Transparent conducting (TC) films of single-walled carbon nanotubes (SWNTs) have the potential to replace conventional TC oxides in a wide variety of optoelectronic devices. [1][2][3][4][5] TC-SWNT films are particularly attractive for photovoltaics (PV) due to their high transparency over much of the solar spectrum, excellent electrical conductivity, and the potential for inexpensive roll-to-roll processing. SWNT films have been used, by us and others, in cadmium telluride, [6] copper indium gallium diselenide, [7] and organic PV (OPV) devices. [8][9][10] In several reports, SWNTelectrodes for OPV have been prepared by filtering a sodium dodecyl sulfate (SDS)-stabilized dispersion of SWNTs to form a thin film. [9,10] The film can be released by dissolution of the filter, and then transferred to a transparent substrate.[11] This so-called ''transfer method'' produces highly transparent films with excellent conductivity, but the films possess irregular morphologies and significant roughness, which can lead to short-circuits and overall poor reproducibility during device fabrication.[12] Moreover, the process is not scalable. TC-SWNT films have also been produced for optical and electrical studies by air-brush spraying using surfactant-stabilized SWNT inks. Such films are inhomogeneous because SWNTs sprayed from surfactant solutions agglomerate on heated substrates. To move TC-SWNT electrodes beyond the proof-of-concept stage for PV and other optoelectronic applications, methods are required for producing large-area, transparent, conducting SWNT films that are smooth and homogeneous over large areas.Here, we report methods to prepare SWNT films with high transparency, electrical conductivity, and uniformity, with exceptionally low surface roughness, on arbitrarily large (6 inch  6 inch) substrates by ultrasonic spraying. A side-by-side comparison of OPV devices fabricated on SWNT and indiumdoped tin oxide (ITO) electrodes showed very good performance with energy-conversion efficiencies of $3.1 and 3.6%, respectively, under AM 1.5 illumination. Several factors are critical to the success of the approach. First, we prepared aqueous SWNT dispersions using a high-molecular-weight (MW $90 000) polymeric derivative of cellulose (sodium carboxymethyl cellulose (CMC)). CMC has been previously reported as an excellent agent for dispersing SWNTs in water, [13] and transparent films have been drop-cast, [14] but this is the first report of CMC-based dispersions for spraying SWNT films. A second advance is the use of ultrasonic spraying, which, when combined with the CMC-based dispersions, permits precise amounts of SWNTs to be reproducibly and uniformly dispensed over arbitrarily large areas. In fact, by measuring the weight and optical properties of films as a function of the number of deposited layers, the SWNT absorption coefficient could be accurately determined. Finally, we used SWNTs produced by laser vaporization (LV), which have lower defect densities [15,16] than tubes produced by chemical vapor deposition (CVD). Th...
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.
Networks made of single-walled carbon nanotubes (SWNTs) and metallic nanowire networks, graphene, and ultra-thin metal films have all been proposed as replacements for transparent conducting oxides (TCOs) in photovoltaic and other applications. However, only limited comparisons of nanostructured networks and TCOs are available. Several common figures of merit that are often used to compare the electrical and optical performance of the transparent contacts are evaluated here, and the merits of each method of comparison are discussed. Calculating the current loss due to absorption in the TCO is the most useful metric for evaluating new materials for use in solar cells with well-defined sheet resistance requirements and known quantum efficiencies. The 'Haacke' figure of merit, Φ H , correlates fairly well with current loss and is a good metric for evaluating electro-optical performance for more general applications. The analyses presented here demonstrate that silver nanowire networks are much closer to achieving optimal electrical and optical properties than carbon-based networks.
We report that organic semiconductors such as -sexithiophene (-6T) have magnetoresistance (MR) with unexpected sign changes; depending on applied voltage, temperature, and layer thickness, the resistance may either increase or decrease upon application of a small magnetic field (<100 mT). We propose that MR and the inversion of MR are due to the role of hyperfine interaction in a magnetic field, as illustrated by the recombination-limited regime.
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