Break-junctions; Conductance measurement; Custom-built electronics; Electrical conductance; Multivariate approach; Scanning tunnelling microscopes; Single molecule; Single molecule level; Thermal offset; Thermoelectric measurements; Electronic, Optical and Magnetic Materials; Energy (all); Physical and Theoretical Chemistry; Surfaces, Coatings and Films
Abstract :
[en] We report a method using scanning tunneling microscope single molecular break junction to simultaneously measure and correlate the single-molecule thermopower and electrical conductance. In contrast to previously reported approaches, it does not require custom-built electronics and takes advantage of a trace-by-trace calibration of the thermal offset at the Au/Au contact, thus greatly facilitating thermoelectric measurements at the single-molecule level. We report measurements of three molecules, 1,4-di(4-(ethynyl(phenylthioacetate))) benzene, 1,8-octanedithiol, and 4,4′-bipyridine, and determine single-molecule Seebeck coefficients of 12(3), 5(2), and -5(2) μV K-1, respectively. Furthermore, the method statistically correlates the Seebeck voltage offset, electrical conductance, and stretching displacement of the single-molecule junction and allows for direct comparison with current-distance spectroscopy results obtained at constant bias.
Disciplines :
Chemistry Physics
Author, co-author :
Hamill, Joseph ; Université de Liège - ULiège > Molecular Systems (MolSys) ; School of Chemistry, University of Birmingham, Edgbaston Campus, Birmingham, United Kingdom
Weaver, Christopher; School of Chemistry, University of Birmingham, Edgbaston Campus, Birmingham, United Kingdom
Albrecht, Tim ; School of Chemistry, University of Birmingham, Edgbaston Campus, Birmingham, United Kingdom
Language :
English
Title :
Multivariate Approach to Single-Molecule Thermopower and Electrical Conductance Measurements
Publication date :
02 December 2021
Journal title :
Journal of Physical Chemistry. C, Nanomaterials and interfaces
EPSRC - Engineering and Physical Sciences Research Council
Funding text :
This work was supported by EPSRC Grants EP/N032977/1 and EP/N032977/2 (JMH, TA) and funding for a PhD studentship from the University of Birmingham (CW).
Cullen, J. M.; Allwood, J. M. Theoretical Efficiency Limits for Energy Conversion Devices. Energy 2010, 35, 2059-2069, 10.1016/j.energy.2010.01.024
Forman, C.; Muritala, I. K.; Pardemann, R.; Meyer, B. Estimating the Global Waste Heat Potential. Renewable Sustainable Energy Rev. 2016, 57, 1568-1579, 10.1016/j.rser.2015.12.192
Seebeck, T. J. Magnetische Polarisation der Metalle und Erze durch Temperatur-Differenz. In Abhandlungen Der Königlichen Akademie Der Wissenschaften Zu Berlin, Reimer, G. Ed., Deutsche Akademie Der Wissenschaften Zu Berlin, Berlin, 1822; pp 265-373.
Volta, A.; Banks, J. On the Electricity Excited by the Mere Contact of Conducting Substances of Different Kinds. Philos. Mag. 1800, 7, 289-311, 10.1080/14786440008562590
Telkes, M. The Efficiency of Thermoelectric Generators. J. Appl. Phys. 1947, 18, 1116-1127, 10.1063/1.1697593
Lambert, C. J. Quantum Transport in Nanostructures and Molecules: An Introduction to Molecular Electronics, IOP Publishing Ltd., 2021.
Lambert, C. J.; Sadeghi, H.; Al-Galiby, Q. Quantum-Interference-Enhanced Thermoelectricity in Single Molecules and Molecular Films. C. R. Phys. 2016, 17, 1084-1095, 10.1016/j.crhy.2016.08.003
Famili, M.; Grace, I.; Sadeghi, H.; Lambert, C. J. Suppression of Phonon Transport in Molecular Christmas Trees. ChemPhysChem 2017, 18, 1234-1241, 10.1002/cphc.201700147
Cui, L.; Miao, R.; Jiang, C.; Meyhofer, E.; Reddy, P. Perspective: Thermal and Thermoelectric Transport in Molecular Junctions. J. Chem. Phys. 2017, 146, 092201 10.1063/1.4976982
Rincón-García, L.; Evangeli, C.; Rubio-Bollinger, G.; Agraït, N. Thermopower Measurements in Molecular Junctions. Chem. Soc. Rev. 2016, 45, 4285-4306, 10.1039/C6CS00141F
Dubi, Y.; Di Ventra, M. Colloquium: Heat Flow and Thermoelectricity in Atomic and Molecular Junctions. Rev. Modern Phys. 2011, 83, 131-155, 10.1103/RevModPhys.83.131
Zhang, J.; Kuznetsov, A. M.; Medvedev, I. G.; Chi, Q.; Albrecht, T.; Jensen, P. S.; Ulstrup, J. Single-Molecule Electron Transfer in Electrochemical Environments. Chem. Rev. 2008, 108, 2737-2791, 10.1021/cr068073+
Lemmer, M.; Inkpen, M. S.; Kornysheva, K.; Long, N. J.; Albrecht, T. Unsupervised Vector-based Classification of Single-Molecule Charge Transport Data. Nat. Commun. 2016, 7, 12922 10.1038/ncomms12922
Reddy, P.; Jang, S.-Y.; Segalman, R. A.; Majumdar, A. Thermoelectricity in Molecular Junctions. Science 2007, 315, 1568-1571, 10.1126/science.1137149
Malen, J. A.; Doak, P.; Baheti, K.; Don Tilley, T.; Majumdar, A.; Segalman, R. A. Identifying the Length Dependence of Orbital Alignment and Contact Coupling in Molecular Heterojunctions. Nano Lett. 2009, 9, 1164-1169, 10.1021/nl803814f
Widawski, J. R.; Darancet, P.; Neaton, J. B.; Venkataraman, L. Simultaneous Determination of Conductance and Thermopower of Single Molecule Junctions. Nano Lett. 2012, 12, 354-358, 10.1021/nl203634m
Li, Y.; Xiang, L.; Palma, J. L.; Asai, Y.; Tao, N. Thermoelectric Effect and its Dependence on Molecular Length and Sequence in Single DNA Molecules. Nat. Commun. 2016, 7, 11294 10.1038/ncomms11294
Yzambart, G.; Rincón-García, L.; Al-Jobory, A. A.; Ismael, A. K.; Rubio-Bollinger, G.; Lambert, C. J.; Agraït, N.; Bryce, M. R. Thermoelectric Properties of 2,7-Dipyridylfluorene Derivatives in Single-Molecule Junctions. J. Phys. Chem. C 2018, 122, 27198-27204, 10.1021/acs.jpcc.8b08488
Gehring, P.; van der Star, M.; Evangeli, C.; Roy, J. J. L.; Bogani, L.; Kolosov, O. V.; van der Zant, H. S. J. Efficient Heating of Single-Molecule Junctions for Thermoelectric Studies at Cryogenic Temperatures. Appl. Phys. Lett. 2019, 115, 073103 10.1063/1.5118861
Albrecht, T.; Slabaugh, G.; Alonso, E.; Al-Arif, M. R. Deep Learning for Single-Molecule Science. Nanotechnology 2017, 28, 423001 10.1088/1361-6528/aa8334
Huang, C.; Rudnev, A. V.; Hong, W.; Wandlowski, T. Break Junction under Electrochemical Gating: Testbed for Single-Molecule Electronics. Chem. Soc. Rev. 2015, 44, 889-901, 10.1039/C4CS00242C
Ratner, M. A. Brief History of Molecular Electronics. Nat. Nanotechnol. 2013, 8, 378-381, 10.1038/nnano.2013.110
Ludoph, B.; van Ruitenbeek, J. M. Thermopower of Atomic-size Metallic Contacts. Phys. Rev. B 1999, 59, 12290-12293, 10.1103/PhysRevB.59.12290
Tsutsui, M.; Morikawa, T.; Arima, A.; Taniguchi, M. Thermoelectricity in Atom-sized Junctions at Room Temperatures. Sci. Rep. 2013, 3, 3326 10.1038/srep03326
Evangeli, C.; Matt, M.; Rincón-García, L.; Pauly, F.; Nielaba, P.; Rubio-Bollinger, G.; Cuevas, J. C.; Agraït, N. Quantum Thermopower of Metallic Atomic-Size Contacts at Room Temperature. Nano Lett. 2015, 15, 1006-1011, 10.1021/nl503853v
Hamill, J. M.; Zhao, X. T.; Mészáros, G.; Bryce, M. R.; Arenz, M. Fast Data Sorting with Modified Principal Component Analysis to Distinguish Unique Single Molecular Break Junction Trajectories. Phys. Rev. Lett. 2018, 120, 016601 10.1103/PhysRevLett.120.016601
Cabosart, D.; Abbassi, M. E.; Stefani, D.; Frisenda, R.; Calame, M.; van der Zant, H. S. J.; Perrin, M. L. A Reference-free Clustering Method for the Analysis of Molecular Break-Junction Measurements. Appl. Phys. Lett. 2019, 114, 143102 10.1063/1.5089198
Pearson, K. Contributions to the Mathematical Theory of Evolution, In Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, The Royal Society, 1894; Vol 185, pp 71-110.
Jain, A. K.; Murty, M. N.; Flynn, P. J. Data Clustering: a Review. ACM Comput. Surv. 1999, 31, 264-323, 10.1145/331499.331504
Mayor, M.; Weber, H. B. Statistical Analysis of Single-Molecule Junctions. Angew. Chem., Int. Ed. 2004, 43, 2882-2884, 10.1002/anie.200301733
Quan, R.; Pitler, C. S.; Ratner, M. A.; Reuter, M. G. Quantitative Interpretations of Break Junction Conductance Histograms in Molecular Electron Transport. ACS Nano 2015, 9, 7704-7713, 10.1021/acsnano.5b03183
Vladyka, A.; Albrecht, T. Unsupervised Classification of Single-Molecule Data with Autoencoders and Transfer Learning. Mach. Learn.: Sci. Technol. 2020, 1, 035013 10.1088/2632-2153/aba6f2
Miao, R.; Xu, H.; Skripnik, M.; Cui, L.; Wang, K.; Pedersen, K. G. L.; Leijnse, M.; Pauly, F.; Wärnmark, K.; Meyhofer, E.; Reddy, P.; Linke, H. Influence of Quantum Interference on the Thermoelectric Properties of Molecular Junctions. Nano Lett. 2018, 18, 5666-5672, 10.1021/acs.nanolett.8b02207
Inkpen, M. S.; Lemmer, M.; Fitzpatrick, N.; Milan, D. C.; Nichols, R. J.; Long, N. J.; Albrecht, T. New Insights into Single-Molecule Junctions Using a Robust, Unsupervised Approach to Data Collection and Analysis. J. Am. Chem. Soc. 2015, 137, 9971-9981, 10.1021/jacs.5b05693
Kim, T.; Darancet, P.; Widawsky, J. R.; Kotiuga, M.; Quek, S. Y.; Neaton, J. B.; Venkataraman, L. Determination of Energy Level Alignment and Coupling Strength in 4,4′-Bipyridine Single-Molecule Junctions. Nano Lett. 2014, 14, 794-798, 10.1021/nl404143v
Paulsson, M.; Datta, S. Thermoelectric effect in molecular electronics. Phys. Rev. B 2003, 67, 241403 10.1103/PhysRevB.67.241403
Roychowdhury, S.; Ghosh, T.; Arora, R.; Samanta, M.; Xie, L.; Singh, N. K.; Soni, A.; He, J.; Waghmare, U. V.; Biswas, K. Enhanced Atomic Ordering Leads to High Thermoelectric Performance in AgSbTe2. Science 2021, 371, 722-727, 10.1126/science.abb3517
Bergfield, J. P.; Solis, M. A.; Stafford, C. A. Giant Thermoelectric Effect from Transmission Supernodes. ACS Nano 2010, 4, 5314-5320, 10.1021/nn100490g
Sánchez, D.; López, R. Scattering Theory of Nonlinear Thermoelectric Transport. Phys. Rev. Lett. 2013, 110, 026804 10.1103/PhysRevLett.110.026804
