Nikos Kopidakis

Inverted bulk-heterojunction organic photovoltaic device using a solution-derived ZnO underlayer

Inverted organic photovoltaic devices based on a blend of poly(3-hexylthiophene) and a fullerene have been developed by inserting a solution-processed ZnO interlayer between the indium tin oxide (ITO) electrode and the active layer using Ag as a hole-collecting back contact. Efficient electron extraction through the ZnO and hole extraction through the Ag, with minimal loss in open-circuit potential, is observed with a certified power conversion efficiency of 2.58%. The inverted architecture removes the need for the use of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) as an ITO modifier and for the use of a low-work-function metal as the back contact in the device.

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.

Spatial location of transport-limiting traps in TiO2 nanoparticle films in dye-sensitized solar cells

The dependence of the electron diffusion coefficient and photoinduced electron density on the internal surface area of TiO2 nanoparticle films in dye-sensitized solar cells was investigated by photocurrent transient measurements. The internal surface area was varied by altering the average particle size of the films. The density of electron traps in the films is found to change in direct proportion with the internal surface area, indicating that the traps are located predominately at the surface of TiO2 particles instead of in the bulk of the particles or at interparticle grain boundaries. The observed scaling of the electron diffusion coefficient with the internal surface area suggests that surface traps limit transport in TiO2 nanoparticle films. These results address a long-standing issue in the understanding of electron transport in dye-sensitized TiO2 solar cells.

Performance of Bulk Heterojunction Photovoltaic Devices Prepared by Airbrush Spray Deposition

We have used airbrush spray deposition to fabricate organic photovoltaic devices with an active layer composed of a blend of poly(3-hexylthiophene) and [6,6]-phenyl-C61 butyric acid methyl ester. Working devices were prepared in ambient conditions from a variety of common organic solvents; active layers prepared from chlorobenzene exhibit improved homogeneity, resulting in narrower distributions of the relevant device parameters. Further studies on devices prepared from chlorobenzene showed that annealing at 120°C for 10min resulted in optimum performance, and that an active layer thickness of 150nm resulted in a maximum efficiency of 2.35% under AM1.5 illumination at 1sun.

Narrowband light detection via internal quantum efficiency manipulation of organic photodiodes

Spectrally selective light detection is vital for full-colour and near-infrared (NIR) imaging and machine vision. This is not possible with traditional broadband-absorbing inorganic semiconductors without input filtering, and is yet to be achieved for narrowband absorbing organic semiconductors. We demonstrate the first sub-100 nm full-width-at-half-maximum visible-blind red and NIR photodetectors with state-of-the-art performance across critical response metrics. These devices are based on organic photodiodes with optically thick junctions. Paradoxically, we use broadband-absorbing organic semiconductors and utilize the electro-optical properties of the junction to create the narrowest NIR-band photoresponses yet demonstrated. In this context, these photodiodes outperform the encumbent technology (input filtered inorganic semiconductor diodes) and emerging technologies such as narrow absorber organic semiconductors or quantum nanocrystals. The design concept allows for response tuning and is generic for other spectral windows. Furthermore, it is material-agnostic and applicable to other disordered and polycrystalline semiconductors.

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.

Prolonging Charge Separation in P3HT−SWNT Composites Using Highly Enriched Semiconducting Nanotubes

Single-walled carbon nanotubes (SWNTs) have potential as electron acceptors in organic photovoltaics (OPVs), but the currently low-power conversion efficiencies of devices remain largely unexplained. We demonstrate effective redispersion of isolated, highly enriched semiconducting and metallic SWNTs into poly(3-hexylthiophene) (P3HT). We use these enriched blends to provide the first experimental evidence of the negative impact of metallic nanotubes. Time-resolved microwave conductivity reveals that the long-lived carrier population can be significantly increased by incorporating highly enriched semiconducting SWNTs into semiconducting polymer composites.

The synthesis and properties of solution processable phenyl cored thiophene dendrimers

In this paper we describe the convergent synthesis of a new class of phenyl cored thiophene dendrimers, which are promising candidates for use in organic semiconductor devices. We have prepared dendrimers with three and four dendrons around the core as well as dendrimers with 1st and 2nd generation dendrons. All the dendrimers were soluble in common organic solvents such as chloroform, THF and toluene. The structures and size properties are confirmed by a number of techniques including NMR, GPC and MALDI-TOF-MS. Decomposition was studied by TGA with initial breakdown of the hexyl surface groups followed by the aromatic core. The spectroscopic properties were studied by UV-vis and PL spectrometry which demonstrated substantial differences between the dendrimers with three and four dendrons. Optical band gaps varied between 2.34 and 2.60 eV for thin films of the dendrimers and electronic band gaps were, on average, 0.3 eV greater than the optical band gaps. The smallest band gap was measured for the dendrimer with four 2nd generation dendrons around the phenyl core. Fluorescence lifetimes of the molecules in solution ranged from 200 to 560 ps. This range in values was attributed to differences in internal conversion rates associated with varying degrees of flexibility of the extended dendrons.

Photovoltaic Charge Generation in Organic Semiconductors Based on Long-Range Energy Transfer

For efficient charge generation in organic solar cells, photogenerated excitons must migrate to a donor/acceptor interface where they can be dissociated. This migration is traditionally presumed to be based on diffusion through the absorber material. Herein we study an alternative migration route--two-step exciton dissociation--whereby the exciton jumps from the donor to acceptor before charge creation takes place. We study this process in a series of multilayer donor/barrier/acceptor samples, where either poly(3-hexylthiophene) (P3HT) or copper phthalocyanine (CuPc) is the donor, fullerene (C60) is the acceptor, and N,N-diphenyl-N,N-bis(3-methylphenyl)-[1,1-bisphenyl]-4,4-diamine (TPD) acts as a barrier to energy transfer. By varying the thickness of the barrier layer, we find that energy transfer from P3HT to C60 proceeds over large distances (∼50% probability of transfer across a 11 nm barrier), and that this process is consistent with long-range Förster resonance energy transfer (FRET). Finally, we demonstrate a fundamentally different architecture concept that utilizes the two-step mechanism to enhance performance in a series of P3HT/CuPc/C60 devices.

Direct synthesis of CdSe nanoparticles in poly(3-hexylthiophene).

A new approach was developed for the synthesis of nearly monodisperse CdSe nanoparticles directly in a polymer-containing solution in the absence of any other surface capping molecules. The comparatively high synthesis temperature reaction produces good quality crystalline CdSe nanoparticles. Time-resolved microwave conductivity measurements show that photoinduced charge separation occurs at the interface between the CdSe quantum dots and the polymer. This method can be extended to the synthesis of other II-VI semiconductor nanomaterials directly in a polymer-containing solution.