Longji Cui

Radiative heat transfer in the extreme near field

Radiative transfer of energy at the nanometre length scale is of great importance to a variety of technologies including heat-assisted magnetic recording, near-field thermophotovoltaics and lithography. Although experimental advances have enabled elucidation of near-field radiative heat transfer in gaps as small as 20–30 nanometres (refs 4, 5, 6), quantitative analysis in the extreme near field (less than 10 nanometres) has been greatly limited by experimental challenges. Moreover, the results of pioneering measurements differed from theoretical predictions by orders of magnitude. Here we use custom-fabricated scanning probes with embedded thermocouples, in conjunction with new microdevices capable of periodic temperature modulation, to measure radiative heat transfer down to gaps as small as two nanometres. For our experiments we deposited suitably chosen metal or dielectric layers on the scanning probes and microdevices, enabling direct study of extreme near-field radiation between silica–silica, silicon nitride–silicon nitride and gold–gold surfaces to reveal marked, gap-size-dependent enhancements of radiative heat transfer. Furthermore, our state-of-the-art calculations of radiative heat transfer, performed within the theoretical framework of fluctuational electrodynamics, are in excellent agreement with our experimental results, providing unambiguous evidence that confirms the validity of this theory for modelling radiative heat transfer in gaps as small as a few nanometres. This work lays the foundations required for the rational design of novel technologies that leverage nanoscale radiative heat transfer.

Quantized thermal transport in single-atom junctions

Calorimetry reaches an atomic junction Electrical and thermal conductivity in metals are linked at the macroscopic length scale because electrons carry both heat and current. Cui et al. found that this relationship, the Wiedemann-Franz law, holds down to the atomic scale in gold and platinum (see the Perspective by Segal). They made thermal and electrical conductance measurements through a point contact only one atom thick. In gold, the thermal and electrical conductance was quantized, owing to the electronic band structure of the metal. The experiments pave the way for high-resolution calorimetry and other thermal measurements at the nanoscale. Science, this issue p. 1192; see also p. 1125 Thermal and electrical conductance remain tightly connected across gold and platinum single-atom junctions. Thermal transport in individual atomic junctions and chains is of great fundamental interest because of the distinctive quantum effects expected to arise in them. By using novel, custom-fabricated, picowatt-resolution calorimetric scanning probes, we measured the thermal conductance of gold and platinum metallic wires down to single-atom junctions. Our work reveals that the thermal conductance of gold single-atom junctions is quantized at room temperature and shows that the Wiedemann-Franz law relating thermal and electrical conductance is satisfied even in single-atom contacts. Furthermore, we quantitatively explain our experimental results within the Landauer framework for quantum thermal transport. The experimental techniques reported here will enable thermal transport studies in atomic and molecular chains, which will be key to investigating numerous fundamental issues that thus far have remained experimentally inaccessible.

Study of radiative heat transfer in Ångström- and nanometre-sized gaps

Radiative heat transfer in Ångström- and nanometre-sized gaps is of great interest because of both its technological importance and open questions regarding the physics of energy transfer in this regime. Here we report studies of radiative heat transfer in few Å to 5 nm gap sizes, performed under ultrahigh vacuum conditions between a Au-coated probe featuring embedded nanoscale thermocouples and a heated planar Au substrate that were both subjected to various surface-cleaning procedures. By drawing on the apparent tunnelling barrier height as a signature of cleanliness, we found that upon systematically cleaning via a plasma or locally pushing the tip into the substrate by a few nanometres, the observed radiative conductances decreased from unexpectedly large values to extremely small ones—below the detection limit of our probe—as expected from our computational results. Our results show that it is possible to avoid the confounding effects of surface contamination and systematically study thermal radiation in Ångström- and nanometre-sized gaps.

Perspective: Thermal and thermoelectric transport in molecular junctions

With the advent of molecular electronics, tremendous attention has been paid towards understanding the structure-function relationship of molecular junctions. Understanding how heat is transported, dissipated, and converted into electricity in molecular junctions is of great importance for designing thermally robust molecular circuits and high-performance energy conversion devices. Further, the study of thermal and thermoelectric phenomena in molecular junctions provides novel insights into the limits of applicability of classical laws. Here, we present a review of the computational and experimental progress made in probing thermoelectric effects, thermal conduction, heat dissipation, and local heating/cooling in self-assembled monolayer and single molecule junctions. We also discuss some outstanding challenges and potential future directions.

Peltier cooling in molecular junctions

The study of thermoelectricity in molecular junctions is of fundamental interest for the development of various technologies including cooling (refrigeration) and heat-to-electricity conversion1–4. Recent experimental progress in probing the thermopower (Seebeck effect) of molecular junctions5–9 has enabled studies of the relationship between thermoelectricity and molecular structure10,11. However, observations of Peltier cooling in molecular junctions—a critical step for establishing molecular-based refrigeration—have remained inaccessible. Here, we report direct experimental observations of Peltier cooling in molecular junctions. By integrating conducting-probe atomic force microscopy12,13 with custom-fabricated picowatt-resolution calorimetric microdevices, we created an experimental platform that enables the unified characterization of electrical, thermoelectric and energy dissipation characteristics of molecular junctions. Using this platform, we studied gold junctions with prototypical molecules (Au–biphenyl-4,4′-dithiol–Au, Au–terphenyl-4,4′′-dithiol–Au and Au–4,4′-bipyridine–Au) and revealed the relationship between heating or cooling and charge transmission characteristics. Our experimental conclusions are supported by self-energy-corrected density functional theory calculations. We expect these advances to stimulate studies of both thermal and thermoelectric transport in molecular junctions where the possibility of extraordinarily efficient energy conversion has been theoretically predicted2–4,14.A calorimetry technique with picowatt sensitivity enables the experimental observation of cooling in molecular junctions.

Publisher Correction: Study of radiative heat transfer in Ångström- and nanometre-sized gaps

This corrects the article DOI: 10.1038/ncomms14479.

Influence of Quantum Interference on the Thermoelectric Properties of Molecular Junctions

Molecular junctions offer unique opportunities for controlling charge transport on the atomic scale and for studying energy conversion. For example, quantum interference effects in molecular junctions have been proposed as an avenue for highly efficient thermoelectric power conversion at room temperature. Toward this goal, we investigated the effect of quantum interference on the thermoelectric properties of molecular junctions. Specifically, we employed oligo(phenylene ethynylene) (OPE) derivatives with a para-connected central phenyl ring ( para-OPE3) and meta-connected central ring ( meta-OPE3), which both covalently bind to gold via sulfur anchoring atoms located at their ends. In agreement with predictions from ab initio modeling, our experiments on both single molecules and monolayers show that meta-OPE3 junctions, which are expected to exhibit destructive interference effects, yield a higher thermopower (with ∼20 μV/K) compared with para-OPE3 (with ∼10 μV/K). Our results show that quantum interference effects can indeed be employed to enhance the thermoelectric properties of molecular junctions.

Thermal transport: Harmony with superatoms

The thermal conductivities of superatom crystals have significant contributions from extended phonon states and show a remarkable temperature dependence due to orientational ordering.

Radiative heat transfer across nanometer-size gaps

Radiative transfer of energy at the nanometer length scale is of great importance to a variety of technologies including heat-assisted magnetic recording, near-field thermophotovoltaics and lithography [1]. Although experimental advances have enabled elucidation of near-field radiative heat transfer in gaps as small as 20-30 nanometers, quantitative analysis in the extreme near field (less than 10 nanometers) has been greatly limited by experimental challenges. Moreover, the results of pioneering measurements [2] differed from theoretical predictions by orders of magnitude. Here we use custom-fabricated scanning probes with embedded thermocouples, in conjunction with new microdevices capable of periodic temperature modulation, to measure radiative heat transfer down to gaps as small as two nanometers. For our experiments we deposited suitably chosen metal or dielectric layers on the scanning probes and microdevices, enabling direct study of extreme near-field radiation between silica-silica, silicon nitride-silicon nitride and gold-gold surfaces to reveal marked, gap-size-dependent enhancements of radiative heat transfer. Furthermore, our state-of-the-art calculations of radiative heat transfer, perfomed within the theoretical framework of fluctuational electrodynamics, are in excellent agreement with our experimental results, providing unambiguous evidence that confirms the validity of this theory for modeling radiative heat transfer in gaps as small as a few nanometers. This work [3] lays the foundations required for the rational design of novel technologies that leverage nanoscale radiative heat transfer.