Pramod Reddy

Thermoelectricity in Molecular Junctions

By trapping molecules between two gold electrodes with a temperature difference across them, the junction Seebeck coefficients of 1,4-benzenedithiol (BDT), 4,4′-dibenzenedithiol, and 4,4′′-tribenzenedithiol in contact with gold were measured at room temperature to be +8.7 ± 2.1 microvolts per kelvin (μV/K), +12.9 ± 2.2 μV/K, and +14.2 ± 3.2 μV/K, respectively (where the error is the full width half maximum of the statistical distributions). The positive sign unambiguously indicates p-type (hole) conduction in these heterojunctions, whereas the Au Fermi level position for Au-BDT-Au junctions was identified to be 1.2 eV above the highest occupied molecular orbital level of BDT. The ability to study thermoelectricity in molecular junctions provides the opportunity to address these fundamental unanswered questions about their electronic structure and to begin exploring molecular thermoelectric energy conversion.

Role of electron–phonon coupling in thermal conductance of metal–nonmetal interfaces

We theoretically show that the thermal conductance associated with electron–phonon coupling in a metal near a metal–nonmetal interface can be estimated as hep=Gkp, where G is the volumetric electron–phonon coupling constant and kp is the phonon or lattice thermal conductivity of the metal. The expression suggests hep≈1/T at temperatures comparable to the Debye temperature of the metal. The predicted values of hep fall within the range of conductance values experimentally observed (0.3–1 GW/m2 K), suggesting that it cannot be ignored, and could even play a dominant role at high temperatures. Predictions of the total thermal conductance, that include both electron–phonon and phonon–phonon interfacial conductances, show reasonable agreement in its temperature dependence with experimental data for TiN/MgO interfaces.

Probing the Chemistry of Molecular Heterojunctions Using Thermoelectricity

Thermopower measurements offer an alternative transport measurement that can characterize the dominant transport orbital and is independent of the number of molecules in the junction. This method is now used to explore the effect of chemical structure on the electronic structure and charge transport. We interrogate junctions, using a modified scanning tunneling microscope break junction technique, where: (i) the 1,4-benzenedithiol (BDT) molecule has been modified by the addition of electron-withdrawing or -donating groups such as fluorine, chlorine, and methyl on the benzene ring; and (ii) the thiol end groups on BDT have been replaced by the cyanide end groups. Cyanide end groups were found to radically change transport relative to BDT such that transport is dominated by the lowest unoccupied molecular orbital in 1,4-benzenedicyanide, while substituents on BDT generated small and predictable changes in transmission.

Diffuse mismatch model of thermal boundary conductance using exact phonon dispersion

The acoustic mismatch model (AMM) and the diffuse mismatch model (DMM) have been traditionally used to calculate the thermal boundary conductance of interfaces. In these calculations, the phonon dispersion relationship is usually approximated by a linear relationship (Debye approximation). This is accurate for wave vectors close to the zone center, but deviates significantly for wave vectors near the zone edges. Here, we present DMM calculations of the thermal conductance of Al–Si, Al–Ge, Cu–Si, and Cu–Ge interfaces by taking into account the full phonon dispersion relationship over the entire Brillouin zone obtained using the Born-von Karman model (BKM). The thermal boundary conductance thus calculated deviates significantly from DMM predictions obtained using the Debye model in all cases.

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.

Effect of Length and Contact Chemistry on the Electronic Structure and Thermoelectric Properties of Molecular Junctions

We present a combined experimental and computational study that probes the thermoelectric and electrical transport properties of molecular junctions. Experiments were performed on junctions created by trapping aromatic molecules between gold electrodes. The end groups (-SH, -NC) of the aromatic molecules were systematically varied to study the effect of contact coupling strength and contact chemistry. When the coupling of the molecule with one of the electrodes was reduced by switching the terminal chemistry from -SH to -H, the electrical conductance of molecular junctions decreased by an order of magnitude, whereas the thermopower varied by only a few percent. This has been predicted computationally in the past and is experimentally demonstrated for the first time. Further, our experiments and computational modeling indicate the prospect of tuning thermoelectric properties at the molecular scale. In particular, the thiol-terminated aromatic molecular junctions revealed a positive thermopower that increased linearly with length. This positive thermopower is associated with charge transport primarily through the highest occupied molecular orbital, as shown by our computational results. In contrast, a negative thermopower was observed for a corresponding molecular junction terminated by an isocyanide group due to charge transport primarily through the lowest unoccupied molecular orbital.

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.

Enhancement of near-field radiative heat transfer using polar dielectric thin films

Thermal radiative emission from a hot surface to a cold surface plays an important role in many applications, including energy conversion, thermal management, lithography, data storage and thermal microscopy. Recent studies on bulk materials have confirmed long-standing theoretical predictions indicating that when the gap between the surfaces is reduced to tens of nanometres, well below the peak wavelength of the blackbody emission spectrum, the radiative heat flux increases by orders of magnitude. However, despite recent attempts, whether such enhancements can be obtained in nanoscale dielectric films thinner than the penetration depth of thermal radiation, as suggested by theory, remains experimentally unknown. Here, using an experimental platform that comprises a heat-flow calorimeter with a resolution of about 100 pW (ref. 7), we experimentally demonstrate a dramatic increase in near-field radiative heat transfer, comparable to that obtained between bulk materials, even for very thin dielectric films (50-100 nm) when the spatial separation between the hot and cold surfaces is comparable to the film thickness. We explain these results by analysing the spectral characteristics and mode shapes of surface phonon polaritons, which dominate near-field radiative heat transport in polar dielectric thin films.

Nanoscale thermometry using point contact thermocouples.

Probing temperature fields with nanometer resolution is critical to understanding nanoscale thermal transport as well as dissipation in nanoscale devices. Here, we demonstrate an atomic force microscope (AFM)-based technique capable of mapping temperature fields in metallic films with approximately 10 mK temperature resolution and <100 nm spatial resolution. A platinum-coated AFM cantilever placed in soft mechanical contact with a metallic (gold) surface is used to sequentially create point contact thermocouples on a grid. The local temperature at each point contact is obtained by measuring the thermoelectric voltage of the platinum-gold point contact and relating it to the local temperature. These results demonstrate a direct measurement of the temperature field of a metallic surface without using specially fabricated scanning temperature-probes.