Disubstituted perylene diimides in organic field-effect transistors: Effect of the alkyl side chains and thermal annealing on the device performance

Accepted Manuscript Disubstituted perylene diimides in organic field-effect transistors: Effect of the alkyl side chains and thermal annealing on the device performance Lidiya I. Kuznetsova, Alexey A. Piryazev, Denis V. Anokhin, Alexander V. Mumyatov, Diana K. Susarova, Dimitri A. Ivanov, Pavel A. Troshin PII:

S1566-1199(18)30132-0

DOI:

10.1016/j.orgel.2018.03.026

Reference:

ORGELE 4584

To appear in:

Organic Electronics

Received Date: 19 November 2017 Revised Date:

10 March 2018

Accepted Date: 13 March 2018

Please cite this article as: L.I. Kuznetsova, A.A. Piryazev, D.V. Anokhin, A.V. Mumyatov, D.K. Susarova, D.A. Ivanov, P.A. Troshin, Disubstituted perylene diimides in organic field-effect transistors: Effect of the alkyl side chains and thermal annealing on the device performance, Organic Electronics (2018), doi: 10.1016/j.orgel.2018.03.026. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT Disubstituted perylene diimides in organic field-effect transistors: effect of the

alkyl side chains and thermal annealing on the device performance Lidiya I. Kuznetsovaa, Alexey A. Piryazevb, Denis V. Anokhina,b, Alexander V. Mumyatova,

a

IPCP RAS, Semenov Prospect 1, Chernogolovka, 141432, Russia

b

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Diana K. Susarovaa, Dimitri A. Ivanovb,c and Pavel A. Troshin*,d,a

Lomonosov Moscow State University, Faculty of Fundamental Physical and Chemical Engineering, GSP-1, 1-51 Leninskie Gory, Moscow, 119991, Russia c

Institut de Sciences des Mateґriaux de Mulhouse, CNRS UMR 7361, 15 Jean Starcky, F-68057 Mulhouse,

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France d

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Skolkovo Institute of Science and Technology, Nobel st. 3, Moscow, 143026, Russian Federation

Graphical Abstract

N

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initial mobility mobility for annealed films

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PDIs

Highlights

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2 -1 -1 µ sat ,µcme, V cms V s sat

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Alkyl chains attached to the PDI core define electrical properties of these materials

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Thermal annealing is crucial for achieving best performance of PDIs resulted in OFETs

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Optimal thermal annealing regimes correlate with the phase transitions of PDIs

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OFET performance of PDIs correlates with their phase transition enthalpies

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DSC measurements can speed up screening of organic semiconductors in OFETs

* Corresponding author: e-mail [email protected], Phone: +7 496522 1418, Fax: +7 496515 5420

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Keywords

organic semiconductors, organic field-effect transistors, thin-film crystal structure, perylene diimides, thermal analysis

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Abstract Using a series of eight substituted perylene diimides (PDIs) we have explored the effects of the side chains and thermal annealing of the semiconductor films on their electrical characteristics in

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organic field-effect transistors (OFETs). Clear correlations between the thermally-induced improvement in the crystallinity of PDI films, their phase transition temperatures determined by

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DSC measurements and the electrical characteristics of the OFETs have been revealed. It has been also demonstrated that the best charge carrier mobilities are delivered by PDIs showing the highest enthalpies of the phase transitions, manifesting particularly strong intermolecular interactions in these crystalline solids. On the other hand, the length of alkyl side chains

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represent a crucial parameter governing the device performance. PDIs with the linear C6-C8 alkyl side chains showed the highest charge-carrier mobilities when annealed in optimal regimes, which correlates well with the thermal and structural characteristics of these materials. Finally,

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we show that DSC can be considered as a very useful technique to speed up the discovery of new promising semiconductor materials via screening for the highest phase transition enthalpies and

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performing film annealing near the phase transition temperatures.

1. Introduction

Organic electronics represents one of the most rapidly progressing fields in materials science. A great progress has been made in the development of organic solar cells, field-effect transistors (OFETs) and light-emitting diodes. It is assumed that OFETs might become a basis for designing high-tech products for mass applications: RFID tags, various sensors, matrix analyzers,

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photodetectors and medical diagnostics devices. For example, OFET-based chemical sensors operating in gas and liquid media have already demonstrated record-breaking characteristics including ultra-high sensitivity and excellent selectivity achieved via use of biological receptor molecules such as antibodies or DNA aptamers [1,2].

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Nowadays the concept of “green” electronics becomes more and more attractive to both research community and industry focusing on the development of new innovative products. It is known that conventional electronics generates a lot of “electronic” waste, which can hardly be recycled

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using standard approaches due to the presence of numerous toxic components such as heavy metals and other dangerous elements, including selenium, cadmium, antimony, arsenic, mercury

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and etc. [3]. On the contrary, organic electronics opens unique opportunities for designing electronic products, which can be completely safe for consumers and have no negative impact on the environment at the production, usage and recycling stages of the life cycle. To achieve this goal, one has to focus on the development of low toxicity and environmentally friendly organic

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materials with the semiconductor, dielectric and metal-type conductor functionalities. It has been demonstrated previously that many such materials can be identified while considering approved food and cosmetics components, particularly, the colorants.

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Perylene diimides (PDIs) represent a well-known family of promising organic semiconductor

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materials demonstrating good charge-transport properties in combination with low acute toxicity [4]. For instance, some of the PDI derivatives are used as red pigments in a lipstick [5]. OFETs using PDIs as semiconductor materials showed the n-type charge carrier mobilities of >1 cm2V1 -1

s [6]. Additionally, some of the functionalized PDIs were considered as promising materials

for the single-molecule electronic devices and as active components of the gas sensors [7,8]. On the one hand, the electrical performance of organic field-effect transistors (OFETs) depends strongly on the supramolecular orientation of semiconductor molecules in thin films. On the other hand, the self-assembly of the semiconductor molecules is governed by the alkyl

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substituents attached to the conjugated backbone. In particular, we have shown recently that the length of the alkyl substituents attached to the PDI core affects both the charge-carrier mobility and the on-off current ratio of the transistors [9]. Some reports also showed that thermal treatment can improve significantly the electrical performance of certain PDI derivatives [10–

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13]. However, to the best of our knowledge, no detailed studies were performed in order to correlate the thermal behaviour of PDI derivatives with their performance in OFETs in the context of the length of the attached alkyl substituents.

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In the present work we have addressed this challenge via a systematic investigation of thermal properties of eight disubstituded PDIs with C4-C12 linear alkyl side chains, their supramolecular

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organization in thin films annealed at different temperatures as well as the dependences of their electrical characteristics (field-effect mobility) on the annealing temperatures and the phase transition enthalpies.

The synthesis of PDIs with different alkyl substituents (Fig. 1) was carried out according to a

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known procedure involving the condensation of perylene-3,4,9,10-tetracarboxylic dianhydride with an appropriate aliphatic amine in a high-boiling solvent (quinoline) with the addition of a catalytic amount of zinc acetate (Scheme S1) [14]. The materials were purified by multiple

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thermal gradient sublimation in vacuum as described previously [10].

Figure 1 Chemical structures of the investigated PDIs.

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2. Results and discussion

The investigation of the thermal behavior of the materials was carried out using differential scanning calorimetry (DSC) in the temperature range from 25 to 300 0С. All PDIs have shown rather characteristic DSC curves with different number of phase transitions (Fig. 2 and Fig. S1 in

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SI). The thermal properties of PDIs are summarized in Table S1 (SI). It should be noted that characteristics of PDI-C7, PDI-C8, PDI-C12 were fully consistent with the previous reports

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[15,16].

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PDI-C6

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Figure 2 Representative DSC profiles of several PDIs recorded in heating and cooling regimes

ACCEPTED MANUSCRIPT Virtually all observed phase transitions were reversible, i.e. repeatedly appearing in both heating and cooling regimes. It should be noted that the temperature difference between the peaks, corresponding to the same phase transition and recorded while heating and cooling the sample,

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was shown to be dependent on the molecular structure of the material. The smallest thermal hysteresis was revealed by compounds PDI-C5, PDI-EH, PDI-C10, PDI-C12, while the largest was observed for PDIs with the medium length C6-C8 alkyl substituents. The latter compounds,

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in particular PDI-C6, have highly crystalline structures and their transition to new polymorphs is associated with the substantial thermal effects. As it was shown previously for

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dialkylquaterthiophenes, the DSC peak at lower temperature is associated with the crystal-tocrystal transition [17]. For high-temperature crystal modification the molecular conformation is different due to partial disordering of alkyl substituents. Evidently, thermal stability of this phase strongly depends on the volume fraction of the alkyl periphery. During annealing at the

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temperatures above the first transition, significant molecular rearrangements are possible resulting in ordering of the crystal phase and growth of the crystalline domains. The electrical performance of PDIs was investigated in the bottom-gate top-contact transistor

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geometry using Al2O3 as a gate dielectric and benzocyclobutene-silicon resin (BCB) as a

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thermally stable passivation coating [18,19]. The semiconductor films were deposited by thermal evaporation of PDIs in high vacuum. The deposited films were generally annealed at 80, 130, 220, 250 0С within 30 min and afterwards source and drain electrodes were deposited. The fieldeffect mobilities of as-deposited and thermally annealed films estimated in the saturation regime are presented in Table S2 (SI). Thermal treatment had a different impact on the OFET performance of PDIs with different side chains. For example, thin films of PDI-C12 were insensitive to the annealing and showed charge carrier mobility ranging from 5.0×10-2 cm2V-1s-1 to 1.0×10-1 cm2V-1s-1 depending on the

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annealing temperature (Fig. 3a-b and Table S2, SI). A completely different behaviour was exhibited by other perylenediimides. In particular, the mobility of PDI-C6 was increased by a factor of 25 by annealing of the thin films at 220 0C. Most remarkable improvement was observed for PDI-EH, which showed 700 times higher mobility after annealing at 220 0C (Fig.

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3b). It is interesting to note that PDI-C12 was showing the highest mobility before annealing, while the PDI-EH was giving the lowest one. However, applying thermal annealing to thin films of these PDIs resulted in very comparable electrical performance of these two materials as can be

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concluded from the data shown in Fig. 3 and Table S2 (SI).

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Figure 3 Evolution of the transfer characteristics of OFETs based on PDIs C12 and EH upon thermal annealing (a). Temperature dependences of the field-effect mobility for selected PDIs (b). The effect of the thermal annealing on the electrical performance of PDIs with different side chains (c).

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General overview of the effects induced by thermal annealing of PDIs in thin films on their electrical performance is given in Fig. 3c (see also temperature dependences of µ in Fig. S2, SI). Notably, the compounds with the shortest (C4, C5) and the longest (C10, C12) alkyl side chains behave in a similar way and show no significant effects upon thermal annealing. On the contrary,

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the OFET performances of PDIs with medium-length linear alkyl chains (from C6 to C8) were greatly enhanced by annealing at 220-250 oC. The obtained results proved unambiguously that both alkyl side chain length and the thermal annealing have a crucial influence on the electrical

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performance of PDIs. The best-performing devices can be fabricated only using the materials with appropriate side chains (e.g. C6 or C7) annealed under optimal conditions.

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In order to get a mechanistic understanding of the thermal annealing effect on the electrical performance of the PDIs thin films, we explored evolution of their morphology with increase in the temperature using atomic force microscopy (AFM). Figure 4 shows representative behavior of PDI-C6: non-annealed films consist of multiple poorly-ordered small grains, which are not

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well interconnected, while applying thermal treatment resulted in significant increase in the domain size even at 130 oC and the formation of large well-oriented terraces at 220 oC. Such final film structure is supposed to be beneficial for OFET operation due to the dramatically

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reduced number of grain boundaries limiting the lateral charge transport.

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Figure 4 AFM surface topography of thin films of PDI-C6 deposited on BCB before (a) and

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after thermal treatment at: 130 0C (b), 180 0C (c) and 220 0C (d).

Figure 5 GIWAXS patterns and 2D profiles (lower raw) of thin films of PDI-C5, PDI-C6 and PDI-EH before (upper raw) and after (central raw) applying thermal annealing.

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Thermal treatment can also have a strong impact on the film crystallinity and the orientation of the domains with respect to the substrate. Indeed, the Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) images shown in Fig. 5 strongly suggest that annealing results in a substantial improvement of the PDI-C6 film structure, as can be evident from the narrowing of

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the scattering peaks and increase in their intensity. Structural changes of the films during the annealing were studied by the temperature-resolved GIWAXS (Fig. S3, SI). Analysis of the peak positions revealed that the first phase transition of

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PDI-C6 film at ~150oC is accompanied by increase of a-parameter from 17.9 to 19.4 Å. Such behaviour is associated with the partial disordering of alkyl side chains and corresponding

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change of molecular conformation and tilt angle of PDI core in respect to the normal direction. Similar phase transition from highly-ordered crystal phase to locally disordered phase was revealed for dioctyl- and didecyl-substituted quaterthiophenes under thermal annealing [17]. The obtained results are in line with the DSC data.

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Analysis of the crystal structure of PDIs by GIWAXS revealed the triclinic unit cell symmetry and molecular packing similar to that found for PDI-C8 [20]. The ab- and ac-projections of PDIC8 unit cell are presented in Fig.S4. The increase in the alkyl chain length following the series

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PDI-C4 – PDI-C12 results in the increased a-parameter (Table S3). Starting from PDI-C4, the

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dependence of a parameter on the chain length (number of carbon atoms) shows a linear behavior indicating that the conformation of molecules in the crystal lattice is similar for all PDIs. Fig. S5 (SI) shows the molecular tilt angles calculated from the azimuthal position of the peaks at the GIWAXS patterns of PDIs films following the procedure described previously [21]. One can see a minor increase in the tilt angle while going from shorter to longer alkyl chains. Considering the fact that tilt angles are comparable for all PDIs, their electrical properties are influenced mainly by thermal treatment rather than molecular orientation with respect to the substrate.

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Thus, the obtained results have indicated that thermal annealing and side chain length are essential for preparing PDIs films with optimal morphology and crystal structure favoring their application in OFETs. However, revealing optimal annealing temperatures for each material experimentally represents a big effort and can be very time- and material-demanding. Therefore,

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it is essential to find some rational way for identification of the most suitable annealing regimes without performing an extensive empirical screening. We have addressed this challenge and compared the annealing temperatures giving the best OFET performances for the investigated

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PDIs with the temperatures of the phase transitions of these materials observed on the DSC curves recorded in the sample heating regime (Fig. 6a). Indeed, the optimal annealing

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temperatures favoring the device performance are generally localized near the phase transition intervals: the single (C4, C7 and C8), the first (C5 and C10) or the second (C6 and C12). Only the PDI-EH does not follow this dependence: the optimal annealing regime lies well above the phase transition presumably because evolution of its highly disordered structure is kinetically hindered and requires more time and energy (heat) for complete accomplishment. Therefore, while

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optimizing the OFET performance of a new semiconductor material it is recommended first to investigate its thermal properties (DSC), identify the phase transition intervals and then perform

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annealing of the films at these temperatures. Another important feature revealed in these experiments was a pretty good correlation of the

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maximal field-effect mobility achieved for the annealed PDIs films and the enthalpies (∆H) of the corresponding phase transitions (closest to the annealing temperature, Fig. 6b). Indeed, PDIs with the short (C4, C5), long (C10) and branched (EH) alkyl side chains showed the smallest ∆H values and the lowest charge carrier mobilities. On the contrary, PDIs with the medium-length side chains (C6, C7 and C8) revealed the largest enthalpies of the phase transitions and the highest field-effect mobilities. Only PDI-C12 did not follow this trend, since its ∆H is considerably higher, while µ is considerably lower compared to e.g. PDI-C6. This discrepancy can be related

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to the presence of two different polymorphs in the PDI-C12 films, which results in additional disorder and impairs the charge carrier transport.

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Figure 6 Optimal thin film annealing temperatures resulting in the best OFET performances compared to the phase transition temperatures of the used PDIs (a). The correlation between the highest charge-carrier mobility achieved for PDIs and enthalpies of their phase transitions (b).

The observation of the correlation between the phase transition enthalpies of the semiconductor materials and their electrical performance in OFETs was not very surprising. On the one hand,

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the ∆H value can be considered as a figure of merit characterizing in some way the overall energy gain from the intermolecular interactions of the semiconductor molecules in the crystals. On the other hand, transport of the charge carriers in thin films of organic semiconductors depends crucially on π-stacking effects and strength of the electronic coupling between the

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neighboring molecules in the stack [21]. 3. Materials and methods

Solvents: mesitylene, were purchased from Chimmed. The dielectric BCB was obtained under

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the trade name CYCLOTENE 4024 resin as a product of The Dow Chemical Company.

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3.1 OFET fabrication

A 1 mm wide and 200 nm thick aluminum gate electrodes were deposited by thermal evaporation onto 1.5 × 1.5 cm2 glass slides. They were subsequently anodized by immersing in a citric acid solution (0.2 g per 100 mL) in a potentiostatic regime at 10 V to achieve the formation

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of uniform AlOx coating. Afterwards, the samples were rinsed with deionized water and dried in an oven at 80 oC for 30 min. Organic dielectric coatings were deposited immediately after taking

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the samples out from the oven.

Benzocyclobutene derivative BCB was deposited from a commercial CYCLOTENE 4024 resin

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solution diluted with mesitylene in 1:50 v/v ratio. The obtained solution was spin-coated onto the Al/AlOx substrates at 1500 rpm. The resulting coatings were annealed overnight on a hot plate at 280 oC inside argon glove box. Semiconductor films of PDIs were grown on the organic dielectric coating by thermal evaporation from a resistively heated quartz crucible at the pressure of 2 × 10−6 mbar with the rate of 0.6 Ǻ/s. The typical thickness of PDI films was 100 nm. Annealing of thin films of PDIs was carried out for 30 min at 80, 130, 220, 250 0С inside argon glove box at standard pressure (slightly above atmospheric). Silver source and drain electrodes (typically 100 nm) were

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evaporated through a shadow mask (L = 50 µm, W = 2 mm) at the pressure of ~ 10−6 mbar. Transistor characterization was carried out inside an argon glove box with <1 ppm O2 and <1 ppm H2O. The transfer and output characteristics were recorded using Kethley 2612A instrument with LabTracer software.

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3.2 The GIWAXS measurements The GIWAXS measurements were performed on ID10 beamline of ESRF (Grenoble, France) with beam energy of 10keV. Two-dimensional diffraction patterns were recorded at different

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temperature using Pilatus 300k detector with sample-to-detector distance ~24 cm. The incidence

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angle was 0.16°. Linkam heating stage adopted for GIWAXS geometry was used for hightemperature experiments for all experiments. The modulus of the scattering vector s (s = 2sinθ/λ, where θ is the Bragg angle) was calibrated using several diffraction orders of silver behenate powder. The indexing of corrected for geometrical distortions 2D-GIWAXS patterns was

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performed in home-made routine written in Igor Pro software. 3.3 The DSC and AFM measurements

DSC measurements were performed for samples (~10 mg) in aluminum crucibles with lids using

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Perkin Elmer DSC 8500 with 20 deg/min heating rate in nitrogen atmosphere., Standard Perkin

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Elmer software was used for calculating the peak parameters (temperature ranges, enthalpies and etc.). NTEGRA PRIMA instrument (NT MDT, Russia) was used to obtain the AFM images. 4. Conclusions

In conclusion, we have performed a systematic study of the thermal behavior and electrical characteristics for eight different perylene diimides bearing C4-C12 alkyl substituents. It has been shown that both the length of the alkyl side chains attached to the PDI core and the thermal treatment applied to the semiconductor films have a crucial influence on the OFET performance. Thus, PDIs with the shortest (C4-C5) and the longest (C10-C12) alkyl substituents were rather

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insensitive to the thermal treatment since their OFET characteristics were improved just by a factor of 2-5 after thermal annealing. On the contrary, the field-effect mobilities of PDIs with the medium-length (C6-C8) and branched (EH) side chains were significantly enhanced by annealing. In case of PDI-C6 the improvement factor was ~25, while in case of PDI-EH in

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approached spectacular value of >700. AFM microscopy and GIWAXS measurements have shown that superior electrical performance of the annealed PDI films is mostly related to the improved films morphology (larger domain size, better orientation, reduced grain boundaries).

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Particularly exciting was the fact that optimal annealing regimes resulting in the best OFET performances correlated well with the temperatures of the phase transitions of the PDIs used as

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semiconductor materials. This observation can simplify significantly the optimization of the film processing parameters generally applied to all new promising semiconductor materials. Moreover, we have shown that the ultimate electrical performance of PDIs correlates well with the enthalpies of their phase transitions. This means that by running simple DSC measurements

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one might be able to perform a rational high-throughput screening of a wide range of semiconductor materials in order to identify those of them, which show the highest phasetransition enthalpies (translated to the strongest intermolecular coupling in the crystal lattice) and

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have a promise to give the best characteristics in OFETs.

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Acknowledgements

This work was supported by the Russian Science Foundation (project № 16-13-10467). The GIWAXS measurements were supported by the scholarships of the President of the Russian Federation for young scientists and graduate students (№SP-2238.2016.1). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at______ References

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B.A. Jones, A. Facchetti, M.R. Wasielewski, T.J. Marks, Tuning orbital energetics in

arylene diimide semiconductors. Materials design for ambient stability of n-type charge transport, J. Am. Chem. Soc. 129 (2007) 15259–15278. doi:10.1021/ja075242e. [17]

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charge carrier mobility, J. Phys. Chem. C. 116 (2012) 22727-22736. doi:10.1021/jp307054r.

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M. Ullah, D.M. Taylor, R. Schwödiauer, H. Sitter, S. Bauer, N.S. Sariciftci, T.B. Singh,

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Electrical response of highly ordered organic thin film metal-insulator-semiconductor devices, J. Appl. Phys. 106 (2009) 114505. doi:10.1063/1.3267045. [20] A.L. Briseno, S.C.B. Mannsfeld, C. Reese, J.M. Hancock, Y. Xiong, S.A. Jenekhe, Z. Bao,

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Y. Xia, Perylenediimide nanowires and their use in fabricating field-effect transistors and

AC C

complementary inverters, Nano Lett. 7 (2007) 2847-2853. doi: 10.1021/nl071495u. [21]

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Electronic supplementary information for the manuscript

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Disubstituted perylene diimides in organic field-effect transistors: effect of the alkyl side chains and thermal annealing on the device performance By Lidiya I. Kuznetsova, Alexey A. Piryazev, Denis V. Anokhin, Alexander V. Mumyatov, Diana K. Susarova, Dimitri A. Ivanov and Pavel A. Troshin

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Contents Scheme S1 Synthesis of PDIs

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Figure S1. DSC curves for selected PDIs on heating and cooling

Figure S2 Transfer characteristics of OFETs based on

2 2

3

PDI-EH (a,b) and PDI-C12 (c,d) without (a,c) and with thermal annealing at 250 0C (b) and 220 0C (d) respectively

4

Figure S4. ab-(left) and ac-(right) projections of triclinic

5

unit cell of PDI-C8

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Figure S3. Thermal profile of X-ray images for PDI-C6

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Figure S5. Tilt angle of PDI block in respect to normal

5

direction, calculated from X-ray data for different samples Table S1 Thermal characteristics of PDIs determined by

6

AC C

DSC

Table S2. The electron mobilities determined in OFETs for

7

annealed and non-annealed PDI films Table S3. Unit cell parameters for selected PDIs in thin films

8

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Scheme S1 Synthesis of PDIs

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AC C

EP

Q, mW

TE D

PDI-C4

0

0

50

50

100

PDI-C5

PDI-C7

150

200

250

300

PDI-C10

100

150 200 o T, C

250

300

Figure S1. DSC curves for selected PDIs on heating and cooling

ACCEPTED MANUSCRIPT

a

b

1E-6

VDS = 5 V

1E-6

IDS

1E-7

I, A

I, A

1E-8

IGS

1E-10

VDS =5 V

IGS IDS

1E-8 1E-9

2

4

6

VGS, V

0

c

d

1E-6

1E-6

VDS = 5 V IDS

1E-8

2

VGS, V

4

VDS = 8 V

IGS

SC

IGS

1E-7

I, A

I, A

1E-7

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1E-10

1E-12

IDS

1E-8 1E-9

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1E-9

1E-10

1E-10 0

2

VGS, V

4

0

4

VGS, V

8

AC C

EP

TE D

Figure S2. Transfer characteristics of OFETs based on PDI-EH (a,b) and PDIC12 (c,d) without (a,c) and with thermal annealing at 250 0C (b) and 220 0C (d) respectively.

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AC C

EP

TE D

Figure S3. Thermal profile of X-ray images for PDI-C6.

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AC C

EP

TE D

Figure S4. ab-(left) and ac-(right) projections of triclinic unit cell of PDI-C8.

Figure S5. Tilt angle of PDI block with respect to the normal direction, calculated from X-ray data for different samples.

ACCEPTED MANUSCRIPT Table S1 Thermal characteristics of PDIs determined by DSC. heating

cooling

∆ H, J/g

Tpt, 0C

∆ H, J/g

-

-

-

-

114

5.98

107

6.90

215

16.17

196

32.64

132

30.11

PDI-С6

250

11.00

218

8.06

PDI-С7

214

43.73

129

43.13

PDI-С8

224

44.21

167

48.22

PDI-EH

69

3.59

73

1.34

193

43.30

91

10.54

PDI-С10

163 PDI-С12 180

AC C

64 32 85 57

54

4.24

15

70

1.04

6

166

45.26

27

76

13.66

15 20

21.88

143

41.30

18.90

172

0.31

1.62

180

0.77

EP

211

7

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PDI-С5

TE D

PDI-С4

∆Tpt

SC

Tpt, 0C

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PDIs

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Table S2. The electron mobilities determined in OFETs for annealed and nonannealed PDI films PDIs

µ

sat av.(

µ

max)

*, cm2V-1s-1

µ

/µ max

Non0

C5

PDIC6

PDIC7

PDIC8

PDIC10

PDI-

1.2×10-2

2.0×10-2

3.2×10-2

2.2×10-2

±9.9×10-4

±3.7×10-3

±4.8×10-3

±7.1×10-3

±2.1×10-3

(1.3×10-2)

(2.4×10-2)

(3.5×10-2)

(3.2×10-2)

(2.8×10-2)

9.0×10-3

2,7×10-2

5.4×10-2

1.3×10-2

8.5×10-3

7.3×10-3

±1.6×10-3

±8,7×10-3

±8.5×10-3

±3.6×10-3

±1.1×10-3

±3.8×10-4

(1.1×10-2)

(4,0×10-2)

(6.6×10-2)

(1.9×10-2)

(9.8×10-3)

(7.5×10-3)

5.8×10-3

2.2×10-2

4.3×10-2

5.0×10-2

1.5×10-1

1.2×10-1

±2.9×10-4

±2.9×10-3

±2.0×10-2

±2.1×10-2

±3.4×10-2

±2.7×10-2

(6.1×10-3)

(2.4×10-2)

(7.4×10-2)

(7.6×10-2)

(1.8×10-1)

(1.5×10-1)

2.4×10-2

4.8×10-2

6.5×10-2

1.4×10-1

1.0×10-1

1.6×10-2

±2.8×10-2 (8.6×10-2)

220

250

2.7×10-2

-

SC

180

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PDI-

130

TE D

C4

80

EP

PDI-

annealed

2.6

±1.1×10-2

±6.4×10-3

±5.2×10-2

±2.1×10-2

±5.5×10-3

(6.3×10-2)

(7.0×10-2)

(2.2×10-1)

(1.2×10-1)

(2.1×10-2)

AC C

T, C

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T

1.8×10-2

1.5×10-2

2.4×10-2

6.8×10-2

1.0×10-1

8.5×10-2

±2.0×10-3

±3.9×10-3

±5.3×10-3

±2.0×10-2

±3.3×10-2

±2.4×10-2

(1.9×10-2)

(1.9×10-2)

(3.1×10-2)

(8.9×10-2)

(1.2×10-1)

(1.1×10-1)

2.7×10-2

3.9×10-2

7.1×10-2

3.9×10-2

4.0×10-2

4.0×10-2

±7.4×10-3

±1.8×10-2

±2.5×10-3

±5.6×10-3

±3.9×10-3

±4.5×10-4

(3.6×10-2)

(7.0×10-2)

(7.4×10-2)

(4.4×10-2)

(4.3×10-2)

(4.1×10-2)

5.0×10-2

4.7×10-2

4.0×10-2

7.1×10-2

8.0×10-2

9.3×10-2

6.0

25

5.8

5.6

2.6

1.9

R

±1.7×10

±1.3×10

±3.8×10-3

±5.0×10-3

(5.0×10-2)

(6.5×10-2)

(8.8×10-2)

(8.3×10-2)

(1.0×10-1)

9.5×10-5

6.5×10-5

1.7×10-4

1.1×10-2

6.7×10-2

5.8×10-2

±2.4×10-5

±1.7×10-5

±1.2×10-4

±8.5×10-3

±8.2×10-3

±1.1×10-2

(1.1×10-4)

(8.0×10-5)

(2.6×10-4)

(2.4×10-2)

(7.3×10-2)

(6.4×10-2)

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(5.6×10-2)

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708

*- The saturation mobility represents the average value for at least 4 devices. Maximum values are given in parentheses.

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Table S3. Unit cell parameters for selected PDIs in thin films PDIs

a=15.3 Å, b=8.3 Å, c=4.7 Å;

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PDI-C4

Cell parameters

α=91.1o, β=93.1o, γ=78.1o

PDI-C5

a=17 Å, b=8.5 Å, c=4.7 Å; α=85.4o, β=102.1o, γ=95.4o

PDI-C6

a=17.9 Å, b=8.3 Å, c=4.7 Å;

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EH

±3.4×10-3

α=87.3o, β=71.6o, γ=61.8o

PDI-C7

a=20.18 Å, b=8.34 Å, c=4.73 Å; α=76.4o, β=97.0o, γ=90o

EP

PDI-

±5.1×10-3

PDI-C8

AC C

C12

PDI-C10

a=22.3 Å, b=9.3 Å, c=5.2 Å; α=111.5o, β=104o, γ=93.3o a=24.2 Å, b=8.6 Å,c=4.8 Å; α=79o, β=106o, γ=101o