Guillermo C. Bazan

Processing additives for improved efficiency from bulk heterojunction solar cells.

Two criteria for processing additives introduced to control the morphology of bulk heterojunction (BHJ) materials for use in solar cells have been identified: (i) selective (differential) solubility of the fullerene component and (ii) higher boiling point than the host solvent. Using these criteria, we have investigated the class of 1,8-di(R)octanes with various functional groups (R) as processing additives for BHJ solar cells. Control of the BHJ morphology by selective solubility of the fullerene component is demonstrated using these high boiling point processing additives. The best results are obtained with R = Iodine (I). Using 1,8-diiodooctane as the processing additive, the efficiency of the BHJ solar cells was improved from 3.4% (for the reference device) to 5.1%.

Solution-processed small-molecule solar cells with 6.7% efficiency

Organic photovoltaic devices that can be fabricated by simple processing techniques are under intense investigation in academic and industrial laboratories because of their potential to enable mass production of flexible and cost-effective devices. Most of the attention has been focused on solution-processed polymer bulk-heterojunction (BHJ) solar cells. A combination of polymer design, morphology control, structural insight and device engineering has led to power conversion efficiencies (PCEs) reaching the 6-8% range for conjugated polymer/fullerene blends. Solution-processed small-molecule BHJ (SM BHJ) solar cells have received less attention, and their efficiencies have remained below those of their polymeric counterparts. Here, we report efficient solution-processed SM BHJ solar cells based on a new molecular donor, DTS(PTTh(2))(2). A record PCE of 6.7% under AM 1.5 G irradiation (100 mW cm(-2)) is achieved for small-molecule BHJ devices from DTS(PTTh(2))(2):PC(70)BM (donor to acceptor ratio of 7:3). This high efficiency was obtained by using remarkably small percentages of solvent additive (0.25% v/v of 1,8-diiodooctane, DIO) during the film-forming process, which leads to reduced domain sizes in the BHJ layer. These results provide important progress for solution-processed organic photovoltaics and demonstrate that solar cells fabricated from small donor molecules can compete with their polymeric counterparts.

Electrochemical considerations for determining absolute frontier orbital energy levels of conjugated polymers for solar cell applications.

Narrow bandgap conjugated polymers in combination with fullerene acceptors are under intense investigation in the field of organic photovoltaics (OPVs). The open circuit voltage, and thereby the power conversion efficiency, of the devices is related to the offset of the frontier orbital energy levels of the donor and acceptor components, which are widely determined by cyclic voltammetry. Inconsistencies have appeared in the use of the ferrocenium/ferrocene (Fc + /Fc) redox couple, as well as the values used for the absolute potentials of standard electrodes, which can complicate the comparison of materials properties and determination of structure/property relationships.

Streamlined microwave-assisted preparation of narrow-bandgap conjugated polymers for high-performance bulk heterojunction solar cells

The most efficient plastic solar cells comprise a blend of conjugated polymer and a suitable electron acceptor, typically a fullerene derivative. Therefore narrow-bandgap conjugated polymers are currently sought for the fabrication of such devices. A significant challenge is being able to predict device function and performance from consideration of the molecular connectivity and dimensions of the partners within the active layer. Improved chemical syntheses are therefore required to make structurally varied polymers and enable the delineation of structure-function relationships with the aim of improving power conversion efficiencies. Here, we demonstrate that microwave heating in combination with the screening of comonomer reactant ratios can be used to obtain donor-acceptor copolymers with high average molecular weights and properties that make them suitable for solar cell incorporation. Furthermore, we highlight the importance of high molecular weight and the contribution of solubilizing side groups in determining the final device properties.

Non‐Basic High‐Performance Molecules for Solution‐Processed Organic Solar Cells

A new small molecule, p-DTS(FBTTh(2))(2), is designed for incorporation into solution-fabricated high-efficiency organic solar cells. Of primary importance is the incorporation of electron poor heterocycles that are not prone to protonation and thereby enable the incorporation of commonly used interlayers between the organic semiconductor and the charge collecting electrodes. These features have led to the creation of p-DTS(FBTTh(2))(2)/PC(71)BM solar cells with power conversion efficiencies of up to 7%.

DNA detection using water-soluble conjugated polymers and peptide nucleic acid probes

The light-harvesting properties of cationic conjugated polymers are used to sensitize the emission of a dye on a specific peptide nucleic acid (PNA) sequence for the purpose of homogeneous, “real-time” DNA detection. Signal transduction is controlled by hybridization of the neutral PNA probe and the negative DNA target. Electrostatic interactions bring the hybrid complex and cationic polymer within distances required for Förster energy transfer. Conjugated polymer excitation provides fluorescein emission >25 times higher than that obtained by exciting the dye, allowing detection of target DNA at concentrations of 10 pM with a standard fluorometer. A simple and highly sensitive assay with optical amplification that uses the improved hybridization behavior of PNA/DNA complexes is thus demonstrated.

Ultrafast long-range charge separation in organic semiconductor photovoltaic diodes.

Early Separation In photovoltaic devices, electrons excited by the absorption of light must travel across a junction, while the positively charged “holes” they leave behind effectively migrate in the opposite direction. If the electrons and holes do not separate efficiently, they can recombine and fail to produce any appreciable current. Gélinas et al. (p. 512, published online 12 December; see the Perspective by Bredas) studied this separation process by ultrafast optical absorption spectroscopy in thiophene-derived donor-fullerene acceptor systems common in organic photovoltaics and report a rate significantly faster than simple charge diffusion would suggest. The results implicate a coherent charge delocalization process, likely to involve fullerene π-electron states. Ultrafast spectroscopy shows electrons and holes separating faster than simple diffusion would imply in organic photovoltaics. [Also see Perspective by Bredas] Understanding the charge-separation mechanism in organic photovoltaic cells (OPVs) could facilitate optimization of their overall efficiency. Here we report the time dependence of the separation of photogenerated electron hole pairs across the donor-acceptor heterojunction in OPV model systems. By tracking the modulation of the optical absorption due to the electric field generated between the charges, we measure ~200 millielectron volts of electrostatic energy arising from electron-hole separation within 40 femtoseconds of excitation, corresponding to a charge separation distance of at least 4 nanometers. At this separation, the residual Coulomb attraction between charges is at or below thermal energies, so that electron and hole separate freely. This early time behavior is consistent with charge separation through access to delocalized π-electron states in ordered regions of the fullerene acceptor material.

Endohedral fullerenes for organic photovoltaic devices

So far, one of the fundamental limitations of organic photovoltaic (OPV) device power conversion efficiencies (PCEs) has been the low voltage output caused by a molecular orbital mismatch between the donor polymer and acceptor molecules. Here, we present a means of addressing the low voltage output by introducing novel trimetallic nitride endohedral fullerenes (TNEFs) as acceptor materials for use in photovoltaic devices. TNEFs were discovered in 1999 by Stevenson et al. ; for the first time derivatives of the TNEF acceptor, Lu(3)N@C(80), are synthesized and integrated into OPV devices. The reduced energy offset of the molecular orbitals of Lu(3)N@C(80) to the donor, poly(3-hexyl)thiophene (P3HT), reduces energy losses in the charge transfer process and increases the open circuit voltage (Voc) to 260 mV above reference devices made with [6,6]-phenyl-C(61)-butyric methyl ester (C(60)-PCBM) acceptor. PCEs >4% have been observed using P3HT as the donor material. This work clears a path towards higher PCEs in OPV devices by demonstrating that high-yield charge separation can occur with OPV systems that have a reduced donor/acceptor lowest unoccupied molecular orbital energy offset.

Efficient Solution‐Processed Small‐Molecule Solar Cells with Inverted Structure

We successfully demonstrate inverted structure small-molecule (SM) solar cells with an efficiency of 7.88% using ZnO and PEIE as an interfacial layer. Modification of ZnO with a cost-effective PEIE thin layer increases the efficiency of the inverted cell as a result of reducing the work function of the cathode and suppressing the trap-assisted recombination. In addition to the high efficiency, the inverted SM solar cells are relatively stable in air compared to conventional cells.

Improved Light Harvesting and Improved Efficiency by Insertion of an Optical Spacer (ZnO) in Solution-Processed Small-Molecule Solar Cells

We demonstrate that the power conversion efficiency can be significantly improved in solution-processed small-molecule solar cells by tuning the thickness of the active layer and inserting an optical spacer (ZnO) between the active layer and the Al electrode. The enhancement in light absorption in the cell was measured with UV-vis absorption spectroscopy and by measurements of the photoinduced carriers generation rate. The ZnO layer used to improve the light-harvesting increases the charge collection efficiency, serves as a blocking layer for holes, and reduces the recombination rate. The combined optical and electrical improvements raise the power conversion efficiency of solution-processed small-molecule solar cells to 8.9%, that is, comparable to that of polymer counterparts.