Archival Journals Publications

A. L. Moore and Shi, L., “On Errors in Thermal Conductivity Measurements of Suspended and Supported Nanowires using Micro-thermometer Devices from Low to High Temperatures,” Measurement Science and Technology, vol. 22, pp. 015103, 2011. LinkAbstract
For micro-thermometer devices developed for thermal conductivity measurements of nanowires, it is found using finite element analysis that radiation heat transfer can cause nonlinear temperature profiles in the long supporting beams of the thermometers when the sample stage temperature is considerably higher or lower than room temperature. Although the nonlinearity alone does not introduce errors in the measured thermal conductance, it can cause errors in the measured temperature coefficient of resistance of the thermometers and needs to be minimized with additional radiation shields. For a design where the sample is supported on a silicon dioxide bridge between two micro-thermometers, the numerical analysis reveals that a two-dimensional temperature distribution can cause a 25% error in the sample thermal conductance obtained from a one-dimensional heat conduction analysis for a high-thermal-conductance thin film sample covering only the center part of the oxide bridge. This systematic error is reduced considerably for a low-thermal-conductance nanowire sample. However, care must be taken to ensure that the random uncertainties in the two measured thermal conductance values of the bridge with and without the nanowires are much smaller than the thermal conductance of the nanowires.
M. T. Pettes, Jo, I., Yao, Z., and Shi, L., “Influence of Polymeric Residue on the Thermal Conductivity of Suspended Bi-Layer Graphene,” Nano Letters, vol. 11, no. 3, pp. 1195–1200, 2011. LinkAbstract
The thermal conductivity (κ) of two bilayer graphene samples each suspended between two microresistance thermometers was measured to be 620 ± 80 and 560 ± 70 W m−1 K−1 at room temperature and exhibits a κ T1.5 behavior at temperatures (T) between 50 and 125 K. The lower κ than that calculated for suspended graphene along with the temperature dependence is attributed to scattering of phonons in the bilayer graphene by a residual polymeric layer that was clearly observed by transmission electron microscopy.
I. Jo, Hsu, I. K., Lee, Y. J., Sadeghi, M. M., Kim, S., Cronin, S., Tutuc, E., Banerjee, S. K., Z, Y., and Shi, L., “Low-Frequency Acoustic Phonon Temperature Distribution in Electrically Biased Graphene,” Nano Letters, vol. 11, pp. 85–90, 2011. LinkAbstract
On the basis of scanning thermal microscopy (SThM) measurements in contact and lift modes, the low-frequency acoustic phonon temperature in electrically biased, 6.7−9.7 μm long graphene channels is found to be in equilibrium with the anharmonic scattering temperature determined from the Raman 2D peak position. With 100 nm scale spatial resolution, the SThM reveals the shifting of local hot spots corresponding to low-carrier concentration regions with the bias and gate voltages in these much shorter samples than those exhibiting similar behaviors in the infrared emission maps.
A. J. Heltzel, Shi, L., and Howell, J. R., “Microsphere Coupler for a Nanowire Waveguide Plasmonic Probe for Molecular Imaging,” Nanotechnology, vol. 22, pp. 045203, 2011. LinkAbstract
Highly forward scattering of light by a silica microsphere is predicted by Mie theory. Finite-difference time-domain simulations are used to examine the use of a silica microsphere for coupling light into a ZnO nanowire terminated with a gold nanoparticle (NP) tip, intended for near-field imaging of single molecules immobilized on a gold substrate or gold nanoparticle-labeled cell membranes. The results show that plasmonic coupling at the Au tip is dependent on the incident angle of the excitation. Pre-conditioning the signal with the microsphere amplifies the coupling while reducing background energy levels, significantly boosting the signal-to-noise ratio.
S. S. Chen, Moore, A. L., Cai, W. W., Suk, J. W., An, J., Mishra, C., Amos, C., Magnuson, C., Kang, J., Shi, L., and Ruoff, R. S., “Raman Measurements of Thermal Transport in Suspended Monolayer Graphene of Variable Sizes in Vacuum and Gaseous Environments,” ACS Nano, vol. 5, no. 1, pp. 321–328, 2011. LinkAbstract
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.
M. C. Moore, Kang, M. K., Moore, Z., Singh, V., Sreenivasan, S. V., Shi, L., Huang, R., and Roy, K., “Swelling Behavior of Nanoscale Shape- and Size-specific Hydrogel Particles Fabricated using Imprint Lithography,” Soft Matter, vol. 7, pp. 2879–2887, 2011. LinkAbstract
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.
J. H. Seol, Moore, A. L., Jo, I., Yao, Z., and Shi, L., “Thermal Conductivity Measurement of Graphene Exfoliated on Silicon Dioxide,” Journal of Heat Transfer, vol. 133, pp. 022403, 2011. LinkAbstract
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.
F. Zhou, Moore, A. L., Bolinsson, J., Persson, A., Fröberg, L., Pettes, M. T., Kong, H., Rabenberg, L., Caroff, P., Stewart, D., Mingo, N., Dick, K. A., Samuelson, L., Linke, H., and Shi, L., “Thermal Conductivity of Indium Arsenide Nanowires with Wurtzite and Zinc Blende Phases,” Physical Review B, vol. 83, pp. 205416, 2011. LinkAbstract
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.
F. Zhou, Persson, A., Samuelson, L., Linke, H., and Shi, L., “Thermal Resistance of a Nanoscale Point Contact to an Indium Arsenide Nanowire",” Applied Physics Letters 99, vol. 99, pp. 063110, 2011. LinkAbstract
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.
M. C. Moore, Guimard, N., Shi, L., and Roy, K., “Designer Nanoparticles: Incorporating Size, Shape, and Triggered Release into Nanoscale Drug Carriers,” Expert Opinion on Drug Delivery, vol. 7, no. 4, pp. 479–495, 2010. LinkAbstract
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:
I. K. Hsu, Pettes, M. T., Aykol, M., Shi, L., and Cronin, S. B., “The Effect of Gas Environment on Electrical Heating in Suspended Carbon Nanotubes,” Journal of Applied Physics, vol. 108, pp. 084307, 2010. LinkAbstract
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.
F. Zhou, Moore, A. L., Pettes, M. T., Lee, Y., Seol, J. H., Ye, Q. L., Rabenberg, L., and Shi, L., “Effect of Growth Base Pressure on the Thermoelectric Properties of Indium Antimonide Nanowires,” Journal of Physics D: Applied Physics, vol. 43, pp. 025406, 2010. LinkAbstract
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.
A. Mavrokefalos, Lin, Q., Beekma, M., Seol, J. H., Lee, Y. J., Kong, H. J., Pettes, M. T., Johnson, D. C., and L. Shi,In-Plane Thermal and Thermoelectric Properties of Misfit-Layered [(PbSe)0.99]x(WSe2)x Superlattice Thin Films,” Applied Physics Letters, vol. 96., pp. 181908, 2010. LinkAbstract
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.
N. T. Nguyen, Berseth, P. A., Lin, Q., Chiritescu, C., Cahill, D. G., Mavrokefalos, A., Shi, L., Zschack, P., Anderson, M. D., Anderson, I. M., and Johnson, D. C., “Synthesis and Properties of Turbostratically Disordered Ultrathin WSe2 Films,” Chemistry of Materials, vol. 22, no. 9, pp. 2750–2756, 2010. LinkAbstract
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.
W. W. Cai, Moore, A. L., Zhu, Y., Li, X., Chen, S., Shi, L., and Ruoff, R. S., “Thermal Transport in Suspended and Supported Monolayer Graphene Grown by Chemical Vapor Deposition,” Nano Letters, vol. 10, no. 5, pp. 1645-1651, 2010. LinkAbstract
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.
J. H. Seol, Jo, I., Moore, A. L., Lindsay, L., Aitken, Z. H., Pettes, M. T., Li, X., Yao, Z., Huang, R., Broido, D., Mingo, N., Ruoff, R. S., and Shi, L., “Two Dimensional Phonon Transport in Supported Graphene,” Science, vol. 9, no. 328, pp. 213–216, 2010. LinkAbstract
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.
B. Li, Luo, Z. Q., Shi, L., Zhou, J. P., Rabenberg, L. K., Ho, P. S., Allen, R. A., and Cresswell, M. W., “Controlled Formation and Resistivity Scaling of Nickel Silicide Nanolines,” Nanotechnology 20, vol. 20, pp. 085304, 2009. Link to paperAbstract
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.
J. Baxter, Bian, Z., Chen, G., Danielson, D., Dresselhaus, M. S., Fedorov, A. G., Fisher, T. S., Jones, C. W., Maginn, E., Kortshagen, U., Manthiram, A., Nozik, A., Rolison, D., Sands, T., Shi, L., Sholl, D., and Wu, Y., Nanoscale Design to Enable the Revolution in Renewable Energy, 2nd ed., vol. 2. Energy & Environmental Science, 2009, pp. 559–588. Link to paperAbstract
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.
I. K. Hsu, Pettes, M. T., Bushmaker, A., Aykol, M., Shi, L., and Cronin, S. B., “Optical Absorption and Thermal Transport of Individual Suspended Carbon Nanotube Bundles,” Nano Letters, vol. 9, pp. 590–594, 2009. Link to paperAbstract
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M. T. Pettes and Shi, L., Thermal and Structural Characterizations of Individual Single-, Double-, and Multi- Walled Carbon Nanotubes, vol. 19. Advanced Functional Materials, 2009, pp. 3918–3925. Link to paperAbstract
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.