Yasunari Tamai

High-efficiency polymer solar cells with small photon energy loss

A crucial issue facing polymer-based solar cells is how to manage the energetics of the polymer/fullerene blends to maximize short-circuit current density and open-circuit voltage at the same time and thus the power conversion efficiency. Here we demonstrate that the use of a naphthobisoxadiazole-based polymer with a narrow bandgap of 1.52 eV leads to high open-circuit voltages of approximately 1 V and high-power conversion efficiencies of ∼9% in solar cells, resulting in photon energy loss as small as ∼0.5 eV, which is much smaller than that of typical polymer systems (0.7–1.0 eV). This is ascribed to the high external quantum efficiency for the systems with a very small energy offset for charge separation. These unconventional features of the present polymer system will inspire the field of polymer-based solar cells towards further improvement of power conversion efficiencies with both high short-circuit current density and open-circuit voltage.

Exciton Diffusion in Conjugated Polymers: From Fundamental Understanding to Improvement in Photovoltaic Conversion Efficiency

Singlet exciton diffusion plays a central role in the photovoltaic conversion in organic photovoltaics (OPVs). Upon light absorption, singlet excitons are promptly generated in organic materials instead of charge carriers because the dielectric constant (εr) is small (∼3-4), which is in sharp contrast to inorganic and perovskite solar cells. In order to convert to charge carriers, excitons need to diffuse into an interface between electron donor and acceptor materials before deactivating to the ground state. Therefore, fundamental understanding of exciton diffusion dynamics is one of the most important issues to further improve OPVs. We highlight recent leading studies in this field and describe several approaches for efficient exciton harvesting at the interface in OPVs.

One-Dimensional Singlet Exciton Diffusion in Poly(3-hexylthiophene) Crystalline Domains

Singlet exciton dynamics in crystalline domains of regioregular poly(3-hexylthiophene) (P3HT) films was studied by transient absorption spectroscopy. Upon the selective excitation of crystalline P3HT at the absorption edge, no red shift of the singlet exciton band was observed with an elapse of time, suggesting singlet exciton dynamics in relatively homogeneous P3HT crystalline domains without downhill relaxation in the energetic disorder. Even under such selective excitation conditions, the annihilation rate coefficient γ(t) was still dependent on time, γ(t) ∝ t(-1/2), which is attributed to anisotropic exciton diffusion in P3HT crystalline domains. From the annihilation rate coefficient, the singlet exciton diffusion coefficient D and exciton diffusion length LD in the crystalline domains were evaluated to be 7.9 × 10(-3) cm(2) s(-1) and 20 nm, respectively. The origin of the time-dependent exciton dynamics is discussed in terms of dimensionality.

Interface Engineering for Ternary Blend Polymer Solar Cells with a Heterostructured Near‐IR Dye

Ternary-blend polymer solar cells can be effectively improved by incorporating a heterostructured near-IR dye, which has a hexyl group compatible with the polymer and a benzyl group compatible with the fullerene. Because of the compatibility with both materials, the heterostructured dye can be loaded up to 15 wt% and hence can boost the photocurrent generation by 30%.

Ultrafast Singlet Fission in a Push–Pull Low-Bandgap Polymer Film

Excited-state dynamics in poly[4,6-(dodecyl-thieno[3,4-b]thiophene-2-carboxylate)-alt-2,6-(4,8-dioctoxylbenzo[1,2-b:4,5-b]dithiophene)] (PTB1) was studied by transient absorption spectroscopy. Upon photoexcitation at 400 nm, an additional transient species is promptly generated along with singlet excitons and survives up to nanoseconds, while singlet excitons disappear completely. In order to assign the long-lived species, we measured transient absorption spectra over the wide spectral range from 900 to 2500 nm. As a result, we found that the long-lived species is ascribed not to polarons but to triplet excitons, which is formed through the ultrafast singlet fission (SF). We discuss the ultrafast SF mechanism in push-pull low-bandgap polymer PTB1 films on the basis of the excited-state dynamics under various excitation wavelengths and intensities.

Transient Absorption Spectroscopy for Polymer Solar Cells

Time-resolved spectroscopy is a powerful tool for studying fundamental photophysics in optoelectronic materials on a molecular temporal scale. In this review, we describe transient spectroscopic studies on fundamental photovoltaic conversion processes in polymer solar cells, which consist of a series of conversion processes such as photon absorption, exciton diffusion into a donor/acceptor interface, charge transfer at the interface, charge dissociation into free charge carriers, and charge collection to each electrode. These conversion processes are ultrafast phenomena and are ranging over the wide temporal scale from femtoseconds to microseconds, which can be directly observed by transient spectroscopy.

Dynamical Excimer Formation in Rigid Carbazolophane via Charge Transfer State

Formation dynamics of intramolecular excimer in dioxa[3.3](3,6)carbazolophane (CzOCz) was studied by time-resolved spectroscopic methods and computational calculations. In the ground state, the most stable conformer in CzOCz is the anti-conformation where two carbazole rings are in antiparallel alignment. No other isomers were observed even after the solution was heated up to 150 °C, although three characteristic isomers were found by the molecular mechanics calculation: the first is the anti-conformer, the second is the syn-conformer where two carbazole rings are stacked in the same direction, and the third is the int-conformer where two carbazole rings are aligned in an edge-to-face geometry. Because of the anti-conformation, the interchromophoric interaction in CzOCz is negligible in the ground state. Nonetheless, the intramolecular excimer in CzOCz was dynamically formed in an acetonitrile (MeCN) solution, indicating strong interchromophoric interaction and the isomerization from the anti- to syn-conformation in the excited state. The excimer formation in CzOCz is more efficient in polar solvents than in less polar solvents, suggesting the contribution of the charge transfer (CT) state to the excimer formation. The stabilization in the excited state is discussed in terms of molecular orbital interaction between two carbazole rings. The solvent-polarity-induced excimer formation is discussed in terms of the CT character in the int-conformation.

Ternary blend polymer solar cells with wide-range light harvesting (Conference Presentation)

Polymer-based solar cells have made rapid progress in the last decade and are currently attracting a great deal of attention as a next-generation solar cell. Very recently, they have shown a power conversion efficiency (PCE) of more than 10%, which is comparable to that reported for amorphous silicon solar cells. However, it is still required to improve the photovoltaic performance furthermore for practical applications. In this talk, I will demonstrate ternary blend polymer solar cells, which are a new approach to improving the photocurrent generation. We have recently developed ternary blend polymer solar cells based on a wide-bandgap polymer, poly(3-hexylthiophene) (P3HT), a fullerene derivative (PCBM), and a near-IR dye molecule such as a silicon phthalocyanine derivative (SiPc). Such near-IR dye addition can easily expand the light-harvesting wavelength range up to the near-IR region, and hence can boost the photocurrent furthermore. I will demonstrate how molecular design of near-IR dye molecules can control the location in ternary blend solar cells to improve the photocurrent generation effectively. We also have fabricated ternary blend polymer solar cells based on a wide-bandgap polymer, a low-bandgap polymer, and PCBM. This two-donor polymer blend can also expand the light-harvesting wavelength and hence can boost the photocurrent effectively. Efficient exciton harvesting and charge collection can be designed by combining a wide-bandgap crystalline polymer and a low-bandgap amorphous polymer.