G Model

MRB-6622; No. of Pages 5
Materials Research Bulletin xxx (2013) xxx–xxx

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Materials Research Bulletin
journal homepage: www.elsevier.com/locate/matresbu

Thermoelectric response of carbon nanotube films to Au-nanoparticle incorporation
Gustavo E. Fernandes *, Jin Ho Kim, Jimmy Xu
Brown University, School of Engineering, 182 Hope Street, Providence, RI, 02912, USA



Article history: Received 20 November 2012 Received in revised form 16 March 2013 Accepted 17 April 2013 Available online xxx Keywords: Nanostructures Thin films Thermal conductivity

We report on a study of the effects on the thermoelectric properties of CNT films of incorporating Au nanoparticles of different sizes. Our characterization included measurements of the electrical conductivity, thermal conductivity, and Seebeck coefficient, as well as estimation of the power factor and dimensionless thermoelectric figure of merit for these materials. We found that the thermoelectric properties were significantly affected by the size of Au-nanoparticles used. Addition of Au-nanoparticles of both small (5 nm) and large (60 nm) diameters led to a decrease in the electrical conductivity from 1.8 Â 105 SmÀ1 for the pure CNT film to 6.2 Â 104 and 7.9 Â 104 SmÀ1 for samples functionalized with 5 nm and 60 nm Au-NPs, respectively. Addition of 5 nm Au-nanoparticles also led to a decrease in the thermal conductivity to 73 WmÀ1KÀ1 from 82 WmÀ1KÀ1 for the pure CNT film, whereas the thermal conductivity of the sample with 60 nm Au-nanoparticles increased to 106 WmÀ1KÀ1. The pure CNT film had a Seebeck coefficient of 31 mVKÀ1, while the samples with 5 and 60 nm Au-NPs only achieved 25 mVKÀ1. The best value for the thermoelectric figure of merit (ZT) was 6.04 Â 10À4 for the pure CNT film, and 1.73 Â 10À4 and 1.33 Â 10À4 for the samples with 5 nm and 60 nm Au-NPs. The power factors were found to be 1.67 Â 10À4, 4.2 Â 10À5, and 4.7 Â 10À5 WmÀ1KÀ2 for the pure CNT, and the samples with 5 and 60 nm Au-NPs, respectively. ß 2013 Elsevier Ltd. All rights reserved.

1. Introduction Thin films of randomly dispersed and oriented single walled carbon nanotubes (CNT) comprise an interesting functional material platform, with potential applications in electronics, photonics, transparent conductive coatings, and thermoelectrics [1]. The latter are particularly interesting because many basic science questions still remain open regarding the thermoelectrics of CNTs [2–4]. The thermoelectric properties of a single isolated CNT are determined first and foremost by its chirality [4]. The situation is more complex in thin-film format because, in addition to the single CNT properties, the CNT-to-CNT contacts also play an important role in determining both thermal and electronic transport properties [5–8]. CNT films also possess many desirable properties from a thermoelectric engineering standpoint. They are strong and lightweight [9], conformal [10], electrically [10,11] and thermally conductive [12,13], show very good resistance to chemicals, and are amenable to functionalization with other

* Corresponding author at: 182 Hope Street, Box D, Providence, RI, 02912, USA. Tel.: +1 401 863 2447. E-mail address: Gustavo_Fernandes@Brown.edu (G.E. Fernandes). 0025-5408/$ – see front matter ß 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.materresbull.2013.04.033

materials including polymers [14,15], nanoparticles (NPs), or solution-grown polycrystalline semiconductors and metals. In practical device implementations, the thermoelectric efficiency encompasses both a contribution that depends on the details of the device, as well as a contribution that is intrinsic to the thermoelectric material [16]. This intrinsic material contribution is expressed in terms of the thermoelectric figure of merit, ZT ¼ S2 s =ðke þ kL Þ, where S is the Seebeck coefficient (V/K), s is the electrical conductivity (S/m) and k = ke + kL is the thermal conductivity (WmÀ1KÀ1), which consists of electronic (ke) and lattice (kL) contributions. The quantity S2s (WmÀ1KÀ2) is known as the thermoelectric power factor. ZT is related to the maximum efficiency that a thermoelectric generator made of the specific material would be able to achieve. Currently available bulk homogenous material platforms have a maximum ZT  1 at 300 K. Lead composites [17–19], in particular Na and Ta doped PbTe alloys and Na doped PbTe1ÀxSex have been shown to achieve ZT  1.4 to 1.8 at high temperatures (>750 K). For higher temperatures Si– Ge alloys are found to be the best thermoelectrics, with ZT  0.7 [20]. In order for thermoelectric devices to compete with modern household refrigerators ZT larger than 3 is required. The impetus to meet this mark has brought nanotechnology strategies into the picture. In particular, nanoinclusions and nanopatterning have been used in various attempts to decrease kL and increase S. PbTe/

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temperature difference plot. [30] as well as their surface properties (wetting). Finally. the samples on glass substrates were suspended between a hot Cu block and a cold Cu block that served as heat source and sink. Res. The dispersion of both CNTs and Au-NPs were homogeneous over macroscopic areas spanning the entire film surface (2.5 cm in diameter).5) [21].2013.). The final products were highly uniform films with 50–60 nm in thickness atop a porous alumina membrane substrate. The smaller particles are expected to attach to the outer wall of CNTs and change their phonon dispersion properties. thereby altering both the thermal and electronic transport properties. The transferred films adhered very well to the glass substrates forming a uniform coating without holes. which are discussed in detail below. This finding by itself is neither negative nor positive. recent studies have shown that ZT  0.) and the thermo-voltage was measured with an electrometer (Model 236. followed by rinsing with ethanol and drying in air. Nicolet Inc. Keithley Inc.E. http://dx. While CNTs are not currently perceived as efficient thermoelectric materials.1016/j.. Results and discussion Fig. the porous alumina substrates were dissolved in H3PO4 as described above and the floating CNT membranes were transferred to Cu grids containing circular holes of 54 mm in diameter and arranged hexagonally with a center-to-center separation of 75 mm (Ted Pella Inc.6 Â 1010 Â 60 nm Au-NPs and 4.5 M solution of H3PO4 at 60 8C for 2 h and transferring the floating CNT films to optical glass slides. Fernandes. Films were then formed by vacuum filtering the CNT-Au-NP solutions through porous anodic alumina membrane filters having a mean pore diameter of 20 nm (Whatman Inc. The particles visible in Fig. et al. Overall. Fernandes et al. In order to achieve suspended circular membranes for the thermal conductivity measurements. To obtain composites with AuNPs. / Materials Research Bulletin xxx (2013) xxx–xxx PbSeTe quantum dot arrays have been shown to have ZT  1.5 Â 1013 Â 5 nm Au-NPs. it is worthwhile noting that CNT membranes and CNT composites have ample room for optimization in terms of their many adjustable material parameters. The sheet resistances were measured using a typical four point probe setup [32] and the thicknesses were measured via cross sectional imaging in a scanning electron microscope. The micro-thermocouples were read with a thermocouple reader with two electrically isolated channels (Dataq Inc.). were positively affected.) was focused to a spot 1. this ratio of metallic to semiconducting CNTs was chosen because our preliminary testing revealed that purely metallic or purely semiconducting CNT films had slightly lower Seebeck coefficient.) containing a pre-determined number of Au-NPs. The process was repeated for various powers of the exciting laser.G Model MRB-6622.). with average diameter 1. Comparison of the intensities of the Stokes and Anti-Stokes Glines obtained with a given fixed power of the exciting laser allowed determination of the temperature of the CNT membrane at the laser spot as well as the membrane thermal conductivity. which was important to establish a reliable heat sink at the perimeter of the suspended CNT membranes. 2. This system presents a potentially interesting scenario because.033 . The optical absorption of the CNT membranes at 532 nm. The error bars are one standard deviation wide and the values represent the mean values obtained from measurement of Please cite this article in press as: G. No. The number of Au-NPs was adjusted so that approximately the same total volume of Au was present in each solution. Bull. Measurements of the thermal conductivity via the Raman method at two different powers of the excitation laser are plotted in Fig. Such aggregates were found to have diameters up to 20 nm. was purchased from NanoIntegris Inc.materresbull. In this article we investigate the thermoelectrics of thin CNT membranes functionalized with Au-NPs of different sizes. and our results could be viewed as presenting a first feel for the types of contributions that such externally incorporated NPs may bring to the electrical and thermal conduction and to the thermoelectrics of CNT networks. was measured with a spectrophotometer (Cary 500.04. as well as the fact that this represents the most common yield in various CNT synthesis processes. Electronic transport can be affected by small and large particles alike. were that indeed the inclusion of Au-NPs affected practically all the thermoelectric parameters of the CNT membrane system. the resistance of a random network of high quality nanotubes is dominated by that of the junctions and NP insertions would effectively alter the junctions in number (density) and in resistance. 1 shows SEM images of the prepared films. To date only a few works have investigated the thermoelectric properties of CNT membranes [23–30]. namely.org/10.E. while others. Briefly. with the Au-NPs uniformly dispersed. however. 1(b) correspond to aggregates of many 5 nm Au-NPs. Some parameters. such as s and S were negatively affected in the samples tested. 3. For example. (2013). After thoroughly rinsing in ethanol and drying in air for 1 h. Our findings. Along with each electrical contact a type K micro-thermocouple (100 mm diameter) was also attached to the same location as the electrical lead with silver paste.4 is achievable at high temperature in Ar plasma treated CNT films [23]. Experiment A surfactant-dispersed single-walled CNT solution (1% sodium dodecyl sulfate) composed of 1/3 semiconducting CNTs and 2/3 metallic CNTs. 2. respectively. The thermal conductivity was measured with a Raman spectroscopy based technique [33–36]. This was accomplished by dissolving the alumina filter in a 0. The films were transferred to glass substrates for testing. of Pages 5 2 G.5 at room temperature which is better than that of PbTe or PbTeSe alone (ZT  0.8 mm in diameter at the center of a suspended circular piece of the CNT membrane and served both to locally heat the membrane as well as to excite the Stokes and Anti-Stokes Raman spectra of the CNTs. the membrane formed very good conformal contact with the copper portions of the grid. The Seebeck coefficient was then determined from the slope of the thermo-voltage vs. Silicon nanowires with rough surfaces were also shown to have ZT  1 and recently holey Si membranes were found to be good thermoelectric materials near room temperature [22]. Various suspended circular membranes were thus obtained from a small piece of CNT membrane. the Au-NP inclusions of large and small sizes reduced the thermoelectric power generation capability of these materials. needed for determination of the thermal conductivity. The films were then rinsed several times with acetone to remove the surfactant. and the process of transferring the membranes to glass substrates did not disturb this homogeneity. The chosen numbers of particles were. such as k for the membrane with 5 nm Au-NPs. because the properties of Au-to-CNT contacts depend on the differences in work function between these two materials.). Varian Inc. 2. the Seebeck coefficient may in principle benefit from the introduction of NPs insofar as NP-CNT contacts could introduce energy-dependent electron scattering mechanisms [17]. in theory. In order to measure the Seebeck coefficient. Mater. Electrical contacts consisting of 200 mm diameter Pt wires were attached to the hot and cold sides of the sample with silver paste.4 nm. creases or trapped air bubbles. As discussed before [31]. and could in principle allow altering the lattice contribution to the thermal conductivity on a different scale than that achieved by CNT-CNT contacts. akin to attaching point masses to a vibrating string.doi. 1 ml of the 25 mg/L aqueous CNT solution was pre-mixed with a solution of water-dispersed Au-NPs (Ted Pella Inc. the 532 nm laser from a Raman system (Almega.

0 eV [39]. This model may account at least partially for the behavior observed here.e. 1. bundling of the CNTs was not immediately observed in the SEM studies of the samples in Fig. (1). The reduction in s with Au addition may be explained by contact resistances between CNTs and Au-NPs. In a recent study. which in turn causes s to drop due to increased CNT-CNT contact resistances. Prior to measurement the samples were rinsed in either deionized water or ethanol and allowed to dry. which gave 89 WmÀ1KÀ1. Choi et al. The Seebeck coefficient is generally described by the Mott formula: S¼ p2 kB 2 T 3 e !  dlns ðEÞ . Bull. while increased contact resistances between CNTs due to the presence of Au-NPs could explain the overall decrease in s. The pure CNT film had a Seebeck coefficient of 31 mV/K. The error bars correspond to two standard deviations of measurements performed on 25 samples. given by the slope of the plots. where kB is Boltzmann’s constant. akin to point masses attached to a vibrating string. followed by the 60 nm Au-NP sample and then the 5 nm NP sample. Mater. may lead to different regimes of VRH [11]. Thermal conductivity measured with two different powers of the excitation laser. the random spatial distribution of CNT-CNT and CNT-Au-CNT contacts. the electrical properties of the CNT-Au contacts could generate depletion regions and lead to carrier localization.org/10. Fig. which would account for the observed drop in S.033 . and Au was identified. i. (2013). They found that in addition to work function differences. The Au-NPs may indeed have increased the s of individual CNTs via doping. are summarized in Table 1. of Pages 5 G. 3 shows the thermoelectric voltage as a function of the temperature difference between the hot and cold ends of the CNT films. 1. No. while that for the sample with 5 nm Au-NPs was 72 WmÀ1KÀ1.G Model MRB-6622. [42] found that. According to Eq. The Seebeck coefficients. However. s(E) the contribution to the conductivity from carriers having energy near E. and EF is the Fermi level. Lim et al. suggesting a possible contribution from the CNT-Au contacts. At larger Au-NP concentrations. They found Please cite this article in press as: G. SEM images of Au-NP/CNT films. the Au-NPs are believed to affect the dispersion of CNTs and lead to bundling. Our measurements of the thermal conductivity for the pure CNT sample compare well to other reports available in the literature [12. variable range hopping (VRH) conductivity [40. 25 suspended circular membranes for each sample. although the mean values for the ethanol treated samples were within the error of the water treated samples. We also compared the effects of rinsing the samples with either deionized water or ethanol prior to transfer to the copper grid. (a) Pure CNT film. dE E¼EF (1) Fig. The electrical conductivities (s) of the samples are summarized in Table 1 along with other measured parameters. which agrees well with other reports on films of single walled CNTs [29]. et al. we note that the contact between a CNT and a 60 nm diameter Au-NPs is expected to be larger in area than the contact between two CNTs. The thermal conductivity for the sample with 60 nm Au-NPs (105 WmÀ1KÀ1) was larger than that obtained by a simple mass-weighted average of the thermal conductivities of Au (318 WmÀ1KÀ1) and the pure CNT sample (85 WmÀ1KÀ1). but also cause jSj to drop. Disregarding the electronic properties of the contact. Fernandes et al.38] and alter the thermal transport within the nanotube by creating phonon scattering centers. http://dx. Many 5 nm Au-NPs coalesced into larger clusters 20 nm in size visible in the image. ranging from 4. much better reproducibility was achieved for the ethanol treated samples.04.materresbull. The pure CNT sample had the largest s.1016/j. [39] studied contact resistances for contacts of CNTs with various metals. AuNPs have a doping effect on the CNTs that increases s.2013. / Materials Research Bulletin xxx (2013) xxx–xxx 3 Fig. The smaller particles are more likely to attach to the sidewalls of individual CNTs [37. The work function of Au is 5.1 eV. while single walled CNTs such as those used here are expected to have somewhat smaller work function.41] or carrier localization may lead to strong energy dependence of s(E).5 to 5. among other noble metals.33]. Fernandes. Res. The Au-NPs are seen embedded in the CNT film.doi. 2.E. Moreover. e the electron charge. the wettability of the metal onto the CNT surface plays a significant role in the contact resistances. As discussed above. Yu et al. and 105 WmÀ1KÀ1 for the sample with 60 nm Au-NPs. Good reproducibility in the measurements is achievable with this method in different locations of the sample.. (b) CNT film with 5 nm Au-NPs. as yielding relatively poor contacts with CNTs. Both samples containing Au-NPs had 25% lower Seebeck coefficients compared with the pure CNT film. In particular.E. S increases proportionately with the rate of change of the electrical conductivity with energy. [30] reported on the effects of the reduction of metal ions (Au and Cu) on nanotube membranes on the Seebeck coefficient and the electrical conductivity. While the effect was less pronounced in the pure CNT sample. The thermal conductivity of the pure CNT sample was 85 WmÀ1KÀ1. in moderate quantities. Such CNT-Au-CNT contact effects are not expected to be significant in the case of the 5 nm Au-NPs. This derivative is enhanced when strongly energy dependent carrier scattering processes are present in [17]. (c) CNT film with 60 nm Au-NPs.

indicating that the Au inclusions may either short out thermoelectric pathways in the material (i. Our results agree with those of Yu et al. while k5nm/kpure 0. We note that their approach could potentially experience limitations in the case of thick CNT films. / Materials Research Bulletin xxx (2013) xxx–xxx Table 1 Thermoelectric figures for CNT + Au-NPs membranes at 300 K. Mater. They attributed their findings to large changes in the Fermi level with respect to carrier concentration observed in CNTs.000133 that Au incorporation increased conductance and reduced the Seebeck coefficient of the membranes (the opposite effect was noted for Cu).000604 0.7 4. The thermoelectric power factor was highest for the pure CNT sample at 0. with the pure CNT sample achieving the highest ZT (6. performed direct metal reduction on the CNT surface. significant enhancements in ZT may be achievable.44]. The dashed lines are linear regressions of the data. to investigate potential effects of surfactants.4 at 600 8C for Ar plasma treated CNT membranes. and thus emphasize the role of such experimental probing. 4. Overall. although the room temperature values were considerably smaller at 1. provided that the addition of Au does not significantly disturb the dispersion of CNTs and the final uniformity of the membranes. we found that Au nanoparticle incorporation decreased the electrical conductivity as well.7 ZT 0. led to an increase in the thermal conductivity. in contrast to Yu et al.33 Â 10À4). has the advantage of achieving size uniformity of the nanoparticles.E. Zhao [23] recently reported ZT as large as 0. we performed comparative measurements on annealed samples (8 h. Fig. 3. http://dx. Fernandes. indicating a possible thermal shunt effect from these larger NPs. and that metallic CNTs would have much smaller ZT. Finally. Additionally. Other studies have suggested that the effect of Au-NPs on CNT membranes can be tuned to achieve significant enhancements in s. our results indicate that for such CNT systems the thermal conductivity and ZT can be affected by nanoparticle incorporations. Jiang et al. with s5nm/spure 0. of Pages 5 4 G. In both cases the Seebeck coefficient was found to decrease compared with the pure CNT membrane.020 k (W mÀ1 KÀ1) 83 73 106 S (mV KÀ1) 30.000173 0. Thermoelectric voltage vs. In contrast. Please cite this article in press as: G. followed by the sample with 5 nm Au-NPs (1. to the extent that gold incorporation worsened the Seebeck coefficient. 450 8C.45.919 79. In contrast to their findings. and of being easily extended to thick films. As such.35. while potentially yielding less conformal contacts between CNTs and NPs. our approach based on the incorporation of pre-made Au nanoparticles.88. due to the much smaller Seebeck coefficient of Au compared with that of CNTs) or that the Au-NPs may have a doping effect on individual CNTs thus increasing their s and decreasing their S.. a complete picture of the thermoelectric potential of such CNT membranes requires knowledge of the thermal conductivity in addition to the power factor.16 mWmÀ1KÀ2 followed by the sample with 60 nm Au-NPs (0. We note. Ar at 1 atm) and found no significant differences in our results.7 Â 10À3.04 mWmÀ1KÀ2).2. the thermoelectric performance of the membranes was found to degrade upon addition of Au-NPs. which indicates a possible transfer of carriers from the CNTs to the Au-NP with some depletion of carriers in the CNTs. As discussed in the introduction. with further optimization of the Au-NP amount for small diameter NPs.1016/j.G Model MRB-6622. The decrease in s relative to a pure CNT film was more prominent than the decrease in k.E. the decrease in s that was also observed had an overall detrimental effect.73 Â 10À4) and finally the sample with 60 nm Au-NPs (1. The addition of large Au-NPs of 60 nm in diameter caused k to increase but s to decrease.4 S2s (10À5 W mÀ1 KÀ2) 16. Also. Thus.43.’s work. No. that some trends were observed in the system response – the electrical conductivity invariably decreased with addition of AuNPs.29 and s5nm/spure 0. The thermoelectric figure of merit (ZT) followed a trend similar to the power factor.e. because the strong van-der-Waals forces between CNTs as well as their hydrophobicity might prevent proper infiltration of the metal ion solutions. Yu et al.1 24. as was performed here. Fernandes et al. indicating a possible scattering of phonons in the CNTs following the ‘‘point masses attached to a vibrating string’’ picture described above. Despite the reduction in k obtained in the sample with 5 nm Au-NPs. it is possible that. temperature difference between the hot and cold ends of the AuNP-CNT films.org/10.05 mWmÀ1KÀ2) and finally the sample with 5 nm AuNPs (0. due to doping of the CNTs by the Au-NPs. The power factor values obtained here compare favorably with other studies on the thermoelectric of CNT membranes [23. Conclusion Addition of 5 nm diameter Au-NPs to a 50 nm thick CNT membrane led to lower k but also to lower s. The primary reason for the relatively small ZT values in our membranes can be attributed to the comparatively larger thermal conductivities of our materials. As such they cannot be easily modeled.2013. Sample CNT CNT + 5 nm Au-NP CNT + 60 nm Au-NP d (nm) 50 48 56 s (S/m) 176. Bull. [45] have theoretically predicted that individual semiconducting single walled CNTs can have a maximum ZT 0. Res. while simultaneously increasing the contact resistances between CNTs.materresbull.04 Â 10À4). This result could not be anticipated on principles ground alone.04. et al. the effects of Au-NPs on the transport properties of such CNT membranes are complex and strongly dependent on the contact geometries and surface conditions. (2013). giving k5nm/kpure 1. however.212 61.033 . We believe this difference may stem from the different methodologies used in incorporating the Au nanoparticles into the CNT films.8 26. on the other hand. which is expected to yield electronic-grade contacts between the nanoparticles and the CNTs due to (1) the absence of surfactants and (2) the fact that the nanoparticles are formed directly (and conformally) on the CNT surfaces. The large Au-NPs.2 4.doi. the smaller Au-NPs led to a decrease in the thermal conductivity. which can considerably change the Seebeck coefficient without considerable change in the electrical conductivity.

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