Using micro-Raman spectroscopy, the thermal conductivity of a graphene monolayer grown by chemical vapor deposition and suspended over holes with different diameters ranging from 2.9 to 9.7 μm was measured in vacuum, thereby eliminating errors caused by heat loss to the surrounding gas. The obtained thermal conductivity values of the suspended graphene range from (2.6 ± 0.9) to (3.1 ± 1.0) × 103 Wm−1K−1 near 350 K without showing the sample size dependence predicted for suspended, clean, and flat graphene crystal. The lack of sample size dependence is attributed to the relatively large measurement uncertainty as well as grain boundaries, wrinkles, defects, or polymeric residue that are possibly present in the measured samples. Moreover, from Raman measurements performed in air and CO2 gas environments near atmospheric pressure, the heat transfer coefficient for air and CO2 was determined and found to be (2.9 +5.1/−2.9) and (1.5 +4.2/−1.5) × 104 Wm−2K−1, respectively, when the graphene temperature was heated by the Raman laser to about 510 K.
Recently a number of hydrogel-based micro- and nanoscale drug carriers have been reported including top down fabricated, highly monodisperse nanoparticles of specific sizes and shapes. One critical question on such approaches is whether in vivo swelling of the nanoparticles could considerably alter their geometry to a point where the potential benefit of controlling size or shape could not be realized. Little has been reported on experimental characterization of the swelling behavior of nanoscale hydrogel structures, and current theoretical understanding is largely based on bulk hydrogel systems. Using atomic force microscopy (AFM) and environmental scanning electron microscopy (ESEM) capsules, we have characterized the swelling behavior of nano-imprinted hydrogel particles of different sizes and aspect ratios. Our results indicate a size-dependent swelling which can be attributed to the effect of substrate constraint of as-fabricated particles, when the particles are still attached to the imprinting substrate. Numerical simulations based on a recently developed field theory and a nonlinear finite element method were conducted to illustrate the constraint effect on swelling and drying behavior of substrate-supported hydrogel particles of specific geometries, and compared closely with experimental measurements. Further, we present a theoretical model that predicts the size-dependent swelling behavior for unconstrained sub-micron hydrogel particles due to the effect of surface tension. Both experimental and theoretical results suggest that hydrogel swelling does not significantly alter the shape and size of highly crosslinked nanoscale hydrogel particles used in the present study.
We have developed a nanofabricated resistance thermometer device to measure the thermal conductivity of graphene monolayers exfoliated onto silicon dioxide. The measurement results show that the thermal conductivity of the supported graphene is approximately 600 W/m K at room temperature. While this value is lower than the reported basal plane values for graphite and suspended graphene because of phonon leakage across the graphene-support interface, it is still considerably higher than the values for common thin film electronic materials. Here, we present a detailed discussion of the design and fabrication of the measurement device. Analytical and numerical heat transfer solutions are developed to evaluate the accuracy and uncertainty of this method for thermal conductivity measurement of high-thermal conductivity ultrathin films.
The thermal conductivity of wurtzite and zinc blende indium arsenide nanowires was measured using a microfabricated device, with the crystal structure of each sample controlled during growth and determined by transmission electron microscopy. Nanowires of both phases showed a reduction of the thermal conductivity by a factor of 2 or more compared to values reported for zinc blende indium arsenide bulk crystals within the measured temperature range. Theoretical models were developed to analyze the measurement results and determine the effect of phase on phonon transport. Branch-specific phonon dispersion data within the discretized first Brillouin zone were calculated from first principles and used in numerical models of volumetric heat capacity and thermal conductivity. The combined results of the experimental and theoretical studies suggest that wurtzite indium arsenide possesses similar volumetric heat capacity, weighted average group velocity, weighted average phonon-phonon scattering mean free path, and anharmonic scattering-limited thermal conductivity as the zinc blende phase. Hence, we attribute the differing thermal conductivity values observed in the indium arsenide nanowires of different phases to differences in the surface scattering mean free paths between the nanowire samples.
The thermal resistance of a nanoscale point contact to an indium arsenide nanowire was experimentally determined to be two orders of magnitude larger than the theoretical prediction based on the diffuse mismatch model for a welded contact. The discrepancy is attributed mainly to a much smaller phonontransmission coefficient for the weak van der Waals contact than for a welded contact. The experiment further suggests the need of careful examination of the structure and defects in the nanowire sample for similar thermal transport measurements of individual nanowires.
Importance of the field: Although significant progress has been made in delivering therapeutic agents through micro and nanocarriers, precise control over in vivo biodistribution and disease-responsive drug release has been difficult to achieve. This is critical for the success of next generation drug delivery devices, as newer drugs, designed to interfere with cellular functions, must be efficiently and specifically delivered to diseased cells. The chief constraint in achieving this has been our limited repertoire of particle synthesis methods, especially at the nanoscale. Recent developments in generating shape-specific nanocarriers and the potential to combine stimuli-responsive release with nanoscale delivery devices show great promise in overcoming these limitations.
Areas covered in this review: How recent advances in fabrication technology allow synthesis of highly monodisperse, stimuli-responsive, drug-carrying nanoparticles of precise geometries is discussed. How particle properties, specifically shape and stimuli responsiveness, affect biodistribution, cellular uptake and drug release is also reviewed.
What the reader will gain: The reader is introduced to recent developments in intelligent drug nanocarriers and new nanofabrication approaches that can be combined with disease-responsive biomaterials. This will provide insight into the importance of controlling particle geometry and incorporating stimuli-responsive materials into drug delivery.
Take home message: The integration of responsive biomaterials into shape-specific nanocarriers is one of the most promising avenues towards the development of next generation, advanced drug delivery systems.
Read More: http://informahealthcare.com/doi/abs/10.1517/17425240903579971
We report micro-Raman spectroscopy measurements of the temperature distribution of current-carrying, 5 μm long, suspended carbon nanotubes in different gas environments near atmospheric pressure. At the same heating power, the measuredG band phonontemperature of the nanotube is found to be significantly lower in gaseous environments than in vacuum. Theoretical analysis of these results suggests that about 50%–60% of the heat dissipated in the suspended nanotube is removed by its surrounding gas molecules, and that the thermal boundary conductance is higher in carbon dioxide than in nitrogen, argon, and helium, despite the lower thermal conductivity of carbon dioxide.
We report a study of the effect of the growth base pressure on the thermoelectric (TE) properties of indium antimonide (InSb) nanowires (NWs) synthesized using a vapour–liquid–solid method at different base pressures varying from ambient to high vacuum. A suspended device was used to characterize the TE properties of the NWs, which are zinc-blende structure with 1 1 0 growth direction based on transmission electron microscopy (TEM) characterization of the same NWs assembled on the suspended device. The obtained Seebeck coefficient is negative, with the magnitude being smaller than the literature bulk values and increasing with decreasing growth base pressure. These results are attributed to the loss of In from the source materials due to oxidation by residual oxygen in the growth environment and the consequent formation of Sb-doped NWs. The electron mobility and lattice thermal conductivity in the NWs are lower than the corresponding bulk values because of both surface scattering and stronger dopant scattering in the Sb-doped NWs. Based on these findings, it is suggested that growth from In-rich source materials can be used to achieve composition stoichiometry in the NWs so as to increase the Seebeck coefficient and TE figure of merit.
The in-plane thermal conductivity is measured to be three times lower in misfit-layered [(PbSe)0.99]x(WSe2)xsuperlatticethin films than disordered-layered WSe2 because of interface scattering despite a higher cross-plane value in the former than the latter. While having little effect on the in-plane thermal conductivity,annealing the p-type [(PbSe)0.99]2(WSe2)2films in Se increases the in-plane Seebeck coefficient and electrical conductivity because of decreased defect and hole concentrations. Increasing interface density of the annealedfilms by decreasing x from 4 to 2 has weak influence on the in-plane thermal conductivity but increases the Seebeck coefficient and decreases the room-temperature electrical conductivity.
Turbostratically disordered tungsten diselenide (WSe2) thin films with as few as two c-axis-oriented (basal plane) structural units were synthesized from modulated elemental reactants. By varying the number of elemental W−Se bilayers deposited, the thickness could be controllably varied from two to eighty such structural units. The sample roughness decreases with increasing annealing time and temperature as the crystalline WSe2 basal plane units self-assemble from the amorphous precursors. Low-angle X-ray diffraction data show that the thickness of the WSe2 films is highly uniform after annealing, with estimated roughness of less than 0.2 nm, and highly oriented, with the c axis of the structural units oriented within 0.1° of the substrate normal as determined from rocking curves of the specular 00L-type diffraction peaks. Pole figures of hk0-type reflections indicate that c-axis-oriented basal plane structural units are randomly oriented within the a-b plane. The widths of diffraction peaks of type hk0, 00L, and hkl (h, k ≠ 0; l ≠ 0) indicate coherence lengths of about 6−7 nm in the a−b plane, the full thickness of the film along the c axis, and 1−2 nm in mixed-index directions. Scanning transmission electron microscopy imaging corroborated the X-ray scattering results, providing direct evidence of strong c-axis texture, rotational disorder between adjacent basal plane structural units, and an intraplanar grain size of several nanometers. The combination of intraplanar crystallinity and interplanar rotational disorder explains the significant anisotropy of the thermal conductivity, which is 20−30 times higher in the a−b plane than along the c axis. Electrical measurements within the a−b plane indicate that the films exhibit n-type semiconducting behavior.
Graphene monolayer has been grown by chemical vapor deposition on copper and then suspended over a hole. By measuring the laser heating and monitoring the Raman G peak, we obtain room-temperature thermal conductivity and interface conductance of (370 + 650/−320) W/m K and (28 + 16/−9.2) MW/m2 K for the supported graphene. The thermal conductivity of the suspended graphene exceeds (2500 + 1100/−1050) W/m K near 350 K and becomes (1400 + 500/−480) W/m K at about 500 K.
The reported thermal conductivity (κ) of suspended graphene, 3000 to 5000 watts per meter per kelvin, exceeds that of diamond and graphite. Thus, graphene can be useful in solving heat dissipation problems such as those in nanoelectronics. However, contact with a substrate could affect the thermal transport properties of graphene. Here, we show experimentally that κ of monolayer graphene exfoliated on a silicon dioxide support is still as high as about 600 watts per meter per kelvin near room temperature, exceeding those of metals such as copper. It is lower than that of suspended graphene because of phonons leaking across the graphene-support interface and strong interface-scattering of flexural modes, which make a large contribution to κ in suspended graphene according to a theoretical calculation.
We demonstrate a top-down method for fabricating nickel mono-silicide (NiSi) nanolines (also referred to as nanowires) with smooth sidewalls and line widths down to 15 nm. Four-probe electrical measurements reveal that the room temperature electrical resistivity of the NiSi nanolines remains constant as the line widths are reduced to 23 nm. The resistivity at cryogenic temperatures is found to increase with decreasing line width. This finding can be attributed to electron scattering at the sidewalls and is used to deduce an electron mean free path of 6.3 nm for NiSi at room temperature. The results suggest that NiSi nanolines with smooth sidewalls are able to meet the requirements for implementation at the 22 nm technology node without degradation of device performance.
The creation of a sustainable energy generation, storage, and distribution infrastructure represents a global grand challenge that requires massive transnational investments in the research and development of energy technologies that will provide the amount of energy needed on a sufficient scale and timeframe with minimal impact on the environment and have limited economic and societal disruption during implementation. In this opinion paper, we focus on an important set of solar, thermal, and electrochemical energy conversion, storage, and conservation technologies specifically related to recent and prospective advances in nanoscale science and technology that offer high potential in addressing the energy challenge. We approach this task from a two-fold perspective: analyzing the fundamental physicochemical principles and engineering aspects of these energy technologies and identifying unique opportunities enabled by nanoscale design of materials, processes, and systems in order to improve performance and reduce costs. Our principal goal is to establish a roadmap for research and development activities in nanoscale science and technology that would significantly advance and accelerate the implementation of renewable energy technologies. In all cases we make specific recommendations for research needs in the near-term (2–5 years), mid-term (5–10 years) and long-term (>10 years), as well as projecting a timeline for maturation of each technological solution. We also identify a number of priority themes in basic energy science that cut across the entire spectrum of energy conversion, storage, and conservation technologies. We anticipate that the conclusions and recommendations herein will be of use not only to the technical community, but also to policy makers and the broader public, occasionally with an admitted emphasis on the US perspective.
Thermal conductance measurements of individual single- (S), double- (D), and multi- (M) walled (W) carbon nanotubes (CNTs) grown using thermal chemical vapor deposition between two suspended microthermometers are reported. The crystal structure of the measured CNT samples is characterized in detail using transmission electron microscopy (TEM). The thermal conductance, diameter, and chirality are all determined on the same individual SWCNT. The thermal contact resistance per unit length is obtained as 78–585 m K W−1 for three as-grown 10–14 nm diameter MWCNTs on rough Pt electrodes, and decreases by more than 2 times after the deposition of amorphous platinum–carbon composites at the contacts. The obtained intrinsic thermal conductivity of approximately 42–48, 178–336, and 269–343 W m−1 K−1 at room-temperature for the three MWCNT samples correlates well with TEM-observed defects spaced approximately 13, 20, and 29 nm apart, respectively; whereas the effective thermal conductivity is found to be limited by the thermal contact resistance to be about 600 W m−1 K−1 at room temperature for the as-grown DWCNT and SWCNT samples without the contact deposition.
Carbon nanofibers (CNFs) were incorporated into nylon 11 to form nylon 11-carbon nanofiber nanocomposites via twin screw extrusion. Injection molding has been employed to fabricate specimens that possess enhanced mechanical strength and fire retardancy. The thermal conductivity of these polymer nanocomposites was measured using a guarded hot plate method. The measurement results show that the room temperature thermal conductivity increases with the CNF loading from 0.24±0.01 W/m K for pure Nylon 11 to 0.30±0.02 W/m K at 7.5 wt % CNF loading. The effective medium theory has been used to determine the interface thermal resistance between the CNFs and the matrix to be in the range of 2.5–5.0×10−6 m2 K/W from the measured thermal conductivity of the nanocomposite.
The thermal conductivity of individual bismuth nanowires was characterized using a suspended microdevice and correlated with the crystal structure and growth direction obtained by transmission electron microscopy on the same nanowires. Compared to bulk bismuth in the same crystal direction perpendicular to the trigonal axis, the thermal conductivity of a single-crystal bismuth nanowire of 232 nm diameter was found to be three to six times smaller than bulk in the temperature range between 100 and 300 K, and those of polycrystalline bismuth nanowires of 74–255 nm diameter are reduced by factors of 18–78 over the same temperature range. The thermal conductivity suppression in the single-crystal nanowire can be explained by a transport model that considers diffuse phonon-surface scattering, partially diffuse surface scattering of electrons and holes, and scattering of phonons and charge carriers by ionized impurities such as oxygen and carbon of a concentration on the order of 1019 cm−3. The comparable thermal conductivity values measured for polycrystalline nanowires of different diameters suggests a grain boundary scattering mean free path for all heat carriers in the range of 15–40 nm, which is smaller than the nanowire diameters.
The temperature distributions in current-carrying carbon nanotubes have been measured with a scanning thermal microscope. The obtained temperature profiles reveal diffusive and dissipative electron transport in multiwalled nanotubes and in single-walled nanotubes when the voltage bias was higher than the 0.1–0.2 eV optical phonon energy. Over 90% of the Joule heat in a multiwalled nanotube was found to be conducted along the nanotube to the two metal contacts. In comparison, about 80% of the Joule heat was transferred directly across the nanotube-substrate interface for single-walled nanotubes. The average temperature rise in the nanotubes is determined to be in the range of 5–42 K per microwatt Joule heat dissipation in the nanotubes.
The thermoelectric properties and crystal structure of individual electrodepositedbismuth telluride nanowires (NWs) were characterized using a microfabricated measurement device and transmission electron microscopy. Annealing in hydrogen was used to obtain electrical contact between the NW and the supporting Pt electrodes. By fitting the measured Seebeck coefficient with a two-band model, the NW samples were determined to be highly n-type doped. Higher thermal conductivity and electrical conductivity were observed in a 52 nm diameter monocrystalline NW than a 55 nm diameter polycrystalline NW. The electron mobility of the monocrystalline NW was found to be about 19% lower than that of bulk crystal at a similar carrier concentration and about 2.5 times higher than that of the polycrystalline NW. The specularity parameter for electron scattering by the NW surface was determined to be about 0.7 and partially specular and partially diffuse, leading to a reduction in the electron mean-free path from 61 nm in the bulk to about 40 nm in the 52 nm NW. Because of the already short phonon mean-free path of about 3 nm in bulk bismuth telluride, diffuse phonon-surface scattering is expected to reduce the lattice thermal conductivity of the 52–55 nm diameter NWs by only about 20%, which is smaller than the uncertainty in the extracted lattice thermal conductivity based on the measured total thermal conductivity and calculated electron thermal conductivity. Although the lattice thermal conductivity of the polycrystalline NW is likely lower than the bulk values, the lower thermal conductivity observed in this polycrystalline sample is mainly caused by the lower electron concentration and mobility. For both samples, the thermoelectric figure of merit (ZT) increases with temperature and is about 0.1 at a temperature of 400 K. The low ZT compared to that of bulk crystals is mainly caused by a high doping level, suggesting the need for better control of the chemical composition in order to improve the ZT of the electrodeposited NWs. Moreover, bismuth telluride NWs with diameter less than 10 nm would be required for substantial suppression of the lattice thermal conductivity as well as experimental verification of theoretical predictions of power factor enhancement in quantum wires. Such stringent diameter requirement can be relaxed in other NW systems with longer bulk phonon mean-free path or smaller effective mass and thus longer electron wavelength than those in bulk bismuth telluride.