Simultaneous control over both the energy levels and Fermi level, a key breakthrough for inorganic electronics, has yet to be shown for organic semiconductors. Here, energy level tuning and molecular doping are combined to demonstrate controlled shifts in ionisation potential and Fermi level of an organic thin film. This is achieved by p-doping a blend of two host molecules, zinc phthalocyanine and its eight-times fluorinated derivative, with tunable energy levels based on mixing ratio. The doping efficiency is found to depend on host mixing ratio, which is explained using a statistical model that includes both shifts of the host’s ionisation potentials and, importantly, the electron affinity of the dopant. Therefore, the energy level tuning effect has a crucial impact on the molecular doping process. The practice of comparing host and dopant energy levels must consider the long-range electrostatic shifts to consistently explain the doping mechanism in organic semiconductors.

. (2017) Structural stability of naphthyl end-capped oligothiophenes in organic field-effect transistors measured by grazingincidence X-ray diffraction in operando. Organic Electronics. Permanent WRAP URL:http://wrap.warwick.ac.uk/89989 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for-profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP URL' above for details on accessing the published version and note that access may require a subscription. AbstractWe report on microstructural durability of 5,5'-bis(naphth-2-yl)-2,2'-bithiophene (NaT2) in organic field effect transistors (OFETs) in operando monitored by grazing-incidence X-ray diffraction (GIXRD). NaT2 maintains its monoclinic bulk motif in operating OFETs with a = 20.31 ± 0.06Å, b = 6.00 ± 0.01Å, c = 8.17 ± 0.04Å and β = (96.64 ± 0.74)• . Crystallites appear as a mosaic of single crystals reaching through the whole 50 nm thick active layer. The lattice parameters variation (<1%) falls within the statistical error of structure refinement when the OFET gate voltage is varied from 0 V to -40 V; or when the OFET is continuously cycled within this voltage interval over more than 10 h period. Within the first few cycles, both the hole mobility and threshold voltage are changing but then reach stable levels with an average mobility of (3.25 ± 0.04) × 10 −4 cm 2 /Vs and an average threshold voltage of −13.6 ± 0.2 V, both varying less than 4% for the remainder of the 10 h period. This demonstrates crystalline stability of NaT2 in operating OFETs.

We use the electron spin as a probe to gain insight into the mechanism of molecular doping in a p-doped zinc phthalocyanine host across a broad range of temperatures (80–280 K) and doping concentrations (0–5 wt% of F6-TCNNQ).

Copolymers based on diketopyrrolopyrrole (DPP) cores have attracted a lot of attention because of their high p-type as well as n-type carrier mobilities in organic field-effect transistors (FETs) and high power conversion efficiencies in solar cell structures. We report the structural and charge transport properties of n-dialkyl side-chain-substituted thiophene DPP end-capped with a phenyl group (Ph-TDPP-Ph) monomer in FETs which were fabricated by vacuum deposition and solvent coating. Grazing-incidence X-ray diffraction (GIXRD) from bottom-gate, bottom-contact FET architectures was measured with and without biasing. Ph-TDPP-Ph reveals a polymorphic structure with π-conjugated stacking direction oriented in-plane. The unit cell comprises either one monomer with a = 20.89 Å, b = 13.02 Å, c = 5.85 Å, α = 101.4°, β = 90.6°, and γ = 94.7° for one phase (TR1) or two monomers with a = 24.92 Å, b = 25.59 Å, c = 5.42 Å, α = 80.3°, β = 83.5°, and γ = 111.8° for the second phase (TR2). The TR2 phase thus signals a shift from a coplanar to herringbone orientation of the molecules. The device performance is sensitive to the ratio of the two triclinic phases found in the film. Some of the best FET performances with p-type carrier mobilities of 0.1 cm/V s and an on/off ratio of 10 are for films that comprise mainly the TR1 phase. GIXRD from in operando FETs demonstrates the crystalline stability of Ph-TDPP-Ph.