The recent improvements in the power conversion efficiencies of organic photovoltaic devices (OPVs) promise to make these technologies increasingly attractive alternatives to more established photovoltaic technologies. OPVs typically consist of photoactive layers 20-100 nm thick sandwiched between both transparent oxide and metallic electrical contacts. Ideal OPVs rely on ohmic top and bottom contacts to harvest photogenerated charges without compromising the power conversion efficiency of the OPV. Unfortunately, the electrical contact materials (metals and metal oxides) and the active organic layers in OPVs are often incompatible and may be poorly optimized for harvesting photogenerated charges. Therefore, further optimization of the chemical and physical stabilities of these metal oxide materials with organic materials will be an essential component of the development of OPV technologies. The energetic and kinetic barriers to charge injection/collection must be minimized to maximize OPV power conversion efficiencies. In this Account, we review recent studies of one of the most common transparent conducting oxides (TCOs), indium-tin oxide (ITO), which is the transparent bottom contact in many OPV technologies. These studies of the surface chemistry and surface modification of ITO are also applicable to other TCO materials. Clean, freshly deposited ITO is intrinsically reactive toward H(2)O, CO, CO(2), etc. and is often chemically and electrically heterogeneous in the near-surface region. Conductive-tip atomic force microscopy (C-AFM) studies reveal significant spatial variability in electrical properties. We describe the use of acid activation, small-molecule chemisorption, and electrodeposition of conducting polymer films to tune the surface free energy, the effective work function, and electrochemical reactivity of ITO surfaces. Certain electrodeposited poly(thiophenes) show their own photovoltaic activity or can be used as electronically tunable substrates for other photoactive layers. For certain photoactive donor layers (phthalocyanines), we have used the polarity of the oxide surface to accelerate dewetting and "nanotexturing" of the donor layer to enhance OPV performance. These complex surface chemistries will make oxide/organic interfaces one of the key focal points for research in new OPV technologies.
Planar heterojunction organic photovoltaic devices have been created using oxo-titanium phthalocyanine (TiOPc) as the donor layer and fullerene (C60) as the acceptor layer, with comparisons to devices based on copper phthalocyanine (CuPc) as the donor. TiOPc/C60 and CuPc/C60 heterojunctions were first characterized by a combination of UV-photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS) to estimate the frontier orbital energy offset (E D HOMO − E A LUMO), which is related to the open-circuit photopotential (V OC). A small interface dipole effect was seen at the TiOPc/C60 interface (eD ≈ 0.02 eV), whereas a significant interface dipole was observed for the CuPc/C60 interface (eD ≈ 0.3 eV). On the basis of the work presented here and previously reported electrochemical and UPS/XPS studies, we estimate an E D HOMO − E A LUMO energy offset of ca. 1.1 eV for the TiOPc/C60 heterojunction and 0.7 eV for the CuPc/C60 heterojunction. Maximum V OC values observed at room temperature for corresponding planar heterojunction photovoltaic devices were 0.3−0.4 V lower than the energy offset potentials, even at high light intensities, where the maximum V OC, at room temperature, was achieved. TiOPc/C60 heterojunctions offer higher V OC values than CuPc/C60 heterojunctions, but with a lower intrinsic driving force for exciton dissociation (photoinduced charge transfer).
Organic photovoltaic cells (OPV) with good near‐IR photoactivity are created from highly textured titanyl phthalocyanine (TiOPc)/C60 heterojunctions. Vacuum deposited TiOPc thin films are converted to the near‐IR absorbing “Phase II” polymorph using post‐deposition solvent annealing. The Phase I → Phase II transition broadens the absorbance spectrum of the Pc film producing absorptivities (α ≈ 105 cm−1) from 600–900 nm, along with substantial texturing of the Pc layer. Atomic force microscopy and field‐emission scanning electron microscopy of the solvent annealed films show that the surface roughness of the Pc layers is increased by a factor of greater than 2× as a result of the phase transformation. Current–voltage (J–V) responses for white light illumination of ITO (100 nm)/TiOPc (20 nm)/C60 (40 nm)/BCP (10 nm)/Al (100 nm) OPVs show a near doubling of the short‐circuit photocurrent (JSC), with only a small decrease in open‐circuit photopotential (VOC), and a concomitant increase in power conversion efficiency. Incident photon current efficiency (IPCE) plots confirmed the enhanced near‐IR OPV activity, with maximum IPCE values of ca. 30% for devices using Phase II‐only TiOPc films. UV‐photoelectron spectroscopy (UPS) of TiOPc/C60 heterojunctions, for both Phase I and Phase II TiOPc films, suggest that the Phase II polymorph has nearly the same HOMO energy as seen in the Phase I polymorph, and similar frontier orbital energy offsets, EHOMOPc–ELUMOC60, leading to comparable open‐circuit photovoltages. These studies suggest new strategies for the formation of higher efficiency OPVs using processing conditions which lead to enhance near‐IR absorptivities, and extensive texturing of crystalline donor or acceptor films.
Heterojunctions created from thin films of two dissimilar organic semiconductor materials [organic/organic' (O/O') heterojunctions] are an essential component of organic light emitting diode displays and lighting systems (OLEDs, PLEDs) and small molecule or polymer-based organic photovoltaic (solar cell) technologies (OPVs). O/O' heterojunctions are the site for exciton formation in OLEDs, and the site for exciton dissociation and photocurrent production in OPVs. Frontier orbital energy offsets in O/O' heterojunctions establish the excess free energy controlling rates of charge recombination and formation of emissive states in OLEDs and PLEDs. These energy offsets also establish the excess free energy which controls charge separation and the short-circuit photocurrent (J(SC) ) in OPVs, and set the upper limit for the open-circuit photopotential (V(OC) ). We review here how these frontier orbital energy offsets are determined using photoemission spectroscopies, how these energies change as a function of molecular environment, and the influence of interface dipoles on these frontier orbital energies. Recent examples of heterojunctions based on small molecule materials are shown, emphasizing those heterojunctions which are of interest for photovoltaic applications. These include heterojunctions of perylenebisimide dyes with trivalent metal phthalocyanines, and heterojunctions of titanyl phthalocyanine with C(60) , and with pentacene. Organic solar cells comprised of donor/acceptor pairs of each of these last three materials confirm that the V(OC) scales with the energy offsets between the HOMO of the donor and LUMO of the acceptor ($E_{{\rm HOMO}^{\rm D} } - E_{{\rm LUMO}^{\rm A} }$).
Nanocrystal quantum dots (QD) show great promise toward improving solar cell efficiencies through the use of quantum confinement to tune absorbance across the solar spectrum and enable multi-exciton generation. Despite this remarkable potential for high photocurrent generation, the achievable open-circuit voltage (Voc) is fundamentally limited due to non-radiative recombination processes in QD solar cells. Here we report the highest open-circuit voltages to date for colloidal QD based solar cells under one sun illumination. This Voc of 692 ± 7 mV for 1.4 eV PbS QDs is a result of improved passivation of the defective QD surface, demonstrating as a function of the QD bandgap (Eg). Comparing experimental Voc variation with the theoretical upper-limit obtained from one diode modeling of the cells with different Eg, these results clearly demonstrate that there is a tremendous opportunity for improvement of Voc to values greater than 1 V by using smaller QDs in QD solar cells.
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