemistry Chemical Physics, Vol. 20, Issue 15 https://doi.org/10.1039/C7CP07939G	journal	January 2018
Charge driven lateral structural evolution of ions in electric double layer capacitors strongly correlates with differential capacitance Le Ma, Jia; Meng, Qiangqiang; Fan, Jun Physical Chemistry Chemical Physics, Vol. 20, Issue 12 https://doi.org/10.1039/C7CP08075A	journal	January 2018
Time-dependent changes in the growth of ultrathin ionic liquid films on Ag(111) Lexow, Matthias; Talwar, Timo; Heller, Bettina S. J. Physical Chemistry Chemical Physics, Vol. 20, Issue 18 https://doi.org/10.1039/C8CP01411F	journal	January 2018
Imperfections and their passivation in halide perovskite solar cells Chen, Bo; Rudd, Peter N.; Yang, Shuang Chemical Society Reviews, Vol. 48, Issue 14 https://doi.org/10.1039/C8CS00853A	journal	January 2019
Photodecomposition and thermal decomposition in methylammonium halide lead perovskites and inferred design principles to increase photovoltaic device stability Juarez-Perez, Emilio J.; Ono, Luis K.; Maeda, Maki Journal of Materials Chemistry A, Vol. 6, Issue 20 https://doi.org/10.1039/C8TA03501F	journal	January 2018
Practical challenges in the development of photoelectrochemical solar fuels production Spitler, Mark T.; Modestino, Miguel A.; Deutsch, Todd G. Sustainable Energy & Fuels, Vol. 4, Issue 3 https://doi.org/10.1039/C9SE00869A	journal	January 2020
Defect quantification in metal halide perovskites: the solid-state electrochemical alternative De Keersmaecker, Michel; Armstrong, Neal R.; Ratcliff, Erin L. Energy & Environmental Science, Vol. 14, Issue 9 https://doi.org/10.1039/D1EE01525G	journal	January 2021
Mono- and multi-layer adsorption of an ionic liquid on Au(110) Foulston, Richard; Gangopadhyay, Subhashis; Chiutu, Cristina Physical Chemistry Chemical Physics, Vol. 14, Issue 17 https://doi.org/10.1039/c2cp23901a	journal	January 2012
Refined potential model for atomistic simulations of ionic liquid [bmim][PF6] Bhargava, B. L.; Balasubramanian, S. The Journal of Chemical Physics, Vol. 127, Issue 11 https://doi.org/10.1063/1.2772268	journal	September 2007
Ionic liquids behave as dilute electrolyte solutions Gebbie, M. A.; Valtiner, M.; Banquy, X. Proceedings of the National Academy of Sciences, Vol. 110, Issue 24 https://doi.org/10.1073/pnas.1307871110	journal	May 2013
Au(111): A theoretical study of the surface reconstruction and the surface electronic structure Takeuchi, Noboru; Chan, C. T.; Ho, K. M. Physical Review B, Vol. 43, Issue 17 https://doi.org/10.1103/PhysRevB.43.13899	journal	June 1991
Hydroxylation of the surface of PbS nanocrystals passivated with oleic acid Zherebetskyy, D.; Scheele, M.; Zhang, Y. Science, Vol. 344, Issue 6190 https://doi.org/10.1126/science.1252727	journal	May 2014

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