Brian J. Worfolk

Indium tin oxide nanopillar electrodes in polymer/fullerene solar cells

Using high surface area nanostructured electrodes in organic photovoltaic (OPV) devices is a route to enhanced power conversion efficiency. In this paper, indium tin oxide (ITO) and hybrid ITO/SiO(2) nanopillars are employed as three-dimensional high surface area transparent electrodes in OPVs. The nanopillar arrays are fabricated via glancing angle deposition (GLAD) and electrochemically modified with nanofibrous PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(p-styrenesulfonate)). The structures are found to have increased surface area as characterized by porosimetry. When applied as anodes in polymer/fullerene OPVs (architecture: commercial ITO/GLAD ITO/PEDOT:PSS/P3HT:PCBM/Al, where P3HT is 2,5-diyl-poly(3-hexylthiophene) and PCBM is [6,6]-phenyl-C(61)-butyric acid methyl ester), the air-processed solar cells incorporating high surface area, PEDOT:PSS-modified ITO nanoelectrode arrays operate with improved performance relative to devices processed identically on unstructured, commercial ITO substrates. The resulting power conversion efficiency is 2.2% which is a third greater than for devices prepared on commercial ITO. To further refine the structure, insulating SiO(2) caps are added above the GLAD ITO nanopillars to produce a hybrid ITO/SiO(2) nanoelectrode. OPV devices based on this system show reduced electrical shorting and series resistance, and as a consequence, a further improved power conversion efficiency of 2.5% is recorded.

Electrostatic Layer-by-Layer Assembly of CdSe Nanorod/Polymer Nanocomposite Thin Films

Electrostatic layer-by-layer assembly was the basis for the synthesis of multilayer nanorod/polymer composite films. Cationic and water-soluble CdSe nanorods (NRs) were synthesized and partnered with anionic polymers including poly(sodium 4-styrenesulfonate) (PSS) and two polythiophene-based photoactive polymers, sodium poly[2-(3-thienyl)-ethoxy-4-butylsulfonate (PTEBS) and poly[3-(potassium-6-hexanoate)thiophene-2,5-diyl] (P3KHT). Controlled multilayer growth is shown through UV-vis spectroscopy, cross-sectional SEM and surface analytical techniques including atomic force microscopy. The formation of an intimate nanorod/conducting polymer bulk heterojunction is confirmed through cross-sectional SEM, TEM, and scanning Auger analysis. A series of photovoltaic devices was fabricated on ITO electrodes using CdSe NRs in combination with PTEBS or P3KHT. A thorough device analysis showed that performance was limited by low short circuit current although charge transfer was confirmed in the ELBL nanocomposite thin films.

C60 Fullerene Nanocolumns–Polythiophene Heterojunctions for Inverted Organic Photovoltaic Cells

Inverted organic photovoltaic cells have been fabricated based on vertical C(60) nanocolumns filled with spin-coated poly[3-(4-carboxybutyl)thiophene-2,5-diyl] (P3CBT). These C(60) nanocolumns were prepared via glancing angle deposition (GLAD), an efficient synthetic approach that controls the morphology of the resulting film, including intercolumn spacing, nanostructure shapes, and overall film thickness, among others. Intercolumn spacing was tuned to better match the expected P3CBT exciton diffusion length while simultaneously increasing heterointerface area. Due to observed in situ dissolution of the C(60) nanocolumns in solvents typically used to spin-coat polythiophene-based polymers (i.e., chloroform and chlorobenzene), the carboxylic acid-substituted polythiophene, P3CBT, was used as it is soluble in dimethyl sulfoxide (DMSO), a solvent that did not affect the structure of the GLAD-produced C(60) nanostructures. Preservation of the C(60) nanocolumnar structure in the presence of DMSO, with and without P3CBT, was verified by absorbance spectroscopy and SEM imaging. Incorporating these nanostructured C(60)/P3CBT films into photovoltaic devices on indium tin oxide (ITO) showed that the engineered nanomorphology yielded a 5-fold increase in short-circuit current and a power conversion efficiency (PCE) increase from (0.2 ± 0.03)% to (0.8 ± 0.2)% when compared to a planar device. When compared to a standard bulk heterojunction (BHJ) device based upon the same materials, the C(60)-GLAD device outperformed fully solution-processed bulk heterojunctions, which were observed to have PCEs of (0.49 ± 0.03)%.

Self-assembly of carboxylated polythiophene nanowires for improved bulk heterojunction morphology in polymer solar cells

Conjugated regioregular poly[3-(5-carboxypentyl) thiophene-2,5-diyl] (P3CPenT), a derivative of poly(3-hexylthiophene) (P3HT), is introduced as a hole transport layer (HTL) for P3HT:PCBM plastic solar cells (PSCs). P3CPenT, a carboxyl-functionalized polythiophene, is insoluble in solvents typically used in the preparation of photoactive layers such as chloroform, chlorobenzene and dichlorobenzene, allowing successive processing of the photoactive layer without dissolution of the HTL. P3CPenT self-assembles into nanowires in DMSO solution and when cast as a film, reduces concentration gradients of P3HT:PCBM photoactive layers. P3HT:PCBM PSCs incorporating P3CPenT nanowires as the HTL have a higher fill factor (FF, 0.67) and power conversion efficiency (PCE, 3.7%) than devices with conventional PEDOT:PSS HTLs.

Atomic layer deposition of TiN for the fabrication of nanomechanical resonators

Films of titanium nitride were grown by atomic layer deposition (ALD) over a range of temperatures from 120 °C to 300 °C, and their deposition rates were characterized by ellipsometry and reflectometry. The stress state of the films was evaluated by interferometry using a wafer bowing technique and varied from compressive (−18 MPa) to tensile (650 MPa). The crystal structure of the films was assessed by x-ray diffraction. The grain size varied with temperature in the range of 2–9 nm. The chemical composition of the films was ascertained by high-resolution x-ray photoelectron spectroscopy and showed the presence of O, Cl, and C contaminants. A mildly tensile (250 MPa) stressed film was employed for the fabrication (by electron beam lithography and reactive ion etching) of doubly clamped nanoresonator beams. The resonance frequency of resonators was assayed using an interferometric resonance testing apparatus. The devices exhibited sharp mechanical resonance peaks in the 17–25 MHz range. The uniformity and ...