skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Ultrasensitive Photothermal Spectroscopy: Harnessing the Seebeck Effect for Attogram-Level Detection
Molecular-level spectroscopy is crucial for sensing and imaging applications, yet detecting and quantifying minuscule quantities of chemicals remains a challenge, especially when they surface-adsorb in low numbers. Here, we introduce a photothermal spectroscopic technique that enables the sensing and quantification 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 non-radiative decay of molecular adsorbates' vibrational states on the tip. We demonstrate the detection of physisorbed trinitrotoluene (TNT) and dimethyl methylphosphonate (DMMP) molecules, as well as representative polymers, with an estimated mass sensitivity of 10-18 g and a temperature resolution of 40 mK.  more » « less
Award ID(s):
2029375
PAR ID:
10447277
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Nano Letters
ISSN:
1530-6984
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; ; ; ; et al (, Nature Communications)
    Abstract Whether the presence of adsorbates increases or decreases thermal conductivity in metal-organic frameworks (MOFs) has been an open question. Here we report observations of thermal transport in the metal-organic framework HKUST-1 in the presence of various liquid adsorbates: water, methanol, and ethanol. Experimental thermoreflectance measurements were performed on single crystals and thin films, and theoretical predictions were made using molecular dynamics simulations. We find that the thermal conductivity of HKUST-1 decreases by 40 – 80% depending on the adsorbate, a result that cannot be explained by effective medium approximations. Our findings demonstrate that adsorbates introduce additional phonon scattering in HKUST-1, which particularly shortens the lifetimes of low-frequency phonon modes. As a result, the system thermal conductivity is lowered to a greater extent than the increase expected by the creation of additional heat transfer channels. Finally, we show that thermal diffusivity is even more greatly reduced than thermal conductivity by adsorption. 
    more » « less
  2. ; ; ; ; ; ; (, Science Advances)
    The detection of mid-infrared (MIR) light is technologically important for applications such as night vision, imaging, sensing, and thermal metrology. Traditional MIR photodetectors either require cryogenic cooling or have sophisticated device structures involving complex nanofabrication. Here, we conceive spectrally tunable MIR detection by using two-dimensional metal halide perovskites (2D-MHPs) as the critical building block. Leveraging the ultralow cross-plane thermal conductivity and strong temperature-dependent excitonic resonances of 2D-MHPs, we demonstrate ambient-temperature, all-optical detection of MIR light with sensitivity down to 1 nanowatt per square micrometer, using plastic substrates. Through the adoption of membrane-based structures and a photonic enhancement strategy unique to our all-optical detection modality, we further improved the sensitivity to sub–10 picowatt-per-square-micrometer levels. The detection covers the mid-wave infrared regime from 2 to 4.5 micrometers and extends to the long-wave infrared wavelength at 10.6 micrometers, with wavelength-independent sensitivity response. Our work opens a pathway to alternative types of solution-processable, long-wavelength thermal detectors for molecular sensing, environmental monitoring, and thermal imaging. 
    more » « less
  3. ; ; ; (, The Journal of Chemical Physics)
    With the objective of understanding microscopic principles governing thermal energy flow in nanojunctions, we study phononic heat transport through metal-molecule-metal junctions using classical molecular dynamics (MD) simulations. Considering a single-molecule gold-alkanedithiol-gold junction, we first focus on aspects of method development and compare two techniques for calculating thermal conductance: (i) The Reverse Nonequilibrium MD (RNEMD) method, where heat is inputted and extracted at a constant rate from opposite metals. In this case, the thermal conductance is calculated from the nonequilibrium temperature profile that is created at the junction. (ii) The Approach-to-Equilibrium MD (AEMD) method, with the thermal conductance of the junction obtained from the equilibration dynamics of the metals. In both methods, simulations of alkane chains of a growing size display an approximate length-independence of the thermal conductance, with calculated values matching computational and experimental studies. The RNEMD and AEMD methods offer different insights, and we discuss their benefits and shortcomings. Assessing the potential application of molecular junctions as thermal diodes, alkane junctions are made spatially asymmetric by modifying their contact regions with the bulk, either by using distinct endgroups or by replacing one of the Au contacts with Ag. Anharmonicity is built into the system within the molecular force-field. We find that, while the temperature profile strongly varies (compared with the gold-alkanedithiol-gold junctions) due to these structural modifications, the thermal diode effect is inconsequential in these systems—unless one goes to very large thermal biases. This finding suggests that one should seek molecules with considerable internal anharmonic effects for developing nonlinear thermal devices. 
    more » « less
  4. ; ; ; ; ; ; ; ; ; (, Biosensors and Bioelectronics)
    This paper presents a microneedle thermocouple probe designed for temperature measurements in biological samples, addressing a critical need in the field of biology. Fabricated on a Silicon-On-Insulator (SOI) wafer, the probe features a doped silicon (Si) /chrome (Cr) /gold (Au) junction, providing a high Seebeck coefficient, rapid response times, and excellent temperature resolution. The microfabrication process produces a microneedle with a triangular sensing junction. Finite Element Analysis (FEA) was employed to evaluate the thermal time constant and structural integrity in tissue, supporting the probe’s suitability for biological applications. Experimental validation included temperature measurements in ex-vivo tissue and live Xenopus laevis oocytes. Notably, intracellular thermogenesis was detected by increasing extracellular potassium concentration to depolarize the oocyte membrane, resulting in a measurable temperature rise. These findings highlight the probe's potential as a robust tool for monitoring temperature variations in biological systems. 
    more » « less
  5. ; (, The Journal of Chemical Physics)
    Plasmon-driven photocatalysis has emerged as a paradigm-shifting approach, based on which the energy of photons can be judiciously harnessed to trigger interfacial molecular transformations on metallic nanostructure surfaces in a regioselective manner with nanoscale precision. Over the past decade, the formation of aromatic azo compounds through plasmon-driven oxidative coupling of thiolated aniline-derivative adsorbates has become a testbed for developing detailed mechanistic understanding of plasmon-mediated photochemistry. Such photocatalytic bimolecular coupling reactions may occur not only between thiolated aniline-derivative adsorbates but also between their nonthiolated analogs. How the nonthiolated adsorbates behave differently from their thiolated counterparts during the plasmon-driven coupling reactions, however, remains largely unexplored. Here, we systematically compare an alkynylated aniline-derivative, para-ethynylaniline, to its thiolated counterpart, para-mercaptoaniline, in terms of their adsorption conformations, structural flexibility, photochemical reactivity, and transforming kinetics on Ag nanophotocatalyst surfaces. We employ surface-enhanced Raman scattering as an in situ spectroscopic tool to track the detailed structural evolution of the transforming molecular adsorbates in real time during the plasmon-driven coupling reactions. Rigorous analysis of the spectroscopic results, further aided by density functional theory calculations, lays an insightful knowledge foundation that enables us to elucidate how the alteration of the chemical nature of metal–adsorbate interactions profoundly influences the transforming behaviors of the molecular adsorbates during plasmon-driven photocatalytic reactions. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email