Tunneling diodes based on polymer infiltrated vertically aligned carbon nanotube forests.

We report the fabrication and characterization of metal-insulator-metal diodes incorporating vertically aligned carbon nanotube (VACNT) arrays encased in polymer for applications in high frequency optoelectronics. Polydimethylsiloxane (PDMS) and epoxy infiltrating media are used in this study. VACNT forests are embedded with polymer to form a planarized surface over which an array of tunneling diodes is fabricated. Diodes comprising Al2O3 and HfO2 dielectric multilayers achieve highly nonlinear and asymmetric current-voltage characteristics. Results show that asymmetry in excess of 92 can be achieved with multi-insulator barrier tuning, though there is a strong correlation between asymmetry, resistance, and device longevity. With our best performing and most stable device structure (PDMS-VACNT/Al2O3-HfO2-Al2O3-HfO2/PEDOT:PSS), we provide a demonstration of optical-to-d.c. rectification at 638 nm, realizing a current responsivity of 0.65 µA W-1. Our approach to fabricating these VACNT diode arrays is facile and highly scalable. It is capable of being integrated with solution-processed materials and soft lithography techniques to create flexible devices for optical and infrared detection.

Deformation response of conformally coated carbon nanotube forest.

The deformation mechanism and mechanical properties of carbon nanotube (CNT) forests conformally coated with alumina using atomic layer deposition (ALD) are investigated using in situ and ex situ micro-indentation. While micro-indentation of a CNT forest coated with a thin discontinuous layer using 20 ALD cycles results in a deformation response similar to the response of uncoated CNT forests, a similar test on a CNT forest coated with a sufficiently thick and continuous layer using 100 ALD cycles causes fracture of both the alumina coatings and the core CNTs. With a 10 nm coating, 4-fold and 14-fold stiffness increases are measured using a flat punch and a Berkovich tip, respectively. Indentation testing with the Berkovich tip also reveals increased recoverability at relatively low strains. The results show that ALD coated CNT forests could be useful for applications that require higher stiffness or recoverability. Also, fracturing of the nanotubes shows that upper limits exist in the loading of conformally coated CNT forests.

Carbon nanotube thermal interfaces enhanced with sprayed on nanoscale polymer coatings.

Vertical carbon nanotube (CNT) forests bonded at room temperature with sprayed on nanoscale polymer coatings are found by measurement to produce thermal resistances that are on a par with those of conventional metallic solders. These results are achieved by reducing the high contact resistance at CNT tips, which has hindered the development of high performance thermal interface materials based on CNTs. A spray coating process is developed for depositing nanoscale coatings of polystyrene and poly-3-hexylthiophene onto CNT forests, as a bonding agent that mitigates thermal resistance by enhancing the area available for heat transfer at CNT contacts. Resistances as low as 4.9 ± 0.3 mm(2) K W(-1) are achieved for the entire polymer coated CNT interface structure. The suitability of the spray coating process for large-scale implementation and the role of polymer and CNT forest thickness in determining the thermal resistance are also examined.

Harvesting waste thermal energy using a carbon-nanotube-based thermo-electrochemical cell.

Low efficiencies and costly electrode materials have limited harvesting of thermal energy as electrical energy using thermo-electrochemical cells (or "thermocells"). We demonstrate thermocells, in practical configurations (from coin cells to cells that can be wrapped around exhaust pipes), that harvest low-grade thermal energy using relatively inexpensive carbon multiwalled nanotube (MWNT) electrodes. These electrodes provide high electrochemically accessible surface areas and fast redox-mediated electron transfer, which significantly enhances thermocell current generation capacity and overall efficiency. Thermocell efficiency is further improved by directly synthesizing MWNTs as vertical forests that reduce electrical and thermal resistance at electrode/substrate junctions. The efficiency of thermocells with MWNT electrodes is shown to be as high as 1.4% of Carnot efficiency, which is 3-fold higher than for previously demonstrated thermocells. With the cost of MWNTs decreasing, MWNT-based thermocells may become commercially viable for harvesting low-grade thermal energy.

A metallization and bonding approach for high performance carbon nanotube thermal interface materials.

A method has been developed to create vertically aligned carbon nanotube (VACNT) thermal interface materials that can be attached to a variety of metallized surfaces. VACNT films were grown on Si substrates using standard CVD processing followed by metallization using Ti/Au. The coated CNTs were then bonded to metallized substrates at 220 °C. By reducing the adhesion of the VACNTs to the growth substrate during synthesis, the CNTs can be completely transferred from the Si growth substrate and used as a die attachment material for electronic components. Thermal resistance measurements using a photoacoustic technique showed thermal resistances as low as 1.7 mm(2) K W(-1) for bonded VACNT films 25-30 µm in length and 10 mm(2) K W(-1) for CNTs up to 130 µm in length. Tensile testing demonstrated a die attachment strength of 40 N cm(-2) at room temperature. Overall, these metallized and bonded VACNT films demonstrate properties which are promising for next-generation thermal interface material applications.

Tunable Thermal Energy Transport across Diamond Membranes and Diamond-Si Interfaces by Nanoscale Graphoepitaxy.

The development of electronic devices, especially those that involve heterogeneous integration of materials, has led to increased challenges in addressing their thermal operational temperature demands. The heat flow in these systems is significantly influenced or even dominated by thermal boundary resistance at the interface between dissimilar materials. However, controlling and tuning heat transport across an interface and in the adjacent materials has so far drawn limited attention. In this work, we grow chemical vapor-deposited diamond on silicon substrates by graphoepitaxy and experimentally demonstrate tunable thermal transport across diamond membranes and diamond-silicon interfaces. We observed the highest diamond-silicon thermal boundary conductance (TBC) measured to date and increased diamond thermal conductivity due to strong grain texturing in the diamond near the interface. Additionally, nonequilibrium molecular dynamics simulations and a Landauer approach are used to understand the diamond-silicon TBC. These findings pave the way for tuning or increasing thermal conductance in heterogeneously integrated electronics that involve polycrystalline materials and will impact applications including electronics thermal management and diamond growth.

Sub-diffractional waveguiding by mid-infrared plasmonic resonators in semiconductor nanowires.

Chains of nanoscale plasmonic resonators are capable of sub-diffractional waveguiding and have applications in nanophotonics and thermal radiation transport. Practical uses have largely been limited, however, due to high optical losses or low group velocities. Here, we predict the waveguide performance of a material structure capable of overcoming these limitations: plasmonic resonators embedded in high-dielectric nanowires. Due to the enhanced near-field coupling between resonators, we find that the group velocities and propagation lengths for doped Si plasmonic resonators in intrinsic Si nanowires can be increased by up to an order of magnitude compared to the case of isotropic vacuum surroundings. We investigate the impact of resonator aspect ratio, doping, and spacing on waveguide performance, and we find that propagation lengths are maximized for large aspect ratios and high dopant concentrations at small spacings. To study these complex anisotropic systems, we develop a new analytical "absorption spectra" method to extract waveguide information from simple far-field absorption experiments (or simulations) of only two coupled resonators.

Probing Growth-Induced Anisotropic Thermal Transport in High-Quality CVD Diamond Membranes by Multifrequency and Multiple-Spot-Size Time-Domain Thermoreflectance.

The maximum output power of GaN-based high-electron mobility transistors is limited by high channel temperature induced by localized self-heating, which degrades device performance and reliability. Chemical vapor deposition (CVD) diamond is an attractive candidate to aid in the extraction of this heat and in minimizing the peak operating temperatures of high-power electronics. Owing to its inhomogeneous structure, the thermal conductivity of CVD diamond varies along the growth direction and can differ between the in-plane and out-of-plane directions, resulting in a complex three-dimensional (3D) distribution. Depending on the thickness of the diamond and size of the electronic device, this 3D distribution may impact the effectiveness of CVD diamond in device thermal management. In this work, time-domain thermoreflectance is used to measure the anisotropic thermal conductivity of an 11.8 µm-thick high-quality CVD diamond membrane from its nucleation side. Starting with a spot-size diameter larger than the thickness of the membrane, measurements are made at various modulation frequencies from 1.2 to 11.6 MHz to tune the heat penetration depth and sample the variation in thermal conductivity. We then analyze the data by creating a model with the membrane divided into ten sublayers and assume isotropic thermal conductivity in each sublayer. From this, we observe a two-dimensional gradient of the depth-dependent thermal conductivity for this membrane. The local thermal conductivity goes beyond 1000 W/(m K) when the distance from the nucleation interface only reaches 3 µm. Additionally, by measuring the same region with a smaller spot size at multiple frequencies, the in-plane and cross-plane thermal conductivities are extracted. Through this use of multiple spot sizes and modulation frequencies, the 3D anisotropic thermal conductivity of CVD diamond membrane is experimentally obtained by fitting the experimental data to a thermal model. This work provides an improved understanding of thermal conductivity inhomogeneity in high-quality CVD polycrystalline diamond that is important for applications in the thermal management of high-power electronics.

Carbon Nanotubes and Related Nanomaterials: Critical Advances and Challenges for Synthesis toward Mainstream Commercial Applications.

Advances in the synthesis and scalable manufacturing of single-walled carbon nanotubes (SWCNTs) remain critical to realizing many important commercial applications. Here we review recent breakthroughs in the synthesis of SWCNTs and highlight key ongoing research areas and challenges. A few key applications that capitalize on the properties of SWCNTs are also reviewed with respect to the recent synthesis breakthroughs and ways in which synthesis science can enable advances in these applications. While the primary focus of this review is on the science framework of SWCNT growth, we draw connections to mechanisms underlying the synthesis of other 1D and 2D materials such as boron nitride nanotubes and graphene.

High Power Density Electrochemical Thermocells for Inexpensively Harvesting Low-Grade Thermal Energy.

Continuously operating thermo-electrochemical cells (thermocells) are of interest for harvesting low-grade waste thermal energy because of their potentially low cost compared with conventional thermoelectrics. Pt-free thermocells devised here provide an output power of 12 W m-2 for an interelectrode temperature difference (ΔT) of 81 °C, which is sixfold higher power than previously reported for planar thermocells operating at ambient pressure.

High Thermal and Electrical Conductivity of Template Fabricated P3HT/MWCNT Composite Nanofibers.

Nanoporous alumina membranes are filled with multiwalled carbon nanotubes (MWCNTs) and then poly(3-hexylthiophene-2,5-diyl) (P3HT) melt, resulting in nanofibers with nanoconfinement induced coalignment of both MWCNT and polymer chains. The simple sonication process proposed here can achieve vertically aligned arrays of P3HT/MWCNT composite nanofibers with 3 wt % to 55 wt % MWCNT content, measured using thermogravimetric methods. Electrical and thermal transport in the composite nanofibers improves drastically with increasing carbon nanotube content where nanofiber thermal conductivity peaks at 4.7 ± 1.1 Wm(-1)K(-1) for 24 wt % MWCNT and electrical percolation occurs once 20 wt % MWCNT content is surpassed. This is the first report of the thermal conductivity of template fabricated composite nanofibers and the first proposed processing technique to enable template fabrication of composite nanofibers with high filler content and long aspect ratio fillers, where enhanced properties can also be realized on the macroscale due to vertical alignment of the nanofibers. These materials are interesting for thermal management applications due to their high thermal conductivity and temperature stability.

Thermal Conductance of Poly(3-methylthiophene) Brushes.

A wide variety of recent work has demonstrated that the thermal conductivity of polymers can be improved dramatically through the alignment of polymer chains in the direction of heat transfer. Most of the polymeric samples exhibit high conductivity in either the axial direction of a fiber or in the in-plane direction of a thin film, while the most useful direction for thermal management is often the cross-plane direction of a film. Here we show poly(3-methylthiophene) brushes grafted from phosphonic acid monolayers using surface initiated polymerization can exhibit through-plane thermal conductivity greater than 2 W/(m K), a 6-fold increase compared to spin-coated poly(3-hexylthiophene) samples. The thickness of these films (10-40 nm) is somewhat less than that required in most applications, but the method demonstrates a route toward higher thermal conductivity in covalently grafted, aligned polymer films.

A carbon nanotube optical rectenna.

An optical rectenna--a device that directly converts free-propagating electromagnetic waves at optical frequencies to direct current--was first proposed over 40 years ago, yet this concept has not been demonstrated experimentally due to fabrication challenges at the nanoscale. Realizing an optical rectenna requires that an antenna be coupled to a diode that operates on the order of 1 PHz (switching speed on the order of 1 fs). Diodes operating at these frequencies are feasible if their capacitance is on the order of a few attofarads, but they remain extremely difficult to fabricate and to reliably couple to a nanoscale antenna. Here we demonstrate an optical rectenna by engineering metal-insulator-metal tunnel diodes, with a junction capacitance of ∼2 aF, at the tip of vertically aligned multiwalled carbon nanotubes (∼10 nm in diameter), which act as the antenna. Upon irradiation with visible and infrared light, we measure a d.c. open-circuit voltage and a short-circuit current that appear to be due to a rectification process (we account for a very small but quantifiable contribution from thermal effects). In contrast to recent reports of photodetection based on hot electron decay in a plasmonic nanoscale antenna, a coherent optical antenna field appears to be rectified directly in our devices, consistent with rectenna theory. Finally, power rectification is observed under simulated solar illumination, and there is no detectable change in diode performance after numerous current-voltage scans between 5 and 77 °C, indicating a potential for robust operation.

Poly(3-hexylthiophene) nanotube array surfaces with tunable wetting and contact thermal energy transport.

Solution casting using a sacrificial template is a simple technique to fabricate vertical arrays of polymer nanotubes. However, because of their close proximity and high aspect ratios, large capillary forces cause nanotubes to cluster as the array dries; researchers often use special drying techniques to avoid this clustering. Here, we exploit the clustering of regioregular poly(3-hexylthiophene) (rr-P3HT) nanotubes in a unique template etching process to create surfaces that exhibit tunable wetting and contact thermal energy transport. Vertical arrays of rr-P3HT nanotubes are cast from solution in nanoscale alumina templates, and a solution etching process is used to partially release the nanotubes from the template. The clustering of rr-P3HT nanotube tips upon template etching produces hierarchical surface structuring with a distinct pattern of interconnected ridges, and the spacing between the ridges increases with increased template etch times. These changes in morphology cause the water contact angle to increase from 141° to 168° as the etch time is increased from 4 to 12 min. When assembled into an interface, the morphological changes cause the thermal contact resistance of the vertical rr-P3HT nanotube arrays to increase linearly at a rate of approximately 6 mm(2)·K/W per 2 min etch interval (after 6 min of etching is surpassed). The effective thermal conductivity of the rr-P3HT nanotube arrays is 1 ± 0.2 W/mK independent of the etch time, which is approximately 5 times higher than the bulk rr-P3HT film value.

High thermal conductivity of chain-oriented amorphous polythiophene.

Polymers are usually considered thermal insulators, because the amorphous arrangement of the molecular chains reduces the mean free path of heat-conducting phonons. The most common method to increase thermal conductivity is to draw polymeric fibres, which increases chain alignment and crystallinity, but creates a material that currently has limited thermal applications. Here we show that pure polythiophene nanofibres can have a thermal conductivity up to ∼ 4.4 W m(-1) K(-1) (more than 20 times higher than the bulk polymer value) while remaining amorphous. This enhancement results from significant molecular chain orientation along the fibre axis that is obtained during electropolymerization using nanoscale templates. Thermal conductivity data suggest that, unlike in drawn crystalline fibres, in our fibres the dominant phonon-scattering process at room temperature is still related to structural disorder. Using vertically aligned arrays of nanofibres, we demonstrate effective heat transfer at critical contacts in electronic devices operating under high-power conditions at 200 °C over numerous cycles.

Enhanced molecular order in polythiophene films electropolymerized in a mixed electrolyte of anionic surfactants and boron trifluoride diethyl etherate.

We synthesized polythiophene (PTh) films on stainless steel electrodes using chronoamperometry in boron trifluoride diethyl etherate (BFEE) electrolyte with anionic surfactants. The presence of the anionic surfactants in BFEE reduced the oxidation potential of thiophene and increased the oxidation current during electropolymerization. The measured in-plane electrical conductivity of PTh films synthesized in the presence of anionic surfactants was up to 300% higher than that of films synthesized under similar conditions without surfactants. The observed increase in conductivity reflects the improved order and packing of polymer chains revealed by X-ray diffraction.

Higher recovery and better energy dissipation at faster strain rates in carbon nanotube bundles: an in-situ study.

We report mechanical behavior and strain rate dependence of recoverability and energy dissipation in vertically aligned carbon nanotube (VACNT) bundles subjected to quasi-static uniaxial compression. We observe three distinct regimes in their stress-strain curves for all explored strain rates from 4 × 10(-2) down to 4 × 10(-4)/sec: (1) a short initial elastic section followed by (2) a sloped plateau with characteristic wavy features corresponding to buckle formation and (3) densification characterized by rapid stress increase. Load-unload cycles reveal a stiffer response and virtually 100% recoverability at faster strain rates of 0.04/sec, while the response is more compliant at slower rates, characterized by permanent localized buckling and significantly reduced recoverability. We propose that it is the kinetics of attractive adhesive interactions between the individual carbon nanotubes within the VACNT matrix that governs morphology evolution and ensuing recoverability. In addition, we report a 6-fold increase in elastic modulus and gradual decrease in recoverability (down to 50%) when VACNT bundles are unloaded from postdensification stage as compared with predensification. Finally, we demonstrate energy dissipation capability, as revealed by hysteresis in load-unload cycles. These findings, together with high thermal and electrical conductivities, position VACNTs in the "unattained-as-of-to-date-space" in the material property landscape.

Effects of morphology on the micro-compression response of carbon nanotube forests.

This study reports the mechanical response of distinct carbon nanotube (CNT) morphologies as revealed by flat punch in situ nanoindentation in a scanning electron microscope. We find that the location of incipient deformation varies significantly by changing the CNT growth parameters. The initial buckles formed close to the growth substrate in 70 and 190 µm tall CNT forests grown with low pressure chemical vapor deposition (LPCVD) and moved to ∼100 µm above the growth substrate when the height increased to 280 µm. Change of the recipe from LPCVD to CVD at pressures near atmospheric changed the location of the initial buckling event from the bottom half to the top half of the CNT forest. Plasma pretreatment of the catalyst also resulted in a unique CNT forest morphology in which deformation started by bending and buckling of the CNT tips. We find that the vertical gradients in CNT morphology dictate the location of incipient buckling. These new insights are critical in the design of CNT forests for a variety of applications where mechanical contact is important.