High efficiency graphene solar cells by chemical doping.

We demonstrate single layer graphene/n-Si Schottky junction solar cells that under AM1.5 illumination exhibit a power conversion efficiency (PCE) of 8.6%. This performance, achieved by doping the graphene with bis(trifluoromethanesulfonyl)amide, exceeds the native (undoped) device performance by a factor of 4.5 and is the highest PCE reported for graphene-based solar cells to date. Current-voltage, capacitance-voltage, and external quantum efficiency measurements show the enhancement to be due to the doping-induced shift in the graphene chemical potential that increases the graphene carrier density (decreasing the cell series resistance) and increases the cell's built-in potential (increasing the open circuit voltage) both of which improve the solar cell fill factor.

Electrolyte-induced inversion layer Schottky junction solar cells.

A new type of crystalline silicon solar cell is described. Superficially similar to a photoelectrochemical cell a liquid electrolyte creates a depletion (inversion) layer in an n-type silicon wafer, however no regenerative redox couple is present to ferry charge between the silicon and a counter electrode. Instead holes trapped in the electrolyte-induced inversion layer diffuse along the layer until they come to widely spaced grid lines, where they are extracted. The grid lines consist of a single-walled carbon nanotube film etched to cover only a fraction of the n-Si surface. Modeling and simulation shows the inversion layer to be a natural consequence of the device electrostatics. With electronic gating, recently demonstrated to boost the efficiency in related devices, the cell achieves a power conversion efficiency of 12%, exceeding the efficiency of dye sensitized solar cells.

High current, low voltage carbon nanotube enabled vertical organic field effect transistors.

State-of-the-art performance is demonstrated from a carbon nanotube enabled vertical field effect transistor using an organic channel material. The device exhibits an on/off current ratio >10(5) for a gate voltage range of 4 V with a current density output exceeding 50 mA/cm(2). The architecture enables submicrometer channel lengths while avoiding high-resolution patterning. The ability to drive high currents and inexpensive fabrication may provide the solution for the so-called OLED backplane problem.

Electronic junction control in a nanotube-semiconductor Schottky junction solar cell.

We exploit the low density of electronic states in single wall carbon nanotubes to demonstrate active, electronic modulation of their Fermi level offset relative to n-type silicon in a nanotube-Si (metal-semiconductor) Schottky junction solar cell. Electronic modulation of the Fermi level offset, the junction interface dipole and a field developed across the depletion layer modifies the built-in potential in the device and its power generation characteristics. As produced (before modulation) devices exhibit ∼8.5% power conversion efficiency (PCE). With active modulation the PCE is continuously and reversibly changed from 4 to 11%.

A spray-processable, low bandgap, and ambipolar donor-acceptor conjugated polymer.

Combining a strong donor, tris(dodecyloxy)phenyl)-dithieno[3,2-b:2',3'-d]pyrrole, with a strong acceptor, 4,8-dithien-2-yl-2lambda(4)delta(2)-benzo[1,2-c;4,5-c']bis[1,2,5]thiadiazole, has yielded the lowest bandgap, soluble, spray-processable polymer to date. The polymer has access to four different redox states and shows ambipolar behavior in OFETs. Multiple techniques, including transmission/absorption spectroscopy on SWCNTs and reflectance spectroscopy on gold were used to accurately estimate the optical bandgap at 0.5-0.6 eV, which correlates well to theoretical calculations.

Low band gap EDOT-benzobis(thiadiazole) hybrid polymer characterized on near-IR transmissive single walled carbon nanotube electrodes.

An electron donor/acceptor pi-conjugated polymer composed of a bi-EDOT and benzobis(thiadiazole) repeat unit exhibits two reductions with a band gap ranging from approximately 0.5 to 0.8 eV depending on the method of band gap determination.

On Field-Effect Photovoltaics: Gate Enhancement of the Power Conversion Efficiency in a Nanotube/Silicon-Nanowire Solar Cell.

Recent years have seen a resurgence of interest in crystalline silicon Schottky junction solar cells distinguished by the use of low density of electronic states (DOS) nanocarbons (nanotubes, graphene) as the metal contacting the Si. Recently, unprecedented modulation of the power conversion efficiency in a single material system has been demonstrated in such cells by the use of electronic gating. The gate field induced Fermi level shift in the low-DOS carbon serves to enhance the junction built-in potential, while a gate field induced inversion layer at the Si surface, in regions remote from the junction, keeps the photocarriers well separated there, avoiding recombination at surface traps and defects (a key loss mechanism). Here, we extend these results into the third dimension of a vertical Si nanowire array solar cell. A single wall carbon nanotube layer engineered to contact virtually each n-Si nanowire tip extracts the minority carriers, while an ionic liquid electrolytic gate drives the nanowire body into inversion. The enhanced light absorption of the vertical forest cell, at 100 mW/cm(2) AM1.5G illumination, results in a short-circuit current density of 35 mA/cm(2) and associated power conversion efficiency of 15%. These results highlight the use of local fields as opposed to surface passivation as a means of avoiding front surface recombination. A deleterious electrochemical reaction of the silicon due to the electrolyte gating is shown to be caused by oxygen/water entrained in the ionic liquid electrolyte. While encapsulation can avoid the issue, a nonencapsulation-based approach is also implemented.

Extraordinary hydrogen evolution and oxidation reaction activity from carbon nanotubes and graphitic carbons.

The hydrogen evolution reaction, 2H(+) + 2e(­) → H2, and its converse, the hydrogen oxidation reaction, H2 → 2H(+) + 2e(­), are central to any realization of a hydrogen economy. Various forms of carbon have been used for decades as the precious metal catalyst support in these reactions. Here we report the unexpected result that single-wall carbon nanotubes and some graphitic carbons, activated by brief exposure to electrochemical potentials that induce hydrogen evolution in intercalating acids combined with extended soak times in such acids, acquire an activity for these reactions that exceeds that of known nonprecious metal catalysts.

Improved transfer of graphene for gated Schottky-junction, vertical, organic, field-effect transistors.

An improved process for graphene transfer was used to demonstrate high performance graphene enabled vertical organic field effect transistors (G-VFETs). The process reduces disorder and eliminates the polymeric residue that typically plagues transferred films. The method also allows for purposely creating pores in the graphene of a controlled areal density. Transconductance observed in G-VFETs fabricated with a continuous (pore-free) graphene source electrode is attributed to modulation of the contact barrier height between the graphene and organic semiconductor due to a gate field induced Fermi level shift in the low density of electronic-states graphene electrode. Pores introduced in the graphene source electrode are shown to boost the G-VFET performance, which scales with the areal pore density taking advantage of both barrier height lowering and tunnel barrier thinning. Devices with areal pore densities of 20% exhibit on/off ratios and output current densities exceeding 10(6) and 200 mA/cm(2), respectively, at drain voltages below 5 V.

All the dope on nanotube films.

Transparent, conducting, nanotube thin films have shown promise in a number of applications, the range of which has just been increased significantly. Scientists at the National Renewable Energy Laboratory have done much in recent years to advance the understanding and application of these films. In this issue of ACS Nano, Blackburn and colleagues report their study of the doping power of n-type charge transfer donor dopants, finding that hydrazine effects n-type doping approximately comparable in strength to the p-type doping induced by nitric acid. This expands the potential range of applications for such films to electron injection and collection.

Reorientation of the high mobility plane in pentacene-based carbon nanotube enabled vertical field effect transistors.

The large current densities attained by carbon nanotube enabled vertical field effect transistors using crystalline organic channel materials are somewhat unexpected given the known large anisotropy in the mobility of crystalline organics and their conventional ordering on dielectric surfaces which tends to orient their high mobility axes parallel to the surface. This seeming contradiction is resolved by the finding that the nanotubes induce a molecular ordering that reorients the high mobility axes to favor current flow in a direction perpendicular to the substrate surface.

Engineered macroporosity in single-wall carbon nanotube films.

A key advantage of bulk nanoscale materials in applications ranging from energy storage to chemical catalysis is their inherent high surface area. Single-wall carbon nanotube films possess the additional advantages of high electrical conductivity and robust mechanical integrity. Nevertheless the flexibility of the individual nanotubes and their affinity for each other conspire to obstruct the porosity in such films limiting the perfusion rate of liquids and gases, restricting the accessible surface area and thereby limiting their utility in important applications. Here we demonstrate a simple, effective means to engineer controlled porosity into the nanotube films. The newly incorporated porosity modifies the film electrolytic capacitance and comparative perfusion rates. Pseudocapacitive RuO(2) electrodeposited onto the highest porosity films exhibits a specific capacitance of 1084 F/g. Knowledge of the underlying nanotube capacitance and mass permits extraction of the deposited RuO(2) specific capacitance of 1715 F/g, which closely approaches the predicted theoretical maximum RuO(2) capacitance of 2000 F/g.

Color purity in polymer electrochromic window devices on indium-tin oxide and single-walled carbon nanotube electrodes.

Dual polymer absorptive/transmissive electrochromic (EC) window devices have been assembled using the solution-processable and high-EC-contrast polymer PProDOT-(CH(2)OEtHx)(2) as the EC material, along with a non-color-changing electroactive polymer, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), as the counter electrode material. Indium-tin oxide (ITO) and highly transmissive single-walled carbon nanotube (SWNT) film coated glass electrodes are used as electrode substrates. The use of the EC/non-color-changing polymer combination allowed us to construct window devices that rapidly switch between magenta and highly transmissive (>95% T for ITO and approximately 79% T for SWNT) states with large optical modulation (>71% DeltaT for ITO and 66% DeltaT for SWNT). The devices showed effective coloration and bleaching: the lightness parameter (L*) changing from 67 to 95 for ITO (approximately 50-92 for SWNT), essentially reaching a diffuse white upon oxidation. The color modulates from highly pure magenta with a* = 28 (red hue) and b* = -28 (blue chroma) for ITO (a* = 40 and b* = -36 for SWNT) to nearly colorless with a* = 1 and b* = -1 for ITO (a* = -2 and b* = -3 for SWNT) devices. Increasing the switching voltage from 2.55 V up to 3.5 V resulted in faster SWNT-based window device performance.

An integrated logic circuit assembled on a single carbon nanotube.

Single-walled carbon nanotubes (SWCNTs) have been shown to exhibit excellent electrical properties, such as ballistic transport over several hundred nanometers at room temperature. Field-effect transistors (FETs) made from individual tubes show dc performance specifications rivaling those of state-of-the-art silicon devices. An important next step is the fabrication of integrated circuits on SWCNTs to study the high-frequency ac capabilities of SWCNTs. We built a five-stage ring oscillator that comprises, in total, 12 FETs side by side along the length of an individual carbon nanotube. A complementary metal-oxide semiconductor-type architecture was achieved by adjusting the gate work functions of the individual p-type and n-type FETs used.

Carbon nanotube films for room temperature hydrogen sensing.

Thin, uniform, single-walled carbon nanotube films, made by a simple filtration process, subsequently coated with palladium, are shown to be promising detectors of hydrogen. The films detected hydrogen with relative responses of 20% at 100 ppm and 40% at 500 ppm concentrations. Most of the initial film conductance was recovered within 30 s by exposing the samples to air. This quick and easy recoverability make the Pd-coated nanotubes suitable for practical applications in room temperature hydrogen sensing while consuming only approximately 0.25 mW power. The film fabrication process provides highly reproducible control over the film thickness; an important ingredient for commercial production. In the course of this research strong evidence was obtained indicating that sputter deposition of metal onto the nanotubes, even under very low power, short exposure time conditions, does damage to the nanotubes.

Transparent, conductive carbon nanotube films.

We describe a simple process for the fabrication of ultrathin, transparent, optically homogeneous, electrically conducting films of pure single-walled carbon nanotubes and the transfer of those films to various substrates. For equivalent sheet resistance, the films exhibit optical transmittance comparable to that of commercial indium tin oxide in the visible spectrum, but far superior transmittance in the technologically relevant 2- to 5-micrometer infrared spectral band. These characteristics indicate broad applicability of the films for electrical coupling in photonic devices. In an example application, the films are used to construct an electric field-activated optical modulator, which constitutes an optical analog to the nanotube-based field effect transistor.