Teresa M. Barnes

Organic solar cells with carbon nanotubes replacing In2O3:Sn as the transparent electrode

We report two viable organic excitonic solar cell structures where the conventional In2O3:Sn (ITO) hole-collecting electrode was replaced by a thin single-walled carbon nanotube layer. The first structure includes poly(3,4-ethylenedioxythiophene) (PEDOT) and gave a nonoptimized device efficiency of 1.5%. The second did not use PEDOT as a hole selective contact and had an efficiency of 0.47%. The strong rectifying behavior of the device shows that nanotubes are selective for holes and are not efficient recombination sites. The reported excitonic solar cell, produced without ITO and PEDOT, is an important step towards a fully printable solar cell.

Transparent Conductive Single-Walled Carbon Nanotube Networks with Precisely Tunable Ratios of Semiconducting and Metallic Nanotubes

We present a comprehensive study of the optical and electrical properties of transparent conductive films made from precisely tuned ratios of metallic and semiconducting single-wall carbon nanotubes. The conductivity and transparency of the SWNT films are controlled by an interplay between localized and delocalized carriers, as determined by the SWNT electronic structure, tube-tube junctions, and intentional and unintentional redox dopants. The results suggest that the main resistance in the SWNT thin films is the resistance associated with tube-tube junctions. Redox dopants are found to increase the delocalized carrier density and transmission probability through intertube junctions more effectively for semiconductor-enriched films than for metal-enriched films. As a result, redox-doped semiconductor-enriched films are more conductive than either intrinsic or redox-doped metal-enriched films.

On the formation and stability of p-type conductivity in nitrogen-doped zinc oxide

The behavior of nitrogen in ZnO thin films grown by high-vacuum plasma-assisted chemical vapor deposition is examined. Highly oriented (002) films doped with 0–2at.% N were characterized by x-ray photoelectron spectroscopy, x-ray diffraction (XRD), Seebeck, and Hall measurements. XRD measurements revealed that the zinc oxide lattice constant decreased systematically with nitrogen doping. The as-deposited films were p-type at high doping levels, as confirmed by both Seebeck and Hall measurements. However, it was observed that hole conduction decreased and films reverted to n-type conductivity in a period of several days. This change was accompanied by a simultaneous increase in the lattice constant. The transient electrical behavior may be explained by compensation caused either by hydrogen donors or through defect formation processes common to analogous II-VI semiconductors.

Carbon nanotube network electrodes enabling efficient organic solar cells without a hole transport layer

We report on the effects of replacing both In2O3:Sn (ITO) and the hole transport layer (HTL) in organic photovoltaic (OPV) cells with single-walled carbon nanotube (SWNT) network transparent electrodes. We have produced an OPV device without an HTL exhibiting an NREL-certified efficiency of 2.65% and a short-circuit current density of 11.2 mA/cm2. Our results demonstrate that SWNT networks can be used to replace both ITO and the HTL in efficient OPV devices and that the HTL serves distinctly different roles in ITO- and SWNT-based devices.

Reversibility, Dopant Desorption, and Tunneling in the Temperature-Dependent Conductivity of Type-Separated, Conductive Carbon Nanotube Networks

We present a comprehensive study of the effects of doping and temperature on the conductivity of single-walled carbon nanotube (SWNT) networks. We investigated nearly type-pure networks as well as networks comprising precisely tuned mixtures of metallic and semiconducting tubes. Networks were studied in their as-produced state and after treatments with nitric acid, thionyl chloride, and hydrazine to explore the effects of both intentional and adventitious doping. For intentionally and adventitiously doped networks, the sheet resistance (R(s)) exhibits an irreversible increase with temperature above approximately 350 K. Dopant desorption is shown to be the main cause of this increase and the observed hysteresis in the temperature-dependent resistivity. Both thermal and chemical dedoping produced networks free of hysteresis. Temperature-programmed desorption data showed that dopants are most strongly bound to the metallic tubes and that networks consisting of metallic tubes exhibit the best thermal stability. At temperatures below the dopant desorption threshold, conductivity in the networks is primarily controlled by thermally assisted tunneling through barriers at the intertube or interbundle junctions.

A comparison of plasma-activated N2∕O2 and N2O∕O2 mixtures for use in ZnO:N synthesis by chemical vapor deposition

A high-vacuum plasma-assisted chemical-vapor deposition system was used to systematically study ZnO:N thin film synthesis. Nitrogen doping was achieved by mixing either N2O or N2 with O2 in a high-density inductively coupled plasma (ICP) source. In situ diagnostics showed that the ICP composition was predominantly a function of the elemental oxygen to nitrogen ratio, and relatively insensitive to the choice of N2 or N2O as the molecular precursor. Nitrogen incorporation was measured by both x-ray photoelectron spectroscopy and secondary ion mass spectrometry and was found to increase monotonically with both N2O and N2 addition. Nitrogen doping was correlated with systematic shifts in the lattice spacing, electrical conductivity, and optical absorption. Quantitative comparisons between film properties and gas composition suggest that atomic nitrogen is the primary precursor for doping in this system.

Single-wall carbon nanotube networks as a transparent back contact in CdTe solar cells

Single-wall carbon nanotube (SWCNT) networks form a highly transparent and electrically conductive thin film that can be used to replace traditional transparent conducting oxides (TCOs) in a variety of applications. Here, the authors demonstrate their use as a transparent back contact in a near-infrared (NIR) transparent CdTe solar cell. SWCNT networks are hole-selective conductors and have a significantly greater NIR transparency than TCOs—qualities which could both make them very useful in tandem thin-film solar cells. SWCNT networks can be incorporated into single-junction CdTe devices and in CdTe top cells for mechanically stacked thin-film tandem devices, as described here. The best device efficiency using SWCNTs in the back contact was 12.4%, with 40%–50% transmission between 800 and 1500nm.

n-Type transparent conducting films of small molecule and polymer amine doped single-walled carbon nanotubes.

In this report, we investigate the electrical and optical properties of thin conducting films of SWNTs after treatment with small molecule and polymeric amines. Among those tested, we find hydrazine to be the most effective n-type dopant. We use absorbance, Raman, X-ray photoelectron, and nuclear magnetic resonance spectroscopies on thin conducting films and opaque buckypapers treated with hydrazine to study fundamental properties and spectroscopic signatures of n-type SWNTs and compare them to SWNTs treated with nitric acid, a well-characterized p-type dopant. We find that hydrazine physisorbs to the surface of semiconducting and metallic SWNTs and injects large electron concentrations, raising the Fermi level as much as 0.7 eV above that of intrinsic SWNTs. Hydrazine-treated transparent SWNT films display sheet resistances nearly as low as p-type nitric-acid-treated films at similar optical transmittances, demonstrating their potential for use in photovoltaic devices as low work function transparent electron-collecting electrodes.

Infrared detection of hydrogen-generated free carriers in polycrystalline ZnO thin films

The changes in the free-carrier concentration in polycrystalline ZnO films during exposure to H2 and O2 plasmas were studied using in situ attenuated total reflection Fourier transform infrared spectroscopy. The carrier concentration and mobility were extracted from the free-carrier absorption in the infrared using a model for the dielectric function. The electron density in polycrystalline zinc oxide films may be significantly increased by >1019cm−3 by brief exposures to hydrogen plasma at room temperature and decreased by exposure to O2 plasmas. Room-temperature oxygen plasma removes a fraction of the H at donor sites but both elevated temperatures (∼225°C) and O2 plasma were required to remove the rest. We demonstrate that combinations of O2 and H2 plasma treatments can be used to manipulate the carrier density in ZnO films. However, we also show the existence of significant drifts (∼15%) in the carrier concentrations over very long time scales (hours). Possible sites for H incorporation in polycrystal...

14%-efficient flexible CdTe solar cells on ultra-thin glass substrates

Flexible glass enables high-temperature, roll-to-roll processing of superstrate devices with higher photocurrents than flexible polymer foils because of its higher optical transmission. Using flexible glass in our high-temperature CdTe process, we achieved a certified record conversion efficiency of 14.05% for a flexible CdTe solar cell. Little has been reported on the flexibility of CdTe devices, so we investigated the effects of three different static bending conditions on device performance. We observed a consistent trend of increased short-circuit current and fill factor, whereas the open-circuit voltage consistently dropped. The quantum efficiency under the same static bend condition showed no change in the response. After storage in a flexed state for 24 h, there was very little change in device efficiency relative to its unflexed state. This indicates that flexible glass is a suitable replacement for rigid glass substrates, and that CdTe solar cells can tolerate bending without a decrease in device performance.