An official website of the United States government
In inorganic materials, an alloy is a mixture of two or more substances that generally exhibits electronic and/or physical properties that differ from those of its constituents. In organic systems, the formation of a “molecular alloy” comprising mixtures of molecular organic materials has also been proposed. We test the validity of this concept via the study of the optoelectronic properties of a ternary system that has previously been identified to form a molecular acceptor alloy, namely a blend of a poly(3-hexylthiophene) (P3HT) donor, with two acceptors indene-C 60 bisadduct (ICBA) and phenyl-C 61 -butyric acid methyl ester (PC 61 BM) [R. A. Street, et al. , J. Am. Chem. Soc. , 2013, 135 , 986–989]. Using photoelectron spectroscopy, we find that the ICBA:PC 61 BM blend shows the same highest occupied molecular orbital and exciton energies as that of ICBA, indicating the absence of a new exciton state in the blend. Furthermore, charge transfer state spectra of ternary blends are found to comprise a simple linear superposition of the corresponding binaries. From these results, no evidence of new, emergent electronic states is found to support the existence of a molecular alloy in this system. To our knowledge there is as yet no clear evidence of the existence of an alloy in any organic semiconductor system. We discuss the criteria that should be met by a molecular organic alloy and procedures needed for their unambiguous identification.
more »
« less
Balanced Charge Transport Optimizes Industry‐Relevant Ternary Polymer Solar Cells
Bulk heterojunction polymer solar cells based on a novel combination of materials are fabricated using industry‐compliant conditions for large area manufacturing. The relatively low‐cost polymer PTQ10 is paired with the nonfullerene acceptor 4TIC‐4F. Devices are processed using a nonhalogenated solvent to comply with industrial usage in absence of any thermal treatment to minimize the energy footprint of the fabrication. No solvent additive is used. Adding the well‐known and low‐cost fullerene derivative PC61BM acceptor to this binary blend to form a ternary blend, the power conversion efficiency (PCE) is improved from 8.4% to 9.9% due to increased fill factor (FF) and open‐circuit voltage (VOC) while simultaneously improving the stability. The introduction of PC61BM is able to balance the hole–electron mobility in the ternary blends, which is favourable for high FF. This charge transport behavior is correlated with the bulk heterojunction (BHJ) morphology deduced from grazing‐incidence wide‐angle X‐ray scattering (GIWAXS), atomic force microscopy (AFM), and surface energy analysis. In addition, the industrial figure of merit (i‐FOM) of this ternary blend is found to increase drastically upon addition of PC61BM due to an increased performance–stability–cost balance.
more »
« less
- Award ID(s):
- 1639429
- PAR ID:
- 10240496
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Solar RRL
- Volume:
- 4
- Issue:
- 11
- ISSN:
- 2367-198X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The photocurrent multiplication (PM) effect has been used to boost the device performance of polymer‐based photodetectors (PDs), but its origin is rarely addressed. In this study, the origins of the PM effect in polymer PDs based on the P3HT:PC71BM bulk heterojunction (BHJ) composite thin film, where P3HT is poly(3‐hexylthiophene), and PC71BM is [6,6]phenyl‐C71‐butyric acid methyl ester, through both computational simulation and experimental investigation are reported. Systematic studies indicate that two key factors play an important role in the realization of the PM effect in polymer PDs. One factor is the work function of the metal electrode, and the other is the PC71BM aggregations at the interface between the P3HT:PC71BM BHJ composite thin film and the metal electrode. Moreover, the results from both experimental and computational simulation indicate that the values of the current density under light illumination minus the current density in the dark of polymer PDs are increased simultaneously along with the reduction of the thickness of the P3HT:PC71BM BHJ composite thin film. The results provide an understanding of the PM effect in polymer PDs and guidance for the development of high‐performance polymer PDs based on BHJ composite thin film.more » « less
-
Abstract Ultraviolet (UV), visible, and near‐infrared (NIR) broadband organic photodetectors are fabricated by sequential solution‐based thin film coatings of a polymer electron blocking layer (EBL) and a polymer photoactive layer. To avoid damage to a preceding polymer EBL during a subsequent solution‐based film coating of a polymer photoactive layer due to lack of solvent orthogonality, 2‐(((4‐azido‐2,3,5,6‐tetrafluorobenzoyl)oxy)methyl)−2‐ethylpropane‐1,3‐diyl bis(4‐azido‐2,3,5,6‐tetrafluorobenzoate) (FPA‐3F) is used as a novel organic cross‐linking agent activated by UV irradiation with a wavelength of 254 nm. Solution‐processed poly[N,N′‐bis(4‐butylphenyl)‐N,N′‐bis(phenyl)‐benzidine] (poly‐TPD) films, which are cross‐linked with a FPA‐3F photocrosslinker, are used for a preceding polymer EBL. A ternary blend film composed of PTB7‐Th, COi8DFIC, and PC71BM is used as a NIR‐sensitive organic photoactive layer with strong photosensitivity in multispectral (UV–visible–NIR) wavelengths of 300–1,050 nm. Poly‐TPD films are successfully cross‐linked even with a very small amount of 1 wt% FPA‐3F. Small amounts of FPA‐3F have little detrimental effect on the electrical and optoelectronic properties of the cross‐linked poly‐TPD EBL. Finally, organic NIR photodetectors with a poly‐TPD EBL cross‐linked by the small addition of FPA‐3F (1 wt%) show the detectivity values higher than 1 × 1012Jones for the entire UV–visible–NIR wavelengths from 300 nm to 1050 nm, and the maximum detectivity values of 1.41 × 1013Jones and 8.90 × 1012Jones at the NIR wavelengths of 900 and 1000 nm, respectively.more » « less
-
ABSTRACT Ternary block copolymer (BCP)‐homopolymer (HP) blends offer a simple method for tuning nanostructure sizes to meet application‐specific demands. Comprehensive dissipative particle dynamic (DPD) simulations were performed to study the impact of polymer interactions, molecular weight, and HP volume fraction (φHP) on symmetric ternary blend morphological stability and domain spacing. DPD reproduces key features of the experimental phase diagram, including lamellar domain swelling with increasingφHP, the formation of an asymmetric bicontinuous microemulsion at a critical HP concentration , and macrophase separation with further HP addition. Simulation results matched experimental values for and lamellar swelling as a function of HP to BCP chain length ratio,α = NHP/NBCP. Structural analysis of blends with fixedφHPbut varyingαconfirmed that ternary blends follow the wet/dry brush model of domain swelling with the miscibility of HPs and BCPs depending onα. Longer HPs concentrate in the center of domains, boosting their swelling efficiencies compared to shorter chains. These results advance our understanding of BCP‐HP blend phase behavior and demonstrate the value of DPD for studying polymeric blends. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys.2019,57, 794–803more » « less
-
null (Ed.)We present two-dimensional white-light spectroscopy (2DWL) measurements of binary and ternary bulk heterojunctions of the polymer donor PM6 mixed with state-of-the-art nonfullerene acceptors Y6 or IT4F. The ternary film has a shorter lifetime and faster spectral diffusion than either of the binary films. 2D line shape analysis of the PM6 ground state bleach with a Kubo model determines that all three films have similar amplitudes of fluctuations (Δ = 0.29 fs–1) in their transition frequencies, but different relaxation times (ranging from 102 to 24 fs). The ternary film exhibits faster dynamics than either of the binary films. The short lifetime of the ternary blend is consistent with increased photoexcitation transfer and the fast frequency fluctuations are consistent with structural dynamics of aliphatic side chains. These results suggest that the femtosecond fluctuations of PM6 are impacted by the choice of the acceptor molecules. We hypothesize that those dynamics are either indicative, or perhaps the initial source, of structural dynamics that ultimately contribute to solar cell operation.more » « less
