Timothy J. Coutts

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.

Search for improved transparent conducting oxides: A fundamental investigation of CdO, Cd2SnO4, and Zn2SnO4

The bulk of developmental work on transparent conducting oxides (TCOs) has been somewhat empirical. This statement applies both to more familiar materials such as indium tin oxide (ITO) and to less-well-known materials that have emerged in recent years. In this article, we place a greater emphasis on more fundamental research. Our eventual goal is to gain a thorough understanding of these materials, their potential for further improvement, whether or not they suggest new and potentially superior materials, and the way their properties are influenced by structural and other issues. We also hope to provide guidelines to other researchers working in this area. We have investigated films of cadmium oxide (CdO), cadmium stannate (Cd2SnO4 or CTO), and zinc stannate [Zn2SnO4 (ZTO)]. The CdO was prepared by chemical-vapor deposition, whereas the stannates were prepared by rf sputtering. In both cases, Corning 7059 glass substrates were used. However, some depositions were also made onto tin oxide, which had a pro...

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.

Identification of nitrogen chemical states in N-doped ZnO via x-ray photoelectron spectroscopy

Nitrogen-doped films of ZnO grown by two methods, metalorganic chemical vapor deposition (MOCVD) and reactive sputtering, were studied with x-ray and ultraviolet photoelectron spectroscopy (XPS and UPS). Systematic differences in the N chemical states were observed between films grown by sputtering and MOCVD: only two N chemical states were observed in films grown by reactive sputtering, whereas four N chemical states were observed in MOCVD films. To aid in the assignment of the N chemical states, photoemission data from the polycrystalline films were compared with data taken on N2+-implanted Zn metal and N2+-implanted ZnO. High-resolution core level spectra of the N1s region indicated that nitrogen can occupy at least four different chemical environments in ZnO; these include the NO acceptor, the double donor (N2)O, and two carbon–nitrogen species. Valence band spectra indicate that the Fermi energy of all films studied was near the conduction band minimum, implying that the films remained n-type after n...

Properties of transparent conducting oxides formed from CdO and ZnO alloyed with SnO2 and In2O3

In this article we examine the structural, electrical, and optical properties of several ternary alloy thin films. The alloys are zinc oxide and cadmium oxide, each of which was reacted with both indium oxide and tin oxide to form sputtering targets. The films were deposited by rf sputtering. X-ray diffraction spectroscopy showed that cadmium stannate, cadmium indate, and zinc stannate films were all polycrystalline spinel phase, but only when deposited at room temperature in pure oxygen and then annealed in argon/cadmium sulfide. The fourth alloy, zinc indate, exhibited a hexagonal phase when prepared under identical conditions. Cadmium stannate has one of the lowest resistivities of any transparent conducting oxide (TCO), has low absorbance in the visible spectrum, and is an excellent compromise between electrical and optical requirements. For this material, we show that a single phase is essential for the highest electrical conductivity and lowest optical absorbance. Zinc stannate has a resistivity mor...

Growth and characterization of radio frequency magnetron sputter-deposited zinc stannate, Zn2SnO4, thin films

Single-phase, spinel zinc stannate (Zn2SnO4) thin films were grown by rf magnetron sputtering onto glass substrates. Uniaxially oriented films with resistivities of 10−2–10−3 Ω cm, mobilities of 16–26 cm2/V s, and n-type carrier concentrations in the low 1019 cm−3 range were achieved. X-ray diffraction peak intensity studies established the films to be in the inverse spinel configuration. 119Sn Mossbauer studies identified two octahedral Sn sites, each with a unique quadrupole splitting, but with a common isomer shift consistent with Sn+4. A pronounced Burstein–Moss shift moved the optical band gap from 3.35 to as high as 3.89 eV. Density-of-states effective mass, relaxation time, mobility, Fermi energy level, and a scattering parameter were calculated from resistivity, Hall, Seebeck, and Nernst coefficient transport data. Effective-mass values increased with carrier concentration from 0.16 to 0.26 me as the Fermi energy increased from 0.2 to 0.9 eV above the conduction-band minimum. A bottom-of-the-band ...

High‐efficiency indium tin oxide/indium phosphide solar cells

Solar cells have been fabricated by rf sputter depositing indium tin oxide onto single crystal p‐type indium phosphide. Four different substrate doping densities have been used but in all cases the dopant was zinc and the wafers were 〈100〉 oriented. The optimum doping density from the range studied was 3×1016 cm−3 and devices based on such substrates have yielded total area efficiencies up to 16.2% using the air mass 1.5 spectrum normalized to 100 mW cm−2, which correspond to active area efficiencies of 19.1%. A doping density less than the optimum yielded devices with excessive series resistance. Higher doping densities led to a marked loss of red response.

Hydrogen passivation effect in nitrogen-doped ZnO thin films

The role of hydrogen in nitrogen-doped ZnO thin films was studied by Fourier transform infrared (FTIR) absorption and modeled by first-principles calculations to understand the difficulty of doping ZnO p-type with nitrogen. Nitrogen-doped ZnO films were fabricated by low-pressure metal-organic chemical vapor deposition (MOCVD). High levels of nitrogen incorporation were observed, but the acceptor concentrations remained low. Theoretical analysis suggests there is a high probability that NO− and H+ charged defects combine to form the neutral defect complexes, thereby compensating the nitrogen-related acceptors. Calculated values of the vibrational frequencies of the related infrared modes agree well with the measured spectra. Thus, we believe the difficulty of achieving p-type doping in MOCVD-grown ZnO films is due, at least partially, to inadvertent passivation by hydrogen.

Chemical vapor deposition-formed p-type ZnO thin films

We have fabricated nitrogen-doped zinc oxide (ZnO) films that demonstrate p-type behavior by using metalorganic chemical vapor deposition. In our experiment, diethylzinc is used as a Zn precursor, and NO gas is used to supply both O and N to form a N-doped ZnO (ZnO:N) film. With these precursors, we have routinely reached an N concentration in the ZnO films of about 1–3 at. %. When the N concentration level is higher than 2 at. %, the films demonstrate p-type characteristics. The carrier concentration of the films varies from 1.0×1015 to 1.0×1018 cm−3, and mobilities are mainly in the 10−1 cm2 V−1 s−1 range. The lowest film resistivity achieved is ∼20 Ω cm.

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.