Efficient charge generation by relaxed charge-transfer states at organic interfaces.

Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy.

Self-assembly of broadband white-light emitters.

We use organic cations to template the solution-state assembly of corrugated lead halide layers in bulk crystalline materials. These layered hybrids emit radiation across the entire visible spectrum upon ultraviolet excitation. They are promising as single-source white-light phosphors for use with ultraviolet light-emitting diodes in solid-state lighting devices. The broadband emission provides high color rendition and the chromaticity coordinates of the emission can be tuned through halide substitution. We have isolated materials that emit the "warm" white light sought for many indoor lighting applications as well as "cold" white light that approximates the visible region of the solar spectrum. Material syntheses are inexpensive and scalable and binding agents are not required for film deposition, eliminating problems of binder photodegradation. These well-defined and tunable structures provide a flexible platform for studying the rare phenomenon of intrinsic broadband emission from bulk materials.

A layered hybrid perovskite solar-cell absorber with enhanced moisture stability.

Two-dimensional hybrid perovskites are used as absorbers in solar cells. Our first-generation devices containing (PEA)2(MA)2[Pb3I10] (1; PEA=C6H5(CH2)2NH3(+), MA=CH3NH3(+)) show an open-circuit voltage of 1.18 V and a power conversion efficiency of 4.73%. The layered structure allows for high-quality films to be deposited through spin coating and high-temperature annealing is not required for device fabrication. The 3D perovskite (MA)[PbI3] (2) has recently been identified as a promising absorber for solar cells. However, its instability to moisture requires anhydrous processing and operating conditions. Films of 1 are more moisture resistant than films of 2 and devices containing 1 can be fabricated under ambient humidity levels. The larger bandgap of the 2D structure is also suitable as the higher bandgap absorber in a dual-absorber tandem device. Compared to 2, the layered perovskite structure may offer greater tunability at the molecular level for material optimization.

Molecular packing and solar cell performance in blends of polymers with a bisadduct fullerene.

We compare the solar cell performance of several polymers with the conventional electron acceptor phenyl-C61-butyric acid methyl ester (PCBM) to fullerenes with one to three indene adducts. We find that the multiadduct fullerenes with lower electron affinity improve the efficiency of the solar cells only when they do not intercalate between the polymer side chains. When they intercalate between the side chains, the multiadduct fullerenes substantially reduce solar cell photocurrent. We use X-ray diffraction to determine how the fullerenes are arranged within crystals of poly-(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) and suggest that poor electron transport in the molecularly mixed domains may account for the reduced solar cell performance of blends with fullerene intercalation.

Controlled conjugated backbone twisting for an increased open-circuit voltage while having a high short-circuit current in poly(hexylthiophene) derivatives.

Conjugated polymers with nearly planar backbones have been the most commonly investigated materials for organic-based electronic devices. More twisted polymer backbones have been shown to achieve larger open-circuit voltages in solar cells, though with decreased short-circuit current densities. We systematically impose twists within a family of poly(hexylthiophene)s and examine their influence on the performance of polymer:fullerene bulk heterojunction (BHJ) solar cells. A simple chemical modification concerning the number and placement of alkyl side chains along the conjugated backbone is used to control the degree of backbone twisting. Density functional theory calculations were carried out on a series of oligothiophene structures to provide insights on how the sterically induced twisting influences the geometric, electronic, and optical properties. Grazing incidence X-ray scattering measurements were performed to investigate how the thin-film packing structure was affected. The open-circuit voltage and charge-transfer state energy of the polymer:fullerene BHJ solar cells increased substantially with the degree of twist induced within the conjugated backbone--due to an increase in the polymer ionization potential--while the short-circuit current decreased as a result of a larger optical gap and lower hole mobility. A controlled, moderate degree of twist along the poly(3,4-dihexyl-2,2':5',2''-terthiophene) (PDHTT) conjugated backbone led to a 19% enhancement in the open-circuit voltage (0.735 V) vs poly(3-hexylthiophene)-based devices, while similar short-circuit current densities, fill factors, and hole-carrier mobilities were maintained. These factors resulted in a power conversion efficiency of 4.2% for a PDHTT:[6,6]-phenyl-C(71)-butyric acid methyl ester (PC(71)BM) blend solar cell without thermal annealing. This simple approach reveals a molecular design avenue to increase open-circuit voltage while retaining the short-circuit current.

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.

3,4-Disubstituted polyalkylthiophenes for high-performance thin-film transistors and photovoltaics.

We demonstrate that poly(3,4-dialkylterthiophenes) (P34ATs) have comparable transistor mobilities (0.17 cm(2) V(-1) s(-1)) and greater environmental stability (less degradation of on/off ratio) than regioregular poly(3-alkylthiophenes) (P3ATs). Unlike poly(3-hexylthiophene) (P3HT), P34ATs do not show a strong and distinct π-π stacking in X-ray diffraction. This suggests that a strong π-π stacking is not always necessary for high charge-carrier mobility and that other potential polymer packing motifs in addition to the edge-on structure (π-π stacking direction parallel to the substrate) can lead to a high carrier mobility. The high charge-carrier mobilities of the hexyl and octyl-substituted P34AT produce power conversion efficiencies of 4.2% in polymer:fullerene bulk heterojunction photovoltaic devices. An enhanced open-circuit voltage (0.716-0.771 eV) in P34AT solar cells relative to P3HT due to increased ionization potentials was observed.

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.

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.

Modeling the efficiency of Förster resonant energy transfer from energy relay dyes in dye-sensitized solar cells.

Förster resonant energy transfer can improve the spectral breadth, absorption and energy conversion efficiency of dye sensitized solar cells. In this design, unattached relay dyes absorb the high energy photons and transfer the excitation to sensitizing dye molecules by Förster resonant energy transfer. We use an analytic theory to calculate the excitation transfer efficiency from the relay dye to the sensitizing dye accounting for dynamic quenching and relay dye diffusion. We present calculations for pores of cylindrical and spherical geometry and examine the effects of the Förster radius, the pore size, sensitizing dye surface concentration, collisional quenching rate, and relay dye lifetime. We find that the excitation transfer efficiency can easily exceed 90% for appropriately chosen dyes and propose two different strategies for selecting dyes to achieve record power conversion efficiencies.

Incomplete exciton harvesting from fullerenes in bulk heterojunction solar cells.

We investigate the internal quantum efficiencies (IQEs) of high efficiency poly-3-hexylthiophene:[6,6]-phenyl-C(61)-butyric acid methyl ester (P3HT:PCBM) solar cells and find them to be lower at wavelengths where the PCBM absorbs. Because the exciton diffusion length in PCBM is too small, excitons generated in PCBM decay before reaching the donor-acceptor interface. This result has implications for most state of the art organic solar cells, since all of the most efficient devices use fullerenes as electron acceptors.

Temporal force fluctuations measured by tracking individual particles in granular materials under shear.

The network of forces between contacts in a granular material determines the response of the material to an external perturbation. As the shear stress is increased, a static, rigid material can start to yield and flow as it becomes unjammed. The time- and ensemble-averaged distribution of forces shows a marked change in character at this jamming-unjamming transition. Here, we investigate the temporal fluctuations of the forces between individual particles and the external boundary in a dense, slowly sheared system. We find that the fluctuations occur over a very broad range of time scales, resulting in power spectra characterized by a 1/f -type shape and a rollover to 1/f2 behavior above a turnover frequency f*. At very low frequencies additional enhancements over the 1/f contributions are observed in regions of significant in-plane shear. Moreover, the magnitude of the force fluctuation spectra produced by one particle is different from those produced by its neighbors. Such heterogeneities persist over periods of time exceeding our measurement interval (60 h). In this respect they are reminiscent of the dynamic heterogeneities that occur in liquids supercooled toward the glass transition temperature.

Cesium Lead Halide Perovskites with Improved Stability for Tandem Solar Cells.

A semiconductor that can be processed on a large scale with a bandgap around 1.8 eV could enable the manufacture of highly efficient low cost double-junction solar cells on crystalline Si. Solution-processable organic-inorganic halide perovskites have recently generated considerable excitement as absorbers in single-junction solar cells, and though it is possible to tune the bandgap of (CH3NH3)Pb(BrxI1-x)3 between 2.3 and 1.6 eV by controlling the halide concentration, optical instability due to photoinduced phase segregation limits the voltage that can be extracted from compositions with appropriate bandgaps for tandem applications. Moreover, these materials have been shown to suffer from thermal degradation at temperatures within the processing and operational window. By replacing the volatile methylammonium cation with cesium, it is possible to synthesize a mixed halide absorber material with improved optical and thermal stability, a stabilized photoconversion efficiency of 6.5%, and a bandgap of 1.9 eV.

Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics.

We report on reversible, light-induced transformations in (CH3NH3)Pb(Br x I1-x )3. Photoluminescence (PL) spectra of these perovskites develop a new, red-shifted peak at 1.68 eV that grows in intensity under constant, 1-sun illumination in less than a minute. This is accompanied by an increase in sub-bandgap absorption at ∼1.7 eV, indicating the formation of luminescent trap states. Light soaking causes a splitting of X-ray diffraction (XRD) peaks, suggesting segregation into two crystalline phases. Surprisingly, these photo-induced changes are fully reversible; the XRD patterns and the PL and absorption spectra revert to their initial states after the materials are left for a few minutes in the dark. We speculate that photoexcitation may cause halide segregation into iodide-rich minority and bromide-enriched majority domains, the former acting as a recombination center trap. This instability may limit achievable voltages from some mixed-halide perovskite solar cells and could have implications for the photostability of halide perovskites used in optoelectronics.

Re-evaluating the role of sterics and electronic coupling in determining the open-circuit voltage of organic solar cells.

The effects of sterics and molecular orientation on the open-circuit voltage and absorbance properties of charge-transfer states are explored in model bilayer organic photovoltaics. It is shown that the open-circuit voltage correlates linearly with the charge-transfer state energy and is not significantly influenced by electronic coupling.

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.

The mechanism of burn-in loss in a high efficiency polymer solar cell.

Degradation in a high efficiency polymer solar cell is caused by the formation of states in the bandgap. These states increase the energetic disorder in the system. The power conversion efficiency loss does not occur when current is run through the device in the dark but occurs when the active layer is photo-excited.