Search

Local variations in the Seebeck coefficient in low-dimensional materials-based nanostructures and devices play a major role in their thermoelectric performance. Unfortunately, currently most thermoelectric measurements probe the aggregate characteristics of the device as a whole, failing to observe the effects of the local variations and internal structure. Such variations can be caused by local defects, geometry, electrical contacts or interfaces and often substantially influence thermoelectric properties, most profoundly in two-dimensional (2D) materials. Here, we use Scanning Thermal Gate Microscopy (STGM), a non-invasive method not requiring an electrical contact between the nanoscale tip and the probed sample, to obtain nanoscale resolution 2D maps of the thermovoltage in graphene samples. We investigate a junction formed between single-layer and bilayer graphene and identify the impact of internal strain and Fermi level pinning by the contacts using a deconvolution method to directly map the local Seebeck coefficient. The new approach paves the way for an in-depth understanding of thermoelectric behaviour and phenomena in 2D materials nanostructures and devices., Comment: 19 pages, 14 figures

The energy dependent thermoelectric response of a single molecule contains valuable information about its transmission function and its excited states. However, measuring it requires devices that can efficiently heat up one side of the molecule while being able to tune its electrochemical potential over a wide energy range. Furthermore, to increase junction stability devices need to operate at cryogenic temperatures. In this work we report on a new device architecture to study the thermoelectric properties and the conductance of single molecules simultaneously over a wide energy range. We employ a sample heater in direct contact with the metallic electrodes contacting the single molecule which allows us to apply temperature biases up to $\Delta T = 60$K with minimal heating of the molecular junction. This makes these devices compatible with base temperatures $T_\mathrm{bath} <2$K and enables studies in the linear ($\Delta T \ll T_\mathrm{molecule}$) and non-linear ($\Delta T \gg T_\mathrm{molecule}$) thermoelectric transport regimes.

The influence of nanostructuring and quantum confinement on the thermoelectric properties of materials has been extensively studied. While this has made possible multiple breakthroughs in the achievable figure of merit, classical confinement, and its effect on the local Seebeck coefficient has mostly been neglected, as has the Peltier effect in general due to the complexity of measuring small temperature gradients locally. Here we report that reducing the width of a graphene channel to 100 nm changes the Seebeck coefficient by orders of magnitude. Using a scanning thermal microscope allows us to probe the local temperature of electrically contacted graphene two-terminal devices or to locally heat the sample. We show that constrictions in mono- and bilayer graphene facilitate a spatially correlated gradient in the Seebeck and Peltier coefficient, as evidenced by the pronounced thermovoltage $V_{th}$ and heating/cooling response $\Delta T_{Peltier}$, respectively. This geometry dependent effect, which has not been reported previously in 2D materials, has important implications for measurements of patterned nanostructures in graphene and points to novel solutions for effective thermal management in electronic graphene devices or concepts for single material thermocouples.

We have decoupled the intrinsic optical and electrostatic effects arising in monolayer and few-layer molybdenum disulphide from those influenced by the flake-substrate interaction.

Although it was demonstrated that discrete molecular levels determine the sign and magnitude of the thermoelectric effect in single-molecule junctions, full electrostatic control of these levels has not been achieved to date. Here, we show that graphene nanogaps combined with gold microheaters serve as a testbed for studying single-molecule thermoelectricity. Reduced screening of the gate electric field compared to conventional metal electrodes allows control of the position of the dominant transport orbital by hundreds of meV. We find that the power factor of graphene-fullerene junctions can be tuned over several orders of magnitude to a value close to the theoretical limit of an isolated Breit-Wigner resonance. Furthermore, our data suggest that the power factor of an isolated level is only given by the tunnel coupling to the leads and temperature. These results open up new avenues for exploring thermoelectricity and charge transport in individual molecules and highlight the importance of level alignment and coupling to the electrodes for optimum energy conversion in organic thermoelectric materials.

Atomically thin layers of two-dimensional (2D) materials such as graphene, MoS2 and h-BN have immense potential as sensors and electronic devices thanks to their highly desirable electronic, mechanical, optical and heat transport properties. In particular their extreme stiffness, tensile strength and low density allows for high frequency electronic devices, resonators and ultra-sensitive detectors providing realistic avenues for down-scaling electronic devices and nanoelectromechanical systems (NEMS). Whilst nanoscale morphology and electronic properties of 2D materials can be studied using existing electron or scanning probe microscopy approaches, time-dependant phenomena on the ns and shorter time-scales cannot be readily explored. Here we use the heterodyne principle to reach into this ns time-scale and create a local nanoscale probe for electrostatically induced actuation of a graphene resonator, with amplitude sensitivity down to pm range and time sensitivity in the ns range. We experimentally observed response times of 20-120 ns for resonators with beam lengths of 180 nm to 2.5 um in line with the theoretical predictions for such NEMS devices.

Infrared (IR) spectroscopy, a well established tool for chemical analysis of diverse materials, has significant potential in biomedical applications. While the spatial resolution of traditional IR spectroscopy is limited by the wavelength of the IR light to the few micrometres, it has been shown that nanoscale chemical analysis can be obtained by detecting IR induced local heating photothermal response via Scanning Thermal Microscopy (SThM) or local thermomechanical expansion using Atomic Force Microscopy (AFM). This paper explores the potential of a pulsed ps pulse duration high power free electron laser (FEL) light source for AFM-IR and SThM-IR spectroscopy employing standard AFM and SThM probes. The SThM-IR response was found to have a detrimental strong background signal due to the direct heating of the probe, whereas the AFM IR thermomechanical response allowed to eliminate such a problem for both top down and bottom up illuminations with the FEL IR source. The SThM IR characteristic response time was approximately half that of AFM-IR, in line with finite element analysis simulations. Finally, the advantages and drawbacks of AFM-IR wavelength sensitive spectroscopic response using a ps duration FEL vs a high repetition quantum cascade laser IR source in studies of nanoscale dimension amyloid peptide fibres were explored both experimentally and via finite elements analysis.

In the search for phase change materials (PCM) that may rival traditional random access memory, a complete understanding of the amorphous to crystalline phase transition is required. For the well-known Ge2Sb2Te5 (GST) and GeTe (GT) chalcogenides, which display nucleation and growth dominated crystallization kinetics, respectively, this work explores the nanomechanical morphology of amorphous and crystalline phases in 50 nm thin films. Subjecting these PCM specimens to a lateral thermal gradient spanning the crystallization temperature allows for a detailed morphological investigation. Surface and depth-dependent analyses of the resulting amorphous, transition and crystalline regions are achieved with shallow angle cross-sections, uniquely implemented with beam exit Ar ion polishing. To resolve the distinct phases, ultrasonic force microscopy (UFM) with simultaneous topography is implemented revealing a relative stiffness contrast between the amorphous and crystalline phases of 14% for the free film surface and 20% for the cross-sectioned surface. Nucleation is observed to occur preferentially at the PCM-substrate and free film interface for both GST and GT, while fine subsurface structures are found to be sputtering direction dependent. Combining surface and cross-section nanomechanical mapping in this manner allows 3D analysis of microstructure and defects with nanoscale lateral and depth resolution, applicable to a wide range of materials characterization studies where the detection of subtle variations in elastic modulus or stiffness are required.

Scanning thermal microscopy (SThM) - a type of scanning probe microscopy that allows mapping thermal transport and temperatures in nanoscale devices, is becoming a key approach that may help to resolve heat dissipation problems in modern processors and develop new thermoelectric materials. Unfortunately, performance of current SThM implementations in measurement of high thermal conductivity materials continues to me limited. The reason for these limitations is two-fold - first, SThM measurements of high thermal conductivity materials need adequate high thermal conductivity of the probe apex, and secondly, the quality of thermal contact between the probe and the sample becomes strongly affected by the nanoscale surface corrugations of the studied sample. In this paper we develop analytical models of the SThM approach that can tackle these complex problems - by exploring high thermal conductivity nanowires as a tip apex, and exploring contact resistance between the SThM probe and studied surface, the latter becoming particularly important when both tip and surface have high thermal conductivities. We develop analytical model supported by the finite element analysis simulations and by the experimental tests of SThM prototype using carbon nanotube (CNT) at the tip apex as a heat conducting nanowire. These results elucidate vital relationships between the performance of the probe in SThM from one side and thermal conductivity, geometry of the probe and its components from the other, providing pathway for overcoming current limitations of SThM.

We present a new concept of scanning thermal nanoprobe that utilizes the extreme thermal conductance of a carbon nanotube (CNT) to channel heat between the probe and the sample. The integration of CNT in scanning thermal microscopy (SThM) overcomes the main drawbacks of standard SThM probes, where the low thermal conductance of the apex SThM probe is the main limiting factor. The integration of CNT (CNT- SThM) extends SThM sensitivity to thermal transport measurement in higher thermal conductivity materials such as metals, semiconductors and ceramics, while also improving the spatial resolution. Investigation of thermal transport in ultra large scale integration (ULSI) interconnects, using CNT- SThM probe, showed fine details of heat transport in ceramic layer, vital for mitigating electromigration in ULSI metallic current leads. For a few layer graphene, the heat transport sensitivity and spatial resolution of the CNT-SThM probe demonstrated significantly superior thermal resolution compared to that of standard SThM probes achieving 20-30 nm topography and ~30 nm thermal spatial resolution compared to 50-100 nm for standard SThM probes. The outstanding axial thermal conductivity, high aspect ratio and robustness of CNTs can make CNT-SThM the perfect thermal probe for the measurement of nanoscale thermophysical properties and an excellent candidate for the next generation of thermal microscopes., Comment: E-mail: o.kolosov@lancaster.ac.uk, http://www.nano-science.com

Nanoscale thermal properties are becoming of extreme importance for modern electronic circuits that dissipate increasing power on the length scale of few tens of nanometers, and for chemical and physical properties sensors and biosensors using nanoscale sized features. While Scanning Thermal Microscopy (SThM) is known for its ability to probe thermal properties and heat generation with nanoscale resolution, until today it was perceived impossible to use it in the liquid environment due to dominating direct heat exchange between microfabricated thermal probe and surrounding liquid that would deteriorate spatial resolution. Nonetheless, our theoretical analysis of SThM in liquids showed that for certain design of SThM probe with resistive heater located near the probe tip, their thermal signal is only moderately affected, by less than half on immersion in a dodecane environment. More significantly, its spatial resolution, surprisingly, would remain practically unaffected, and the thermal contact between the tip apex and the studied sample would be beneficially improved. Our experimental trials of such immersion SThM, or iSThM, were fully successful and here we report for the first time nanoscale SThM measurements of thermal conductivity of Ultra Large Scale Integration polymerceramic metal interconnects with the spatial thermal resolution down to 50 nm. Further studies of heat transport in nanoscale graphite flakes in iSThM suggested, in particular, that highly anisotropic thermal conductivity in graphene layers may play significant role in the nanoscale thermal transport in liquid environment. New iSThM opens a wide range of applications from noncontact measurements of thermal transport in semiconductor devices to exploring graphene energy storage, catalytic reactions and heat generation in biological systems., Comment: Supporting materials at end of paper