Electronic supplementary information for the manuscript

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

Contents

Scheme S1 Synthesis of PDIs 2

Figure S1. DSC curves for selected PDIs on heating and

cooling

2

Figure S2 Transfer characteristics of OFETs based on

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

3

Figure S3. Thermal profile of X-ray images for PDI-C6 4

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

unit cell of PDI-C8

5

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

direction, calculated from X-ray data for different samples

5

Table S1 Thermal characteristics of PDIs determined by

DSC

6

Table S2. The electron mobilities determined in OFETs for

annealed and non-annealed PDI films

7

Table S3. Unit cell parameters for selected PDIs in thin

films

8

Scheme S1 Synthesis of PDIs

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

a b

c d

2 4 61E-12

1E-10

1E-8

1E-6 IGS IDS

I, A

VGS, V

VDS = 5 V

0 2 4

1E-10

1E-9

1E-8

1E-7

1E-6

IGS IDS

I, A

VGS, V

VDS =5 V

0 2 4

1E-10

1E-9

1E-8

1E-7

1E-6

IGS IDS

I, A

VGS, V

VDS = 5 V

0 4 8

1E-10

1E-9

1E-8

1E-7

1E-6

IGS IDS

I, A

VGS, V

VDS = 8 V

Figure S2. Transfer characteristics of OFETs based on 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.

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

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.

Table S1 Thermal characteristics of PDIs determined by DSC.PDIs heating cooling

TptTpt, 0C H, J/g Tpt, 0C H, J/g

PDI-С4 -  - -  -

PDI-С5

114 5.98 107 6.90 7

215 16.17

PDI-С6

196 32.64 132 30.11 64

250 11.00 218 8.06 32

PDI-С7 214 43.73 129 43.13 85

PDI-С8 224 44.21 167 48.22 57

PDI-EH 69 3.59 54 4.24 15

PDI-С10

73 1.34 70 1.04 6

193 43.30 166 45.26 27

PDI-С12

91 10.54 76 13.66 15

163 21.88 143 41.30 20

180 18.90  172  0.31

211 1.62  180  0.77

Table S2. The electron mobilities determined in OFETs for annealed and non-annealed PDI films

PDIs

T,

0C

µsat av.(

µmax)

*, cm2V-1s-1

µ

max/

µRT

Non-

annealed 80 130 180 220 250

PDI-

C4

1.2×10-2

±9.9×10-4

(1.3×10-2)

2.0×10-2

±3.7×10-3

(2.4×10-2)

3.2×10-2

±4.8×10-3

(3.5×10-2)

2.2×10-2

±7.1×10-3

(3.2×10-2)

2.7×10-2

±2.1×10-3

(2.8×10-2)

-

2.6

PDI-

C5

9.0×10-3

±1.6×10-3

(1.1×10-2)

2,7×10-2

±8,7×10-3

(4,0×10-2)

5.4×10-2

±8.5×10-3

(6.6×10-2)

1.3×10-2

±3.6×10-3

(1.9×10-2)

8.5×10-3

±1.1×10-3

(9.8×10-3)

7.3×10-3

±3.8×10-4

(7.5×10-3)

6.0

PDI-

C6

5.8×10-3

±2.9×10-4

(6.1×10-3)

2.2×10-2

±2.9×10-3

(2.4×10-2)

4.3×10-2

±2.0×10-2

(7.4×10-2)

5.0×10-2

±2.1×10-2

(7.6×10-2)

1.5×10-1

±3.4×10-2

(1.8×10-1)

1.2×10-1

±2.7×10-2

(1.5×10-1)

25

PDI-

C7

2.4×10-2

±2.8×10-2

(8.6×10-2)

4.8×10-2

±1.1×10-2

(6.3×10-2)

6.5×10-2

±6.4×10-3

(7.0×10-2)

1.4×10-1

±5.2×10-2

(2.2×10-1)

1.0×10-1

±2.1×10-2

(1.2×10-1)

1.6×10-2

±5.5×10-3

(2.1×10-2)

5.8

PDI-

C8

1.8×10-2

±2.0×10-3

(1.9×10-2)

1.5×10-2

±3.9×10-3

(1.9×10-2)

2.4×10-2

±5.3×10-3

(3.1×10-2)

6.8×10-2

±2.0×10-2

(8.9×10-2)

1.0×10-1

±3.3×10-2

(1.2×10-1)

8.5×10-2

±2.4×10-2

(1.1×10-1)

5.6

PDI-

C10

2.7×10-2

±7.4×10-3

3.9×10-2

±1.8×10-2

7.1×10-2

±2.5×10-3

3.9×10-2

±5.6×10-3

4.0×10-2

±3.9×10-3

4.0×10-2

±4.5×10-4

2.6

(3.6×10-2) (7.0×10-2) (7.4×10-2) (4.4×10-2) (4.3×10-2) (4.1×10-2)

PDI-

C12

5.0×10-2

±5.1×10-3

(5.6×10-2)

4.7×10-2

±3.4×10-3

(5.0×10-2)

4.0×10-2

±1.7×10-2

(6.5×10-2)

7.1×10-2

±1.3×10-2

(8.8×10-2)

8.0×10-2

±3.8×10-3

(8.3×10-2)

9.3×10-2

±5.0×10-3

(1.0×10-1)

1.9

PDI-

EH

9.5×10-5

±2.4×10-5

(1.1×10-4)

6.5×10-5

±1.7×10-5

(8.0×10-5)

1.7×10-4

±1.2×10-4

(2.6×10-4)

1.1×10-2

±8.5×10-3

(2.4×10-2)

6.7×10-2

±8.2×10-3

(7.3×10-2)

5.8×10-2

±1.1×10-2

(6.4×10-2)

708

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

are given in parentheses.

Table S3. Unit cell parameters for selected PDIs in thin filmsPDIs Cell parameters

PDI-C4 a=15.3 Å, b=8.3 Å, c=4.7 Å;

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;

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

PDI-C8 a=22.3 Å, b=9.3 Å, c=5.2 Å;

α=111.5o, β=104o, γ=93.3o

PDI-C10 a=24.2 Å, b=8.6 Å,c=4.8 Å;

α=79o, β=106o,  γ=101o