ABSTRACT
We investigate the charge-generation processes limiting the performance of low-offset organic bulk-heterojunction solar cells by studying a series of newly synthesized PBDB-T-derivative donor polymers whose ionisation energy (IE) is tuned via functional group (difluorination or cyanation) and backbone (thiophene or selenophene bridge) modifications. When blended with the acceptor Y6, the series present heterojunction donor-acceptor IE offsets (ΔEIE) ranging from 0.22 to 0.59 eV. As expected, small ΔEIE decrease nonradiative voltage losses but severely suppresses photocurrent generation. We explore the origin of this reduced charge-generation efficiency at low ΔEIE through a combination of opto-electronic and spectroscopic measurements and molecular and device-level modeling. We find that, in addition to the expected decrease in local exciton dissociation efficiency, reducing ΔEIE also strongly reduces the charge transfer (CT) state dissociation efficiency, demonstrating that poor CT-state dissociation can limit the performance of low-offset heterojunction solar cells.
ABSTRACT
One of the main assumptions in the design of new conjugated polymer materials for their use in organic electronics is that higher coplanarity leads to greater conjugation along the polymer backbone. Conventionally, a more planar monomer structure induces a larger backbone coplanarity, thus leading to a greater overlap of the carbon π-orbitals and therefore a higher degree of π-electron delocalisation. However, here we present a case that counters the validity of this assumption. Different diselenophene-based polymers were studied where one polymer possesses two selenophene rings fused together to create a more rigid, planar structure. The effects of this greater polymer coplanarity were examined using Raman spectroscopy and theoretical calculations. Raman spectra showed a large difference between the vibrational modes of the fused and unfused polymers, indicating very different electronic structures. Resonance Raman spectroscopy confirmed the rigidity of the fused selenophene polymer and also revealed, by studying the excitation profiles of the different bands, the presence of two shorter, uncoupled conjugation pathways. Supported by Density Functional Theory (DFT) calculations, we have demonstrated that the reason for this lack of conjugation is a distortion of the selenophene rings due to the induced planarity, forming a new truncated conjugation pathway through the selenophene ß-position and bypassing the beneficial α-position. This effect was studied using DFT in an ample range of derivatives, where substitution of the selenium atom with other heteroatoms still maintained the same unconventional conjugation-planarity relationship, confirming the generality of this phenomenon. This work establishes an important structure-property relationship for conjugated polymers that will help rational design of more efficient organic electronics materials.
ABSTRACT
The synthesis and characterization of asymmetric alkoxy- are reported, fluoro-benzothiadiazole (BT) acceptor core derivatized with a series of six different heterocycles (selenophene, thiophene, furan, 5-thiazole, 2-thiazole and 2-oxazole). The effect of the flanked-heterocycles containing different chalcogen atoms of the six homopolymers (HPX) is studied using optical, thermal, electrochemical, and computational analysis. Computational calculations indicate a strong relationship between the most stable conformation for each homopolymer and their bearing heterocycle, thus homopolymers HPSe', HPTp', HPFu', and HPTzC5, adopted the syn-syn and syn-anti conformations due to their noncovalent interactions with shorter distances, while HPTzC2' and HPOx' demonstrate preference for the anti-anti conformation. Optical property studies of the homopolymers reveal a strong red-shift in solution and film upon exchanging the chalcogen atom from Oxygen < Sulfur < Selenium in HPFu, HPTp, and HPSe, respectively. In addition, deeper highest occupied molecular orbital (HOMO) energy levels are observed when the donor-acceptor moieties (HPSe, HPTp, and HPFu) are substituted for the acceptor-acceptor systems such as HPTzC5, HPTzC2, and HPOx. Improved packing and morphology are exhibited for the donor-acceptor homopolymers. Thus, having a flanked heterocycle containing different chalcogen-atoms in polymeric systems is one way of tuning the physicochemical properties of conjugated materials for optoelectronic applications.
Subject(s)
Chalcogens , Thiadiazoles , Chalcogens/chemistry , Oxygen/chemistryABSTRACT
Ladder-type thiazole-fused S,N-heteroacenes with an extended π-conjugation consisting of six (SN6-Tz) and nine (SN9-Tz) fused aromatic rings have been synthesized and fully characterized. To date, the synthesis of well-defined fused building blocks and polymers of π-conjugated organic compounds based on the thiazole moiety is a considerable synthetic challenge, due to the difficulty in their synthesis. Acceptor-donor building blocks M1 and M2 were successfully polymerized into ladder homopolymers P1-P2 and further copolymerized with a diketopyrrolopyrrole unit to afford step-ladder copolymer P3. The optical, electronic, and thermal properties, in addition to their charge transport behavior in organic thin-film transistors (OTFTs), were investigated. The results showed an interesting effect on the molecular arrangement of the thiazole-based ladder-type heteroacene in the crystal structure revealing skewed π-π-stacking, and expected to possess better p-type semiconducting performance. The polymers all possess good molecular weights and excellent thermal properties. All the polymer-based OTFT devices exhibit annealing temperature dependent performance, and among the polymers P3 exhibits the highest mobility of 0.05 cm2 V-1 s-1.
