Brian E. Hardin

Polymer-based solar cells

A significant fraction of the cost of solar panels comes from the photoactive materials and sophisticated, energy-intensive processing technologies. Recently, it has been shown that the inorganic components can be replaced by semiconducting polymers capable of achieving reasonably high power conversion efficiencies. These polymers are inexpensive to synthesize and can be solution-processed in a roll-to-roll fashion with high throughput. Inherently poor polymer properties, such as low exciton diffusion lengths and low mobilities, can be overcome by nanoscale morphology. We discuss polymer-based solar cells, paying particular attention to device design and potential improvements.

Organic bulk heterojunction solar cells using poly(2,5-bis(3-tetradecyllthiophen-2-yl)thieno[3,2,-b]thiophene)

By transitioning to semicrystalline polymers, the performance of polymer-based solar cells has recently increased to over 5% [W. Ma et al., Adv. Fund. Mater. 15, 1665 (2005); G. Li et al., Nat. Mater. 4, 864 (2005); M. Reyes-Reyes et al., Org. Lett. 7, 5749 (2005); J. Y. Kim et al., Adv. Mater. (Weinheim, Ger.) 18, 572 (2005); J. Peet et al., Nat. Mater. 6, 497 (2007)]. Poly(2,5-bis(3-tetradecyllthiophen-2-yl)thieno[3,2-b]thiophene) (pBTTT) has caused recent excitement in the organic electronics community because of its high reported hole mobility (0.6cm2V−1s−1) that was measured in field effect transistors and its ability to form large crystals. In this letter, we investigate the potential of pBTTT as light absorber and hole transporter in a bulk heterojunction solar cell. We find that the highest efficiency of 2.3% is achieved by using a 1:4 blend of pBTTT and[6,6]-phenyl C61-butyric acid methyl ester. The hole mobility as measured by space charge limited current modeling was found to be 3.8×10−4cm2V−1s...

High Excitation Transfer Efficiency from Energy Relay Dyes in Dye-Sensitized Solar Cells

The energy relay dye, 4-(Dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), was used with a near-infrared sensitizing dye, TT1, to increase the overall power conversion efficiency of a dye-sensitized solar cell (DSC) from 3.5% to 4.5%. The unattached DCM dyes exhibit an average excitation transfer efficiency (ETE) of 96% inside TT1-covered, mesostructured TiO(2) films. Further performance increases were limited by the solubility of DCM in an acetonitrile based electrolyte. This demonstration shows that energy relay dyes can be efficiently implemented in optimized dye-sensitized solar cells, but also highlights the need to design highly soluble energy relay dyes with high molar extinction coefficients.

Panchromatic Response in Solid-State Dye-Sensitized Solar Cells Containing Phosphorescent Energy Relay Dyes

Running relay: Incorporating an energy-relay dye (ERD) into the hole transporter of a dye-sensitized solar cell increased power-conversion efficiency by 29 % by extending light harvesting into the blue region. In the operating mechanism (see picture), absorption of red photons by the sensitizer transfers an electron into TiO2 and a hole into the electrolyte. Blue photons absorbed by the ERD are transferred by FRET to the sensitizer.

Energy and Hole Transfer between Dyes Attached to Titania in Cosensitized Dye-Sensitized Solar Cells

Cosensitization of broadly absorbing ruthenium metal complex dyes with highly absorptive near-infrared (NIR) organic dyes is a clear pathway to increase near-infrared light harvesting in liquid-based dye-sensitized solar cells (DSCs). In cosensitized DSCs, dyes are intimately mixed, and intermolecular charge and energy transfer processes play an important role in device performance. Here, we demonstrate that an organic NIR dye incapable of hole regeneration is able to produce photocurrent via intermolecular energy transfer with an average excitation transfer efficiency of over 25% when cosensitized with a metal complex sensitizing dye (SD). We also show that intermolecular hole transfer from the SD to NIR dye is a competitive process with dye regeneration, reducing the internal quantum efficiency and the electron lifetime of the DSC. This work demonstrates the general feasibility of using energy transfer to boost light harvesting from 700 to 800 nm and also highlights a key challenge for developing highly efficient cosensitized dye-sensitized solar cells.

Silicon-Naphthalo/Phthalocyanine-Hybrid Sensitizer for Efficient Red Response in Dye-Sensitized Solar Cells

Introduction of a naphthalocyanine moiety to phthalocyanine allows for a gradual red shift of the absorption spectrum in the resulting chromophore. Using silicon as a core atom allows for the introduction of additional siloxane side chains which mitigate dye aggregation. A dye-sensitized solar cell with this hybrid sensitizer exhibits a broad and flat IPCE of 80% between 600 and 750 nm and high photocurrent densities of 19.0 mA/cm(2).

Incorporating Multiple Energy Relay Dyes in Liquid Dye-Sensitized Solar Cells

Panchromatic response is essential to increase the light-harvesting efficiency in solar conversion systems. Herein we show increased light harvesting from using multiple energy relay dyes inside dye-sensitized solar cells. Additional photoresponse from 400-590 nm matching the optical window of the zinc phthalocyanine sensitizer was observed due to Förster resonance energy transfer (FRET) from the two energy relay dyes to the sensitizing dye. The complementary absorption spectra of the energy relay dyes and high excitation transfer efficiencies result in a 35% increase in photovoltaic performance.

Probing carrier lifetimes in photovoltaic materials using subsurface two-photon microscopy.

Accurately measuring the bulk minority carrier lifetime is one of the greatest challenges in evaluating photoactive materials used in photovoltaic cells. One-photon time-resolved photoluminescence decay measurements are commonly used to measure lifetimes of direct bandgap materials. However, because the incident photons have energies higher than the bandgap of the semiconductor, most carriers are generated close to the surface, where surface defects cause inaccurate lifetime measurements. Here we show that two-photon absorption permits sub-surface optical excitation, which allows us to decouple surface and bulk recombination processes even in unpassivated samples. Thus with two-photon microscopy we probe the bulk minority carrier lifetime of photovoltaic semiconductors. We demonstrate how the traditional one-photon technique can underestimate the bulk lifetime in a CdTe crystal by 10× and show that two-photon excitation more accurately measures the bulk lifetime. Finally, we generate multi-dimensional spatial maps of optoelectronic properties in the bulk of these materials using two-photon excitation.

Phosphorescent energy relay dye for improved light harvesting response in liquid dye-sensitized solar cells

Energy transfer from phosphorescent ruthenium complex N877 dissolved in the liquid electrolyte to the squaraine sensitizer SQ1 anchored on the titanium oxide surface resulted in a four fold increase in external quantum efficiency in the blue part of the visible spectrum despite complete quenching of the luminescence of N877 by the iodine in the electrolyte.

The importance of dye chemistry and TiCl4 surface treatment in the behavior of Al2O3 recombination barrier layers deposited by atomic layer deposition in solid-state dye-sensitized solar cells

Atomic layer deposition (ALD) was used to fabricate Al(2)O(3) recombination barriers in solid-state dye-sensitized solar cells (ss-DSSCs) employing an organic hole transport material (HTM) for the first time. Al(2)O(3) recombination barriers of varying thickness were incorporated into efficient ss-DSSCs utilizing the Z907 dye adsorbed onto a 2 μm-thick nanoporous TiO(2) active layer and the HTM spiro-OMeTAD. The impact of Al(2)O(3) barriers was also studied in devices employing different dyes, with increased active layer thicknesses, and with substrates that did not undergo the TiCl(4) surface treatment. In all instances, electron lifetimes (as determined by transient photovoltage measurements) increased and dark current was suppressed after Al(2)O(3) deposition. However, only when the TiCl(4) treatment was eliminated did device efficiency increase; in all other instances efficiency decreased due to a drop in short-circuit current. These results are attributed in the former case to the similar effects of Al(2)O(3) ALD and the TiCl(4) surface treatment whereas the insulating properties of Al(2)O(3) hinder charge injection and lead to current loss in TiCl(4)-treated devices. The impact of Al(2)O(3) barrier layers was unaffected by doubling the active layer thickness or using an alternative ruthenium dye, but a metal-free donor-π-acceptor dye exhibited a much smaller decrease in current due to its higher excited state energy. We develop a model employing prior research on Al(2)O(3) growth and dye kinetics that successfully predicts the reduction in device current as a function of ALD cycles and is extendable to different dye-barrier systems.