Thermal conductance of single-molecule junctions.

Single-molecule junctions have been extensively used to probe properties as diverse as electrical conduction1-3, light emission4, thermoelectric energy conversion5,6, quantum interference7,8, heat dissipation9,10 and electronic noise11 at atomic and molecular scales. However, a key quantity of current interest-the thermal conductance of single-molecule junctions-has not yet been directly experimentally determined, owing to the challenge of detecting minute heat currents at the picowatt level. Here we show that picowatt-resolution scanning probes previously developed to study the thermal conductance of single-metal-atom junctions12, when used in conjunction with a time-averaging measurement scheme to increase the signal-to-noise ratio, also allow quantification of the much lower thermal conductance of single-molecule junctions. Our experiments on prototypical Au-alkanedithiol-Au junctions containing two to ten carbon atoms confirm that thermal conductance is to a first approximation independent of molecular length, consistent with detailed ab initio simulations. We anticipate that our approach will enable systematic exploration of thermal transport in many other one-dimensional systems, such as short molecules and polymer chains, for which computational predictions of thermal conductance13-16 have remained experimentally inaccessible.

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

This corrects the article DOI: 10.1038/ncomms14479.

Quantized thermal transport in 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.

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 4-6), 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.

Electrostatic control of thermoelectricity in molecular junctions.

Molecular junctions hold significant promise for efficient and high-power-output thermoelectric energy conversion. Recent experiments have probed the thermoelectric properties of molecular junctions. However, electrostatic control of thermoelectric properties via a gate electrode has not been possible due to technical challenges in creating temperature differentials in three-terminal devices. Here, we show that extremely large temperature gradients (exceeding 1 × 10(9) K m(-1)) can be established in nanoscale gaps bridged by molecules, while simultaneously controlling their electronic structure via a gate electrode. Using this platform, we study prototypical Au-biphenyl-4,4'-dithiol-Au and Au-fullerene-Au junctions to demonstrate that the Seebeck coefficient and the electrical conductance of molecular junctions can be simultaneously increased by electrostatic control. Moreover, from our studies of fullerene junctions, we show that thermoelectric properties can be significantly enhanced when the dominant transport orbital is located close to the chemical potential (Fermi level) of the electrodes. These results illustrate the intimate relationship between the thermoelectric properties and charge transmission characteristics of molecular junctions and should enable systematic exploration of the recent computational predictions that promise extremely efficient thermoelectric energy conversion in molecular junctions.

Heat dissipation in atomic-scale junctions.

Atomic and single-molecule junctions represent the ultimate limit to the miniaturization of electrical circuits. They are also ideal platforms for testing quantum transport theories that are required to describe charge and energy transfer in novel functional nanometre-scale devices. Recent work has successfully probed electric and thermoelectric phenomena in atomic-scale junctions. However, heat dissipation and transport in atomic-scale devices remain poorly characterized owing to experimental challenges. Here we use custom-fabricated scanning probes with integrated nanoscale thermocouples to investigate heat dissipation in the electrodes of single-molecule ('molecular') junctions. We find that if the junctions have transmission characteristics that are strongly energy dependent, this heat dissipation is asymmetric--that is, unequal between the electrodes--and also dependent on both the bias polarity and the identity of the majority charge carriers (electrons versus holes). In contrast, junctions consisting of only a few gold atoms ('atomic junctions') whose transmission characteristics show weak energy dependence do not exhibit appreciable asymmetry. Our results unambiguously relate the electronic transmission characteristics of atomic-scale junctions to their heat dissipation properties, establishing a framework for understanding heat dissipation in a range of mesoscopic systems where transport is elastic--that is, without exchange of energy in the contact region. We anticipate that the techniques established here will enable the study of Peltier effects at the atomic scale, a field that has been barely explored experimentally despite interesting theoretical predictions. Furthermore, the experimental advances described here are also expected to enable the study of heat transport in atomic and molecular junctions--an important and challenging scientific and technological goal that has remained elusive.

Ultra-high vacuum scanning thermal microscopy for nanometer resolution quantitative thermometry.

Understanding energy dissipation at the nanoscale requires the ability to probe temperature fields with nanometer resolution. Here, we describe an ultra-high vacuum (UHV)-based scanning thermal microscope (SThM) technique that is capable of quantitatively mapping temperature fields with ∼15 mK temperature resolution and ∼10 nm spatial resolution. In this technique, a custom fabricated atomic force microscope (AFM) cantilever, with a nanoscale Au-Cr thermocouple integrated into the tip of the probe, is used to measure temperature fields of surfaces. Operation in an UHV environment eliminates parasitic heat transport between the tip and the sample enabling quantitative measurement of temperature fields on metal and dielectric surfaces with nanoscale resolution. We demonstrate the capabilities of this technique by directly imaging thermal fields in the vicinity of a 200 nm wide, self-heated, Pt line. Our measurements are in excellent agreement with computational results-unambiguously demonstrating the quantitative capabilities of the technique. UHV-SThM techniques will play an important role in the study of energy dissipation in nanometer-sized electronic and photonic devices and the study of phonon and electron transport at the nanoscale.