Jao van de Lagemaat

Plasmon-enhanced solar energy conversion in organic bulk heterojunction photovoltaics

Plasmon-active silver nanoparticle layers were included in solution-processed bulk-heterojunction solar cells. Nanoparticle layers were fabricated using vapor-phase deposition on indium tin oxide electrodes. Owing to the increase in optical electrical field inside the photoactive layer, the inclusion of such particle films lead to increased optical absorption and consequently increased photoconversion at solar-conversion relevant wavelengths. The resulting solar energy conversion efficiency for a bulk heterojunction photovoltaic device of poly(3-hexylthiophene)/[6,6]-phenyl C61 butyric acid methyl ester was found to increase from 1.3%±0.2% to 2.2%±0.1% for devices employing thin plasmon-active layers. Based on six measurements, the improvement factor of 1.7 was demonstrated to be statistically significant.

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.

Surface-plasmon enhanced transparent electrodes in organic photovoltaics

Random silver nanohole films were created through colloidal lithography techniques and metal vapor deposition. The transparent electrodes were characterized by uv-visible spectroscopy and incorporated into an organic solar cell. The test cells were evaluated for solar power-conversion efficiency and incident photon-to-current conversion efficiency. The incident photon-to-current conversion efficiency spectra displayed evidence that a nanohole film with 92nm diameter holes induces surface-plasmon-enhanced photoconversion. The nanohole silver films demonstrate a promising route to removing the indium tin oxide transparent electrode that is ubiquitous in organic optoelectronics.

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.

Bulk heterojunction organic photovoltaic devices based on phenyl-cored thiophene dendrimers

Bulk heterojunction organic photovoltaic devices have been fabricated by blending phenyl-cored thiophene dendrimers with a fullerene derivative. A power conversion efficiency of 1.3% under simulated AM1.5 illumination is obtained for a four-arm dendrimer, despite its large optical band gap of 2.1eV. The devices exhibit an increase in short-circuit current and power conversion efficiency as the length of the arm is increased. The fill factors of the devices studied are characteristically low, which is attributed to overly uniform mixing of the blend.

Carrier separation and transport in perovskite solar cells studied by nanometre-scale profiling of electrical potential

Organometal–halide perovskite solar cells have greatly improved in just a few years to a power conversion efficiency exceeding 20%. This technology shows unprecedented promise for terawatt-scale deployment of solar energy because of its low-cost, solution-based processing and earth-abundant materials. We have studied charge separation and transport in perovskite solar cells—which are the fundamental mechanisms of device operation and critical factors for power output—by determining the junction structure across the device using the nanoelectrical characterization technique of Kelvin probe force microscopy. The distribution of electrical potential across both planar and porous devices demonstrates p–n junction structure at the TiO2/perovskite interfaces and minority-carrier diffusion/drift operation of the devices, rather than the operation mechanism of either an excitonic cell or a p-i-n structure. Combining the potential profiling results with solar cell performance parameters measured on optimized and thickened devices, we find that carrier mobility is a main factor that needs to be improved for further gains in efficiency of the perovskite solar cells.

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.

Shape-dependent oriented trapping and scaffolding of plasmonic nanoparticles by topological defects for self-assembly of colloidal dimers in liquid crystals.

We demonstrate scaffolding of plasmonic nanoparticles by topological defects induced by colloidal microspheres to match their surface boundary conditions with a uniform far-field alignment in a liquid crystal host. Displacing energetically costly liquid crystal regions of reduced order, anisotropic nanoparticles with concave or convex shapes not only stably localize in defects but also self-orient with respect to the microsphere surface. Using laser tweezers, we manipulate the ensuing nanoparticle-microsphere colloidal dimers, probing the strength of elastic binding and demonstrating self-assembly of hierarchical colloidal superstructures such as chains and arrays.

Revisiting the Valence and Conduction Band Size Dependence of PbS Quantum Dot Thin Films

We use a high signal-to-noise X-ray photoelectron spectrum of bulk PbS, GW calculations, and a model assuming parabolic bands to unravel the various X-ray and ultraviolet photoelectron spectral features of bulk PbS as well as determine how to best analyze the valence band region of PbS quantum dot (QD) films. X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) are commonly used to probe the difference between the Fermi level and valence band maximum (VBM) for crystalline and thin-film semiconductors. However, we find that when the standard XPS/UPS analysis is used for PbS, the results are often unrealistic due to the low density of states at the VBM. Instead, a parabolic band model is used to determine the VBM for the PbS QD films, which is based on the bulk PbS experimental spectrum and bulk GW calculations. Our analysis highlights the breakdown of the Brillioun zone representation of the band diagram for large band gap, highly quantum confined PbS QDs. We have also determined that in 1,2-ethanedithiol-treated PbS QD films the Fermi level position is dependent on the QD size; specifically, the smallest band gap QD films have the Fermi level near the conduction band minimum and the Fermi level moves away from the conduction band for larger band gap PbS QD films. This change in the Fermi level within the QD band gap could be due to changes in the Pb:S ratio. In addition, we use inverse photoelectron spectroscopy to measure the conduction band region, which has similar challenges in the analysis of PbS QD films due to a low density of states near the conduction band minimum.

Controlling the Optical Properties of Plasmonic Disordered Nanohole Silver Films

Disordered nanohole arrays were formed in silver films by colloidal lithography techniques and characterized for their surface-plasmon activity. Careful control of the reagent concentration, deposition solution ionic strength, and assembly time allowed generation of a wide variety of nanohole densities. The fractional coverage of the nanospheres across the surface was varied from 0.05-0.36. Electrical sheet resistance measurements as a function of nanohole coverage fit well to percolation theory indicating that the electrical behavior of the films is determined by bulk silver characteristics. The transmission and reflection spectra were measured as a function of coverage and the results indicate that the optical behavior of the films is dominated by surface plasmon phenomena. Angle-resolved transmission and reflection spectra were measured, yielding insight into the nature of the excitations taking place on the metal films. The tunability of the colloidal lithography assembly method holds much promise as a means to generate customized transparent electrodes with high surface plasmon activity throughout the visible and NIR spectrum over large surface areas.