Thermoelectric materials, which can generate electricity from waste heat or be used as solid-state Peltier coolers, could play an important role in a global sustainable energy solution. Such a development is contingent on identifying materials with higher thermoelectric efficiency than available at present, which is a challenge owing to the conflicting combination of material traits that are required. Nevertheless, because of modern synthesis and characterization techniques, particularly for nanoscale materials, a new era of complex thermoelectric materials is approaching. We review recent advances in the field, highlighting the strategies used to improve the thermopower and reduce the thermal conductivity.

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Complex thermoelectric materials.

Nanotechnology is a multidisciplinary field, which covers a vast and diverse array of devices derived from engineering, biology, physics and chemistry. These devices include nanovectors for the targeted delivery of anticancer drugs and imaging contrast agents. Nanowires and nanocantilever arrays are among the leading approaches under development for the early detection of precancerous and malignant lesions from biological fluids. These and other nanodevices can provide essential breakthroughs in the fight against cancer.

Cancer nanotechnology: opportunities and challenges.

Rapid progress in the synthesis and processing of materials with structure on nanometer length scales has created a demand for greater scientific understanding of thermal transport in nanoscale devices, individual nanostructures, and nanostructured materials. This review emphasizes developments in experiment, theory, and computation that have occurred in the past ten years and summarizes the present status of the field. Interfaces between materials become increasingly important on small length scales. The thermal conductance of many solid–solid interfaces have been studied experimentally but the range of observed interface properties is much smaller than predicted by simple theory. Classical molecular dynamics simulations are emerging as a powerful tool for calculations of thermal conductance and phonon scattering, and may provide for a lively interplay of experiment and theory in the near term. Fundamental issues remain concerning the correct definitions of temperature in nonequilibrium nanoscale systems. Modern Si microelectronics are now firmly in the nanoscale regime—experiments have demonstrated that the close proximity of interfaces and the extremely small volume of heat dissipation strongly modifies thermal transport, thereby aggravating problems of thermal management. Microelectronic devices are too large to yield to atomic-level simulation in the foreseeable future and, therefore, calculations of thermal transport must rely on solutions of the Boltzmann transport equation; microscopic phonon scattering rates needed for predictive models are, even for Si, poorly known. Low-dimensional nanostructures, such as carbon nanotubes, are predicted to have novel transport properties; the first quantitative experiments of the thermal conductivity of nanotubes have recently been achieved using microfabricated measurement systems. Nanoscale porosity decreases the permittivity of amorphous dielectrics but porosity also strongly decreases the thermal conductivity. The promise of improved thermoelectric materials and problems of thermal management of optoelectronic devices have stimulated extensive studies of semiconductor superlattices; agreement between experiment and theory is generally poor. Advances in measurement methods, e.g., the 3ω method, time-domain thermoreflectance, sources of coherent phonons, microfabricated test structures, and the scanning thermal microscope, are enabling new capabilities for nanoscale thermal metrology.

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Nanoscale thermal transport

Non-invasive precise thermometers working at the nanoscale with high spatial resolution, where the conventional methods are ineffective, have emerged over the last couple of years as a very active field of research. This has been strongly stimulated by the numerous challenging requests arising from nanotechnology and biomedicine. This critical review offers a general overview of recent examples of luminescent and non-luminescent thermometers working at nanometric scale. Luminescent thermometers encompass organic dyes, QDs and Ln3+ions as thermal probes, as well as more complex thermometric systems formed by polymer and organic–inorganic hybrid matrices encapsulating these emitting centres. Non-luminescent thermometers comprise of scanning thermal microscopy, nanolithography thermometry, carbon nanotube thermometry and biomaterials thermometry. Emphasis has been put on ratiometric examples reporting spatial resolution lower than 1 micron, as, for instance, intracellular thermometers based on organic dyes, thermoresponsive polymers, mesoporous silica NPs, QDs, and Ln3+-based up-converting NPs and β-diketonate complexes. Finally, we discuss the challenges and opportunities in the development for highly sensitive ratiometric thermometers operating at the physiological temperature range with submicron spatial resolution.

/pdf/thermometry-at-the-nanoscale-1g42e25p96.pdf

Thermometry at the nanoscale

The field of thermoelectrics has progressed enormously and is now growing steadily because of recently demonstrated advances and strong global demand for cost-effective, pollution-free forms of energy conversion. Rapid growth and exciting innovative breakthroughs in the field over the last 10-15 years have occurred in large part due to a new fundamental focus on nanostructured materials. As a result of the greatly increased research activity in this field, a substantial amount of new data--especially related to materials--have been generated. Although this has led to stronger insight and understanding of thermoelectric principles, it has also resulted in misconceptions and misunderstanding about some fundamental issues. This article sets out to summarize and clarify the current understanding in this field; explain the underpinnings of breakthroughs reported in the past decade; and provide a critical review of various concepts and experimental results related to nanostructured thermoelectrics. We believe recent achievements in the field augur great possibilities for thermoelectric power generation and cooling, and discuss future paths forward that build on these exciting nanostructuring concepts.

Nanostructured Thermoelectrics: Big Efficiency Gains from Small Features

A batch fabrication process has been developed for making cantilever probes for scanning thermal microscopy (SThM) with spatial resolution in the sub-100 nm range. A heat transfer model was developed to optimize the thermal design of the probes. Low thermal conductivity silicon dioxide and silicon nitride were chosen for fabricating the probe tips and cantilevers, respectively, in order to minimize heat loss from the sample to the probe and to improve temperature measurement accuracy and spatial resolution. An etch process was developed for making silicon dioxide tips with tip radius as small as 20 nm. A thin film thermocouple junction was fabricated at the tip end with a junction height that could be controlled in the range of 100-600 nm. These thermal probes have been used extensively for thermal imaging of micro- and nano-electronic devices with a spatial resolution of 50 nm. This paper presents measurement results of the steady state and dynamic temperature responses of the thermal probes and examines the wear characteristics of the probes.

Design and batch fabrication of probes for sub-100 nm scanning thermal microscopy

We studied the cross-plane lattice and electronic thermal conductivities of superlattices made of InGaAlAs and InGaAs films, with the latter containing embedded ErAs nanoparticles (denoted as ErAs:InGaAs). Measurements of total thermal conductivity at four doping levels and a theoretical analysis were used to estimate the cross-plane electronic thermal conductivity of the superlattices. The results show that the lattice and electronic thermal conductivities have marginal dependence on doping levels. This suggests that there is lateral conservation of electronic momentum during thermionic emission in the superlattices, which limits the fraction of available electrons for thermionic emission, thereby affecting the performance of thermoelectric devices. (c) 2006 American Institute of Physics.

/pdf/cross-plane-lattice-and-electronic-thermal-conductivities-of-43nd5lbq43.pdf

Cross-plane lattice and electronic thermal conductivities of ErAs : InGaAs/InGaAlAs superlattices - eScholarship

An automated apparatus capable of measuring the electrical conductivity and thermopower of thin films over a temperature range of 300-750 K is reported. A standard dc resistance measurement in van der Pauw geometry was used to evaluate the electrical conductivity, and the thermopower was measured using the differential method. The design of the instrument, the methods used for calibration, and the measurement procedure are described in detail. Given the lack of a standard National Institute of Standards and Technology (Gaithersburg, Md.) sample for high temperature thermopower calibration, the disclosed calibration procedure shall be useful for calibration of new instruments.

An apparatus for simultaneous measurement of electrical conductivity and thermopower of thin films in the temperature range of 300-750 K.

Ratcheting electrophoresis microchip (REM) for programmable transport and separation of macromolecules

The 3ω method is a well established technique for measuring thermal conductivity of thin films and substrates. The method extracts thermal conductivity by measuring temperature response when current flows through a metal strip heater deposited on the material's surface. The metal strip is used both as heat source and temperature sensor. An important factor in the accuracy of 3ω measurements is that the current should be confined to the metal strip resistor and any leakage to the substrate will invalidate the results. This is because the heat source would no longer be localized on the surface and also because any Schottky behavior at metal/semiconductor interface will create nonlinearities that affect the 3ω signal substantially. These problems are especially important at high temperatures where thermionic emission of electrons through oxide insulation layer becomes important. In this paper we propose thermoreflectance imaging as an additional method to determine thermal conductivity of thin film materials. Because thermoreflectance measures temperatures optically, the method is less dependent on the electrical properties of the metal heater. Additionally, the temperature profile near the heat source can be used to ensure there is no defect in the thin film metal heater. Theory is presented demonstrating thermoreflectance can also be used to measure anisotropic in-plane and cross-plane thermal conductivity in thin films. Preliminary thermoreflectance measurements were analyzed at various locations on the surface of isotropic, InGaAs and anisotropic ScN/ZrN superlattice thin film 3ω test samples. Experimental results are in agreement with simulated temperature distributions.

Measurement of Thin Film Isotropic and Anisotropic Thermal Conductivity Using 3ω and Thermoreflectance Imaging

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