Ultrasensitive Photothermal Spectroscopy: Harnessing the Seebeck Effect for Attogram-Level Detection

Zhao, Yaoli; Chakraborty, Patatri; Passian, Ali; Thundat, Thomas

doi:10.1021/acs.nanolett.3c01710

Ultrasensitive Photothermal Spectroscopy: Harnessing the Seebeck Effect for Attogram-Level Detection

Journal Article · Mon Aug 14 00:00:00 EDT 2023 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.3c01710· OSTI ID:2001395

Zhao, Yaoli ^[1]; Chakraborty, Patatri ^[1]; ^[2]; ^[1]

Univ. at Buffalo, NY (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Molecular-level spectroscopy is crucial for sensing and imaging applications, yet detecting and quantifying minuscule quantities of chemicals remain a challenge, especially when they surface adsorb in low numbers. Here, we introduce a photothermal spectroscopic technique that enables the high selectivity sensing of adsorbates with an attogram detection limit. Our approach utilizes the Seebeck effect in a microfabricated nanoscale thermocouple junction, incorporated into the apex of a microcantilever. We observe minimal thermal mass exhibited by the sensor, which maintains exceptional thermal insulation. The temperature variation driving the thermoelectric junction arises from the nonradiative decay of molecular adsorbates’ vibrational states on the tip. We demonstrate the detection of photothermal spectra of physisorbed trinitrotoluene (TNT) and dimethyl methylphosphonate (DMMP) molecules, as well as representative polymers, with an estimated mass of 10^-18 g.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2001395

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 17 Vol. 23; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (33)

Investigation of the spectral width of quantum cascade laser emission near 5.2 μm by a heterodyne experiment Ganser, Heiko; Frech, Bertold; Jentsch, Andreas Optics Communications, Vol. 197, Issue 1-3 https://doi.org/10.1016/S0030-4018(01)01441-9	journal	September 2001
Polymer-grafted QCM chemical sensor and application to heavy metal ions real time detection Sartore, Luciana; Barbaglio, Marzia; Borgese, Laura Sensors and Actuators B: Chemical, Vol. 155, Issue 2 https://doi.org/10.1016/j.snb.2011.01.003	journal	July 2011
Selective detection of physisorbed hydrocarbons using photothermal cantilever deflection spectroscopy Bagheri, Mehrdad; Chae, Inseok; Lee, Dongkyu Sensors and Actuators B: Chemical, Vol. 191 https://doi.org/10.1016/j.snb.2013.10.078	journal	February 2014
Chemical Sensors and Molecular Selectivity Murray, Royce Analytical Chemistry, Vol. 66, Issue 9 https://doi.org/10.1021/ac00081a600	journal	April 1994
Tuning Sensitivity and Selectivity of Complementary Metal Oxide Semiconductor-Based Capacitive Chemical Microsensors Kummer, Adrian M.; Hierlemann, Andreas; Baltes, Henry Analytical Chemistry, Vol. 76, Issue 9 https://doi.org/10.1021/ac0352272	journal	May 2004
Limits of Recognition for Simple Vapor Mixtures Determined with a Microsensor Array Hsieh, Meng-Da; Zellers, Edward T. Analytical Chemistry, Vol. 76, Issue 7 https://doi.org/10.1021/ac035294w	journal	April 2004
Photothermal Infrared Spectroscopy of Airborne Samples with Mechanical String Resonators Yamada, Shoko; Schmid, Silvan; Larsen, Tom Analytical Chemistry, Vol. 85, Issue 21 https://doi.org/10.1021/ac402585e	journal	October 2013
Femtogram-Scale Photothermal Spectroscopy of Explosive Molecules on Nanostrings Biswas, T. S.; Miriyala, N.; Doolin, C. Analytical Chemistry, Vol. 86, Issue 22 https://doi.org/10.1021/ac503318e	journal	October 2014
Electronic Nose for Recognition of Volatile Vapor Mixtures Using a Nanopore-Enhanced Opto-Calorimetric Spectroscopy Chae, Inseok; Lee, Dongkyu; Kim, Seonghwan Analytical Chemistry, Vol. 87, Issue 14 https://doi.org/10.1021/acs.analchem.5b00915	journal	July 2015
High-Performance Atomically-Thin Room-Temperature NO ₂ Sensor Azizi, Amin; Dogan, Mehmet; Long, Hu Nano Letters, Vol. 20, Issue 8 https://doi.org/10.1021/acs.nanolett.0c02221	journal	July 2020
High-Contrast Plasmonic-Enhanced Shallow Spin Defects in Hexagonal Boron Nitride for Quantum Sensing Gao, Xingyu; Jiang, Boyang; Llacsahuanga Allcca, Andres E. Nano Letters, Vol. 21, Issue 18 https://doi.org/10.1021/acs.nanolett.1c02495	journal	September 2021
Photothermal Electrical Resonance Spectroscopy of Physisorbed Molecules on a Nanowire Resonator Prashanthi, Kovur; Phani, Arindam; Thundat, Thomas Nano Letters, Vol. 15, Issue 8 https://doi.org/10.1021/acs.nanolett.5b02557	journal	July 2015
Simultaneous Chemical and Refractive Index Sensing in the 1–2.5 μm Near-Infrared Wavelength Range on Nanoporous Gold Disks Shih, Wei-Chuan; Santos, Greggy M.; Zhao, Fusheng Nano Letters, Vol. 16, Issue 7 https://doi.org/10.1021/acs.nanolett.6b01959	journal	June 2016
Microscale-Resolution Thermal Mapping Using a Flexible Platform of Patterned Quantum Sensors Andrich, Paolo; Li, Jiajing; Liu, Xiaoying Nano Letters, Vol. 18, Issue 8 https://doi.org/10.1021/acs.nanolett.8b00895	journal	July 2018
Quantum Plasmonic Immunoassay Sensing Kongsuwan, Nuttawut; Xiong, Xiao; Bai, Ping Nano Letters, Vol. 19, Issue 9 https://doi.org/10.1021/acs.nanolett.9b01137	journal	July 2019
Wide-Field Magnetic Field and Temperature Imaging Using Nanoscale Quantum Sensors Foy, Christopher; Zhang, Lenan; Trusheim, Matthew E. ACS Applied Materials & Interfaces, Vol. 12, Issue 23 https://doi.org/10.1021/acsami.0c01545	journal	April 2020
Toward Healthcare Diagnoses by Machine-Learning-Enabled Volatile Organic Compound Identification Zhu, Jianxiong; Ren, Zhihao; Lee, Chengkuo ACS Nano, Vol. 15, Issue 1 https://doi.org/10.1021/acsnano.0c07464	journal	December 2020
Micromachined Chip Scale Thermal Sensor for Thermal Imaging Shekhawat, Gajendra S.; Ramachandran, Srinivasan; Jiryaei Sharahi, Hossein ACS Nano, Vol. 12, Issue 2 https://doi.org/10.1021/acsnano.7b08504	journal	February 2018
Surface Stress, Kinetics, and Structure of Alkanethiol Self-Assembled Monolayers Godin, Michel; Williams, P. J.; Tabard-Cossa, Vincent Langmuir, Vol. 20, Issue 17 https://doi.org/10.1021/la030257l	journal	May 2004
Purity Evaluation of As-Prepared Single-Walled Carbon Nanotube Soot by Use of Solution-Phase Near-IR Spectroscopy Itkis, M. E.; Perea, D. E.; Niyogi, S. Nano Letters, Vol. 3, Issue 3 https://doi.org/10.1021/nl025926e	journal	March 2003
Toward Large Arrays of Multiplex Functionalized Carbon Nanotube Sensors for Highly Sensitive and Selective Molecular Detection Qi, Pengfei; Vermesh, Ophir; Grecu, Mihai Nano Letters, Vol. 3, Issue 3 https://doi.org/10.1021/nl034010k	journal	March 2003
Selective Probing and Imaging of Cells with Single Walled Carbon Nanotubes as Near-Infrared Fluorescent Molecules Welsher, Kevin; Liu, Zhuang; Daranciang, Dan Nano Letters, Vol. 8, Issue 2 https://doi.org/10.1021/nl072949q	journal	February 2008
Dielectrophoresis-Assembled Zeolitic Imidazolate Framework Nanoparticle-Coupled Resonators for Highly Sensitive and Selective Gas Detection Hwang, Yongha; Sohn, Hyunmin; Phan, Anh Nano Letters, Vol. 13, Issue 11 https://doi.org/10.1021/nl4027692	journal	October 2013
Quantitative Measurement with Scanning Thermal Microscope by Preventing the Distortion Due to the Heat Transfer through the Air Kim, Kyeongtae; Chung, Jaehun; Hwang, Gwangseok ACS Nano, Vol. 5, Issue 11 https://doi.org/10.1021/nn2026325	journal	October 2011
Photothermal spectroscopy with femtojoule sensitivity using a micromechanical device Barnes, J. R.; Stephenson, R. J.; Welland, M. E. Nature, Vol. 372, Issue 6501 https://doi.org/10.1038/372079a0	journal	November 1994
Biochemical sensing in graphene-enhanced microfiber resonators with individual molecule sensitivity and selectivity Cao, Zhongxu; Yao, Baicheng; Qin, Chenye Light: Science & Applications, Vol. 8, Issue 1 https://doi.org/10.1038/s41377-019-0213-3	journal	November 2019
Modified cantilever arrays improve sensitivity and reproducibility of nanomechanical sensing in living cells Patil, Samadhan B.; Al-Jehani, Rajai M.; Etayash, Hashem Communications Biology, Vol. 1, Issue 1 https://doi.org/10.1038/s42003-018-0179-3	journal	October 2018
Scanning thermal microscopy using batch fabricated thermocouple probes Mills, G.; Zhou, H.; Midha, A. Applied Physics Letters, Vol. 72, Issue 22 https://doi.org/10.1063/1.121453	journal	June 1998
Scanning thermal microscopy of carbon nanotubes using batch-fabricated probes Shi, Li; Plyasunov, Sergei; Bachtold, Adrian Applied Physics Letters, Vol. 77, Issue 26 https://doi.org/10.1063/1.1334658	journal	December 2000
Trace explosive detection using photothermal deflection spectroscopy Krause, Adam R.; Van Neste, Charles; Senesac, Larry Journal of Applied Physics, Vol. 103, Issue 9 https://doi.org/10.1063/1.2908181	journal	May 2008
Effect of chain length on nanomechanics of alkanethiol self-assembly Desikan, Ramya; Armel, Sarah; Meyer III, Harry M. Nanotechnology, Vol. 18, Issue 42 https://doi.org/10.1088/0957-4484/18/42/424028	journal	September 2007
Photothermal cantilever deflection spectroscopy Kim, Seonghwan; Lee, Dongkyu; Thundat, Thomas EPJ Techniques and Instrumentation, Vol. 1, Issue 1 https://doi.org/10.1140/epjti/s40485-014-0007-1	journal	August 2014
Chemical Selectivity and Sensitivity of a 16-Channel Electronic Nose for Trace Vapour Detection Strle, Drago; Štefane, Bogdan; Trifkovič, Mario Sensors, Vol. 17, Issue 12 https://doi.org/10.3390/s17122845	journal	December 2017

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Ultrasensitive Photothermal Spectroscopy: Harnessing the Seebeck Effect for Attogram-Level Detection

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