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DOI: 10.1002/adma.200800401

Enhanced Thermal Conductivity in a Hybrid Graphite Nanoplatelet Carbon Nanotube Filler for Epoxy Composites**
By Aiping Yu, Palanisamy Ramesh, Xiaobo Sun, Elena Bekyarova, Mikhail E. Itkis, and Robert C Haddon*
The increased heat generated in high density electronics has intensied the search for advanced thermal interface materials (TIMs) and prompted fundamental studies at the nanoscale level to develop ller materials with enhanced thermal performance.[14] Single-walled carbon nanotubes (SWNTs) considerably improve the heat transport in polymer composites as a result of their one-dimensional (1D) structure, high thermal conductivity and high aspect ratio.[512] Recently, two-dimensional (2D) nanostructures such as graphite nanoplatelets (GNPs), have emerged as a promising ller in polymer matrices[1319] and it has been shown that they provide even higher thermal conductivity enhancement than SWNTs.[16] In this study we combine 1D-SWNTs and 2D-GNPs to prepare a series of hybrid graphitic nanollers and we observe a synergistic effect between the GNPs and SWNTs in the enhancement of the thermal conductivity of epoxy composites to the point that at certain ller loadings the hybrid composition outperforms composites utilizing pure GNP or SWNT llers. The increased thermal conductivity is ascribed to the formation of a more efcient percolating nanoparticle network with signicantly reduced thermal interface resistances. The idea of using a hybrid ller comprised of two or more traditional ller materials has already been explored in the literature and it has been demonstrated that improved composite performance can be achieved by combining the advantages of each ller.[20,21] Commercially available thermal greases and adhesives often utilize several components to achieve the desired combination of thermal and electrical conductivities, viscosity and low coefcient of thermal expansion. In our study, we utilize two different nanostructured graphitic llers for incorporation into epoxy resin: puried SWNTs and graphite nanoplatelets (GNPs) comprised
[*] Prof. R. C Haddon, A. Yu, Dr. P. Ramesh, Dr. X. Sun, Dr. E. Bekyarova, Dr. M. E Itkis Center for Nanoscale Science and Engineering Departments of Chemistry and Chemical & Environmental Engineering University of California Riverside Riverside, California 92521 (USA) E-mail: haddon@ucr.edu [**] We acknowledge the nancial support from DOD/DMEA under award # H94003-06-20604 and # H94003-08-2-0803 and technical help in graphite exfoliation from Yasir Khalid Ali and Kimberly Worsley. Supporting Information is available online from Wiley InterScience or from the authors.

of few graphene layer Gn, where n $ 4. The SWNT component of the hybrid ller is electric arc produced puried SWNTs with a typical length of 0.31.0 mm and an average diameter of 1.4 nm. The purication process[22] leaves the SWNTs ends and side-walls functionalized with carboxylic acid groups and this facilitates their homogeneous dispersion into the polymer matrix. In addition, the epoxy curing process is accompanied by a cross-linking reaction between the carboxylic acid groups of the SWNTs and the epoxy groups of the polymer,[23] thus improving the integration of SWNTs into the polymer matrix. GNPs are typically prepared by intercalation and exfoliation of graphite;[2429] and by control of the exfoliation conditions we were able to obtain GNPs comprised of 2 to 8 graphene layers with a lateral dimension of 2001000 nm and an aspect ratio in the range of 50 to 300.[16] This was achieved by thermal shock exfoliation of natural graphite akes at 800 8C[25,26] followed by high shear mixing and sonication in order to separate the exfoliated graphite akes into nanoplatelets.[16] A series of composites were prepared with a hybrid ller loading between 5 wt % and 40 wt % in the epoxy (EPON 682/ EPIKURE) matrix. The ratio of SWNTs and GNPs in the hybrid ller was varied in order to study their efciency in enhancing the thermal conductivity of the composite. The thermal and electrical conductivity measurements were performed using composite disks with a diameter of 2.54 cm and thickness of 412 mm. A detailed composite preparation procedure was reported in our previous publications,[12,16] and it is described briey in the experimental section. Figure 1a shows the thermal conductivity (k) of GNP-SWNT/epoxy composites as a function of the GNP fraction in the hybrid ller at a hybrid ller loading of 10 wt %. The epoxy composites prepared with a 10 wt % loading of the individual llers gave thermal conductivities of kSWNT 0.85 W m1 K1 for the SWNT lled composite[12] and kGNP 1.49 W m1 K1 for the GNP-lled composite.[16] In the case of a hybrid ller (HYB), the thermal conductivity is expected to increase monotonically as the fraction of the more efcient GNP ller increases, in accord with the rule of mixtures. However, the experimental data show a pronounced maximum of kHYB 1.75 W m1 K1 at a GNP:SWNT ller ratio of $3:1 (7.5 wt % GNPs and 2.5 wt % SWNTs in epoxy). Thus the hybrid ller demonstrates a strong synergistic effect and surpasses the performance of the individual SWNT and GNP llers. This synergistic behavior is quite remarkable

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Thermal Conductivity, W/m-K

1.8 1.6 1.4 1.2 1.0 0.8

(a)

GNPX SWNT10-X
0 2 4 6 8 10

SWNT
Electrical Conductivity, S/cm
10 10 10 10 10 10
0

X, Weight%

GNP

(b)

-1

-2

-3

-4

-5

GNPX SWNT10-X
0 2 4 6 8 10

SWNT

X, Weight%

GNP

Figure 1. a) Thermal and b) electrical conductivities of epoxy composites prepared with hybrid GNPxSWNT10-X ller as a function of GNP ller percentage (x); the total ller loading is maintained at 10 wt %. Dashed line in (a) corresponds to the change of thermal conductivity expected from the rule of mixtures. Dotted line in (b) is provided as a guide to the data. Triangles and squares in (a) and (b) correspond to two independent sets of composite sample preparation.

because the substitution of 25 wt % of the GNPs with the less efcient SWNT ller should lead to a decrease in the overall thermal conductivity assuming the rule of mixtures is obeyed (dashed line in Fig. 1a). Figure 1b shows the electrical conductivity of the composites (total ller loading of 10 wt %) as a function of the GNP-SWNT composition. The electrical conductivity (s) of the GNP composite (s 0.3 S cm1) is two orders of magnitude higher than the conductivity of the SWNT-lled composite (s $0.003 S cm1), which suggests that the 2D-GNP material provides a more efcient percolating network[30] compared to the 1D-SWNTs. In the case of composites prepared with a hybrid ller the electrical conductivity shows non-monotonic behavior as a function of the GNP fraction (Fig. 1b) with a minimum in the vicinity of a GNP:SWNT ller ratio of 1:3, which contrasts with the maximum observed in the thermal conductivity data. Thus the introduction of SWNTs into the GNP ller detracts from the electrical transport properties, whereas the thermal transport is augmented at certain compositions. Figure 2 shows SEM and TEM images of epoxy composite with a hybrid ller loading of GNP:SWNT of 3:1 (7.5 wt % of GNPs and 2.5 wt % of SWNTs), which corresponds to the maximum observed in thermal conductivity (Fig. 1a). The

Figure 2. a) SEM and b) TEM images of the cross-section of GNP-SWNT hybrid ller/epoxy composite. Note that SWNTs are bridging adjacent graphite nanoplatelets and SWNTs ends are extended along the nanoplatelet surfaces. c) Schematic representation of GNP-SWNT network in polymer matrix. (see Supporting Information for SEM images of other compositions).

images show complex nanostructures with multiple SWNTs bridging adjacent GNPs (see Supporting Information for SEM images of other compositions). A simple estimate taking into account the average particle size of the GNPs (diameter $350 nm, thickness $2 nm), SWNTs (bundle diameter $5 nm and length $0.5 mm), and densities: GNP (2.26 g cm3), SWNT (1.4 g cm3), epoxy (1.17 g cm3) gives a proportion of $1020 SWNT bundles per GNP and a mean distance between adjacent nanoplatelets of <50 nm, which is in reasonable accord with the microscopy (Fig. 2a and b).

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In order to rationalize the synergistic enhancement of the thermal conductivity in the case of hybrid GNP/SWNT ller we rst consider factors limiting the thermal conductivity of the composites in the cases of individual llers. It is now well established that the thermal conductivity enhancement in SWNT-lled polymers does not reach the theoretically predicted value due to the presence of thermal interface resistance at the SWNT/polymer or SWNT/SWNT boundaries.[3134] It has been suggested that for a SWNT embedded in a polymer matrix the formation of a percolating network for heat ow is suppressed due to the presence of a thin polymer layer which separates the SWNTs in the network and precludes direct SWNT-SWNT phonon transfer.[33,34] Even in case of a direct contact, the geometry of the junctions between two crossed SWNTs leads to a point contact with a very small surface area ($1014 cm2). Thus the interaction between crossed SWNTs is very weak and the surrounding polymer matrix provides the dominant contribution to the heat ow between SWNTs.[34] This interruption of heat ow along the SWNT network due to the involvement of the polymer matrix results in the introduction of a large thermal interface resistance due to the phonon mismatch which is further enhanced by the high curvature of the SWNT surface.[2,35] The GNP ller provides stronger enhancement of the thermal conductivity in comparison with the SWNTs (Fig. 1a) and this is attributed to the following factors: i) the at surface of the graphite nanoplatelets enhances the GNP-polymer matrix interaction, and ii) GNP rigidity allows for better preservation of their high aspect ratio in comparison with the more exible SWNTs.[16] On the other hand, in a 3D-matrix the most probable contact geometry between rigid GNPs is also point-type with a small contact area ($1014 cm2) as in the case of SWNTs; thus direct phonon transport across the GNP junctions is also very weak and heat transfer would require involvement of the polymer matrix resulting in a high thermal interface resistance and suppression of percolation. In the case of hybrid llers (Fig. 2a and b) the 1D-SWNTs are bridging adjacent 2D-nanoplatelets and provide additional channels for the heat ow bypassing the polymer matrix. It can be noticed in the SEM and TEM images (Fig. 2a and b) that the end fragments of some of the bridging SWNTs are aligned along the GNP surfaces by the van der Waals attraction between the graphitic structures and because the full length extension of the exible SWNTs is limited in space by the GNPs; such a hybrid structure is presented schematically in Figure 2c (see Fig. S-3 in Supporting Information). In comparison with individual SWNT or GNP llers the 0D point contact geometry along the ller network is substituted by a 1D linear contact with signicantly increased area of interface junctions within the hybrid ller network. This leads to a decreased thermal interface resistance and may be considered as the major reason for the observed synergistic effect of the 1D and 2D hybrid llers. In contrast, the hybrid network does not provide synergistic enhancement to the electrical conductivity (Fig. 1b). This may

be due to the presence of a thin (few nm) layer of polymer (as described above), which prevents the direct contact between the SWNTs and GNPs (Fig. S-3 Supporting Information) and introduces a scattering layer for the phonon transport as well as an insulating layer in the tunneling barrier for electrical transport.[33,34] According to theoretical modeling,[33,34] an increase in the thickness of the polymer layer from 0 to 10 nm does not affect signicantly the heat transport, however such an increase of the width of the tunneling barrier would effectively eliminate the electrical transport. Because of their rigid shape the GNPs are brought into intimate contact in the highly viscous epoxy matrix during processing; thus the interparticle insulating barrier that is formed between the GNPs may be thinner than in the case of the more exible SWNTs. This can explain the higher electrical conductivity of the GNP-lled composites (Fig. 1b) in comparison with composites prepared with SWNT or SWNT/GNP hybrid llers. Another factor that may mask the potential synergistic behavior in the electrical conductivity is the large difference in the electrical conductivities of the composites with individual llers: s(GNP)/s(SWNT) $100 (Fig. 1b). In comparison the ratio of the thermal conductivities of composites with GNP and SWNTs is k (GNP)/k (SWNT) $1.7 (Fig. 1a and b), thus the sharp drop of the electrical conductivity associated with the decreased GNP fraction (Fig. 1b) is much more difcult to compensate than in the case of the thermal conductivity. Lastly, the electrical conductivity is suppressed due to the presence of Schottky barriers at the GNP/SWNT junction, which depend on the type of SWNTs. A high contact resistance (200 kOhm), exists even in case of junctions between two metallic SWNTs, which is more than an order of magnitude higher than the intrinsic resistance of SWNTs, while contact between metallic and semiconducting SWNTs provides the most resistive junction (>10 MOhm).[36] Thus it is to be expected that there will be a signicant Schottky barrier between the GNPs and the SWNTs particularly for the GNP to semiconducting SWNT contacts. Heat (phonon) transport is expected to be unaffected by the presence of Schottky barriers. Figure 3a presents the thermal conductivity of epoxy composites as a function of hybrid ller loading at GNP:SWNT weight ratio of 3:1. The strength of the synergistic effect can be represented as the ratio (kHYB kGNP)/kGNP (%), and is shown in Figure 3b as a function of the ller loading. In the 10 wt % to 20 wt % loading range the synergistic effect exceeds 20% and the thermal conductivity of the composite with a hybrid ller reaches k 3.35 W m1 K1, the highest value achieved for epoxy composites with a ller loading of less than 20 wt %. The hybrid material provides randomly oriented GNPs and SWNTs in the 3D polymer matrix and the thermal enhancement is isotropic. At higher loadings (greater than 20 wt %), we observed a decrease of the hybrid ller efciency with a crossover in the range of 2530 wt %, and beyond 30 wt % the thermal conductivity provided by the GNP ller became higher than that of the hybrid ller. We suggest that at high hybrid loading the GNP concentration increases to the point that an extended network of GNP conducting pathways is created and

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(a)
6

HYBRID

2 GNP 0
0 10 20 30 40

Weight Loading (%)

30

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(HYBGNP)/GNP(%)

20 10 0 -10 -20 -30

0 10 20 30 40

Weight Loading (%)

800

(c)

600

400

200

CB

SWNT

GNP

Hybrid

Figure 3. a) Thermal conductivity of epoxy composites with GNP-SWNT hybrid ller (red circles, GNP:SWNT 3:1) and GNP ller (black squares) as a function of the ller loading. b) Synergistic effect (kHYB kGNP)/ kGNP(%) associated with the hybrid ller as a function of the ller loading, where kHYB and kGNP are thermal conductivities of hybrid and GNP llers, respectively; (c) thermal conductivity enhancement of epoxy composites for SWNT, GNP and GNP-SWNT hybrid ller at 10 wt % loading in comparison with carbon black (CB).

is 1020 wt % and this loading provides thermal conductivity which would otherwise require 6070 wt % loading of conventional llers.[2] Most likely, the optimum ratio of GNP and SWNT components in the hybrid ller for thermal conductivity enhancement varies with the total ller loading and can shift the point of crossover towards higher loading, but these details of the ller performance are deferred for later study. For comparison, we prepared epoxy composites lled with carbon black (CB), which is one of the most commonly used llers for composites materials. Figure 3c shows that the thermal conductivity enhancements (k k0)/k0 achieved with the GNP-SWNT hybrid ller (775%) exceeds, by more than a factor of 10, the performance of carbon black at the same loading. Currently, the major limitation to the efciency of high aspect ratio carbon-based nanollers (SWNTs and GNPs) and their underperformance in comparison with the theoretical predictions originate from the high thermal interface resistance along the nanoller percolating network and at the interface with the polymer matrix.[3134,3739] This thermal interface resistance can be reduced and the performance of the hybrid GNP-SWNT ller can be signicantly improved by careful engineering of the chemical functionalities on GNP and SWNT surfaces to decrease the thermal interface resistance as theoretically predicted for SWNT composites.[40] In conclusion, by combining 1D-SWNT and 2D-graphitic nanoplatelet llers we achieved a synergistic effect in the thermal conductivity enhancement of epoxy composites. We posit that this synergism originates from the bridging of planar nanoplatelets by the exible SWNTs which lead to a decreased thermal interface resistance along the (2D-1D) hybrid ller network due to the extended area of the SWNT-GNP junctions. The hybrid ller reported herein provides the highest efciency in the thermal conductivity enhancement of composites amongst all reported llers and can be utilized at low ller loading which is important for decreasing the viscosity and improving the processability of thermal interface materials.

Thermal Conductivity Enhancement (%)

(W/m-K)

Experimental
Sample Preparation: The electric arc produced and puried SWNT material (P3-SWNT, average SWNT diameter $1.4 nm, length of 0.51 mm, bundle diameter of 45 nm) was obtained from Carbon Solutions, Inc. Exfoliated graphite was prepared by the acid intercalation and thermal exfoliation of natural graphite akes (500 mm, Asbury Graphite Mills Inc.). The exfoliated graphite particles were subjected to high shear mixing for 30 minutes followed by bath sonication for 24 h (sonic power 270 W) in acetone to obtain graphite nanoplatelets (GNPs). [12] For a typical hybrid sample preparation (ller loading of 10 wt % and GNP:SWNT weight ratio of 3:1), 0.833 g exfoliated graphite and 0.278 g SWNTs were dispersed in 300 mL acetone through 30 min shear mixing and 24 h sonication. Subsequently 7.94 g epoxy (pre-polymer, diglycidyl ether of bisphenol F, EPON 862) was added and shear mixed for another 30 min. The acetone was removed from the dispersion in air and 2.06 g curing agent (diethyltoluenediamine, EPI-KURE) was added. The resulting gel-like material was loaded in a custom-made mold, and cured at 80 8C, 100 8C, and 150 8C for 2h at each temperature in a vacuum oven to prepare the

this dominates the contribution of the SWNT bridges. In our previous study we observed a decreased efciency of the SWNT ller at loadings greater than 5 wt %,[12,16] which was associated with the bending of the SWNTs and decreased effective aspect ratio,[11] as well as increased viscosity of the SWNT-lled epoxy which reduced the processability of the composites and negatively affected the SWNT-polymer matrix bonding.[12] At high hybrid ller loading (>20 wt %) we observed inhomogeneity of the ller distribution in the polymer matrix (see Supporting Information) which may contribute to the suppressed synergistic effect. Thus the optimum range of application for the GNP-SWNT hybrid ller

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disks (diameter 2.54 cm, thickness 4 to 12 mm). For comparison purposes, 1.11 g of carbon black (CB, Vulcan XC72R, 20 nm, Cabot Corp.), SWNTs and GNPs were separately used to prepare composites with 10 wt % loading following the procedure described above. Measurements: Scanning electron microscopy (SEM) images were obtained with a Philips XL30-FEG instrument operating at 10 kV. A number of samples were cut from different locations of the composite disk by razor blade and used for SEM analysis. Other SEM sample preparation techniques included machining, polishing and etching were also used, however the razor blade cutting provided the most representative imaging of the composite samples. High-resolution TEM analysis was performed with Technai12 instrument operating at 120 kV accelerating voltage. TEM samples with a thickness of $200 nm were cut from the composite disks using microtome. Thermal conductivity of disk shaped composite samples with a 2.54 cm diameter was measured using a FOX50 (Laser Comp. Inc.), steady-state heat ow measurement apparatus, employing a dual thickness measurement cycle in order to eliminate the thermal contact resistance of the sample; a value of k0 0.201 W m1 K1 was obtained for neat epoxy. Electrical conductivity was measured by a commercial instrument (Signatone, S-302-4) with four in-line probes. For a specic sample, the testing was performed 10 times at different positions of the disk surface and the nal value was averaged. Correction was made for the nite disk geometry taking into account the disk diameter (2.54 cm), the probe tip spacing (1.59 mm) and the thickness of the disk (4 to 12 mm). [41, 42] Four probe electrical conductivity measurements were also performed by the van der Pauw technique by placing four narrow lines of silver paint at the edge of the disk (908 angle between adjacent contacts) in order to produce 2D current ow. [43, 44] The results from the two sets of measurements were comparable. Received: February 8, 2008 Revised: May 19, 2008 Published online: October 23, 2008

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