Ambipolarity and Dimensionality of Charge Transport in Crystalline Group 14 Phthalocyanines: A Computational Study

Gali, Sai Manoj; Matta, Micaela; Lessard, Benoît H.; Castet, Frédéric; Muccioli, Luca

doi:10.1021/acs.jpcc.7b11588

Cited by 21 publications

(42 citation statements)

References 56 publications

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“…These bulky groups may interfere with packing during film formation, impeding charge transport compared to 1 – 4 . DFT calculations for single crystals of 2–4 have previously been reported, potentially providing insight into the difference in performance between the three materials . Although single crystals of 2 were calculated to have a maximum μ e of 0.09 cm 2 V −1 s −1 , lower than the 0.20 and 0.19 cm 2 V −1 s −1 calculated for 3 and 4 , respectively, it is the only material to theoretically possess 2D charge transport pathways through its single crystal.…”

Section: Resultsmentioning

confidence: 94%

Ambipolarity and Air Stability of Silicon Phthalocyanine Organic Thin‐Film Transistors

Melville

Grant

Mirka

et al. 2019

Adv Elect Materials

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Silicon phthalocyanines (SiPcs) are a class of conjugated, planar molecule that have recently been investigated for use in organic photovoltaics (OPVs), organic light‐emitting diodes (OLEDs), and organic thin‐film transistors (OTFTs) due to their variable structure and ease of synthesis. Bottom‐gate, bottom‐contact OTFTs with four SiPc derivatives used as the semiconducting layers are prepared using physical vapor deposition. Devices using bis(pentafluorophenoxy) silicon phthalocyanine (F10‐SiPc) deposited on 140 °C substrates demonstrate electron field‐effect mobilities (μ) of up to 0.54 cm2 V−1 s−1, among the best currently reported for N‐type phthalocyanine‐based transistors. All materials show dramatic changes in charge transport when characterized under vacuum (P < 0.1 Pa) compared to in air at atmospheric pressure, typically switching from electron majority charge carriers to holes, with the change dependent on material structure and energetics. F10‐SiPc is close to balanced ambipolar in air, with μ around 5 × 10−3 cm2 V−1 s−1 for both holes and electrons. These results demonstrate SiPcs' potential as N‐type semiconductors in OTFTs as well as their adjustable charge transport as affected by operation environment.

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Section: Resultsmentioning

confidence: 94%

Ambipolarity and Air Stability of Silicon Phthalocyanine Organic Thin‐Film Transistors

Melville

Grant

Mirka

et al. 2019

Adv Elect Materials

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“…In summary, the combination of low reorganization energies and close π−π stacking of the LUMOlocalized terminal naphthyl groups leading to high electronic couplings is encouraging for future studies of ITN-C9 and, particularly, of ITzN-C9, where the electronic coupling distribution suggests a high charge transport dimensionality in crystalline domains. Kinetic Monte Carlo mobility calculations within the framework of Marcus−Jortner theory are planned to assess the exact dimensionality of charge transport (49).…”

Section: Resultsmentioning

confidence: 99%

Closely packed, low reorganization energy π-extended postfullerene acceptors for efficient polymer solar cells

Swick

Zhu

Matta

et al. 2018

Proc. Natl. Acad. Sci. U.S.A.

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136

160

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New organic semiconductors are essential for developing inexpensive, high-efficiency, solution-processable polymer solar cells (PSCs). PSC photoactive layers are typically fabricated by film-casting a donor polymer and a fullerene acceptor blend, with ensuing solvent evaporation and phase separation creating discrete conduits for photogenerated holes and electrons. Until recently, n-type fullerene acceptors dominated the PSC literature; however, indacenodithienothiophene (IDTT)-based acceptors have recently enabled remarkable PSC performance metrics, for reasons that are not entirely obvious. We report two isomeric IDTT-based acceptors 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-benz-(5, 6)indanone))-5,5,11,11-tetrakis(4-nonylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']di-thiophene (ITN-C9) and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-benz(6,7)indanone))-5,5,11,11-tetrakis(4-nonylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITzN-C9) that shed light on the exceptional IDTT properties vis-à-vis fullerenes. The neat acceptors and blends with fluoropolymer donor poly{[4,8-bis[5-(2- ethylhexyl)-4-fluoro-2-thienyl]benzo[1,2-b:4,5-]dithiophene2,6-diyl]--[2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo4H,8H-benzo[1,2-:4,5-]dithiophene-1,3-diyl]]} (PBDB-TF) are investigated by optical spectroscopy, cyclic voltammetry, thermogravimetric analysis, differential scanning calorimetry, single-crystal X-ray diffraction, photovoltaic response, space-charge-limited current transport, atomic force microscopy, grazing incidence wide-angle X-ray scattering, and density functional theory-level quantum chemical analysis. The data reveal that ITN-C9 and ITzN-C9 organize such that the lowest unoccupied molecular orbital-rich end groups have intermolecular π-π distances as close as 3.31(1) Å, with electronic coupling integrals as large as 38 meV, and internal reorganization energies as small as 0.133 eV, comparable to or superior to those in fullerenes. ITN-C9 and ITzN-C9 have broad solar-relevant optical absorption, and, when blended with PBDB-TF, afford devices with power conversion efficiencies near 10%. Performance differences between ITN-C9 and ITzN-C9 are understandable in terms of molecular and electronic structure distinctions via the influences on molecular packing and orientation with respect to the electrode.

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“…For this reason, accessing the full mobility tensor is crucial to align the fastest transport pathway with the charge transport direction (electric field direction). The anisotropic mobility can be reflected in a polar plot ( Figure 3 ), 144 where kMC simulations are performed with the electric fields applied in various directions. Even at the pairwise (dimer) level, this type of analysis is useful to rationalize the transport properties of different polymorphs.…”

Section: Beyond Dimersmentioning

confidence: 99%

“… Polar plots of hole (left, filled circles) and electron (right, empty circles) anisotropic mobility, computed for different disorder conditions (black and blue). Reprinted with permission from ref ( 144 ). Copyright 2018 American Chemical Society.…”

Section: Beyond Dimersmentioning

confidence: 99%

Read between the Molecules: Computational Insights into Organic Semiconductors

2018

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The performance and key electronic properties of molecular organic semiconductors are dictated by the interplay between the chemistry of the molecular core and the intermolecular factors of which manipulation has inspired both experimentalists and theorists. This Perspective presents major computational challenges and modern methodological strategies to advance the field. The discussion ranges from insights and design principles at the quantum chemical level, in-depth atomistic modeling based on multiscale protocols, morphological prediction and characterization as well as energy-property maps involving data-driven analysis. A personal overview of the past achievements and future direction is also provided.

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Ambipolarity and Dimensionality of Charge Transport in Crystalline Group 14 Phthalocyanines: A Computational Study

Cited by 21 publications

References 56 publications

Ambipolarity and Air Stability of Silicon Phthalocyanine Organic Thin‐Film Transistors

Ambipolarity and Air Stability of Silicon Phthalocyanine Organic Thin‐Film Transistors

Closely packed, low reorganization energy π-extended postfullerene acceptors for efficient polymer solar cells

Read between the Molecules: Computational Insights into Organic Semiconductors

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