[Organic Semiconductor Group]2022 Research Introduction1

Projects
1

Selective control of molecular orientation✓ Sci. Rep. 2019, 9 (1), 579.

2

Understanding of crystal growth at the substrate interface✓ Appl. Phys. Express 2020, 13 (9), 095505.

3

Control and analysis of on-surface reactions✓ Sci. Rep. 2022, 12 (1), 4448.
✓ J. Phys. Chem. C 2021, 125 (4), 2437–2445.

4Porphyrin-based supramolecular organizations✓ Chem. Commun. 2022, 58 (13), 2116–2119.
✓ Cryst. Growth Des. 2021, 21 (9), 5116–5125.
✓ Chem. Eur. J. 2016, 22 (46), 16539–16546.

2

Projects
1

Selective control of molecular orientation✓ Sci. Rep. 2019, 9 (1), 579.

2

Understanding of crystal growth at the substrate interface✓ Appl. Phys. Express 2020, 13 (9), 095505.

3

Control and analysis of on-surface reactions✓ Sci. Rep. 2022, 12 (1), 4448.
✓ J. Phys. Chem. C 2021, 125 (4), 2437–2445.

4Porphyrin-based supramolecular organizations✓ Chem. Commun. 2022, 58 (13), 2116–2119.
✓ Cryst. Growth Des. 2021, 21 (9), 5116–5125.
✓ Chem. Eur. J. 2016, 22 (46), 16539–16546.

3

Molecular orientation of organic semiconductors
Selective control of molecular orientation

End-onFace-on4

Alternative face-on thin film structure of pentacene
904

0.14g(CH)

737

833

955

End-on

OP
IP

910

0.08

Tsub = 298 K

0.06g(CH)

950

900
850-1
Wavenumber / cm

742

731

733
1000

843
835

01050

Tsub = 210 K

Face-on

892

0.02

905

0.04

956

Absorbance

0.1

729

0.12IP
OP

800

750

OP
700

IP

Achievement of face-on orientation of pentacene on siliconSci. Rep. 2019, 9, 579.

5

Projects1

Selective control of molecular orientation✓ Sci. Rep. 2019, 9 (1), 579.

2

Understanding of crystal growth at the substrate interface✓ Appl. Phys. Express 2020, 13 (9), 095505.

3

Control and analysis of on-surface reactions✓ Sci. Rep. 2022, 12 (1), 4448.
✓ J. Phys. Chem. C 2021, 125 (4), 2437–2445.

4Porphyrin-based supramolecular organizations✓ Chem. Commun. 2022, 58 (13), 2116–2119.
✓ Cryst. Growth Des. 2021, 21 (9), 5116–5125.
✓ Chem. Eur. J. 2016, 22 (46), 16539–16546.

6

Thin-film phases of organic semiconductors
Thin-film phase1.44 nm1.54 nm

Bulk phase001
d001 =
1.54 nmd001 =
1.44 nm

Mattheus et al., Synth. Met. 2003, 138, 475.

1.62 nmIntensity / a.u.

001

55.2

5.4
5.6
2 theta / deg

5.8?
6d001 =
1.62 nm7Hidden thin-film phase of DNTTSoller slit (Conventional)
X-ray

X-ray

Intensity / a.u.

Ge monochromator (High resolution)

003

d001 = 1.624 nm

d001 = 1.633 nm
Conv.

Bulk phaseΔd001 = 0.009 nm

Thin-film phase(cf., 0.10 nm for PEN)High res.

11.2

11.4

11.6

11.8

qz / nm-1

Identification of thin-film phase of DNTT on siliconAppl. Phys. Express 2020, 13, 095505.

8

Projects
1

Selective control of molecular orientation✓ Sci. Rep. 2019, 9 (1), 579.

2

Understanding of crystal growth at the substrate interface✓ Appl. Phys. Express 2020, 13 (9), 095505.

3

Control and analysis of on-surface reactions✓ Sci. Rep. 2022, 12 (1), 4448.
✓ J. Phys. Chem. C 2021, 125 (4), 2437–2445.

4Porphyrin-based supramolecular organizations✓ Chem. Commun. 2022, 58 (13), 2116–2119.
✓ Cryst. Growth Des. 2021, 21 (9), 5116–5125.
✓ Chem. Eur. J. 2016, 22 (46), 16539–16546.

9

Thermal conversion of DNTT precursors
ΔEndo-isomer

3.35 cm2 V-1 s-1

Exo-isomer
OFETmobility

DNTT

0.94 cm2 V-1 s-1[1] Hamaguchi, A. et al. Adv. Mater. 2015. 27, 6606.
[2] Kimura, Y. et al. Adv. Mater. 2015. 27, 727.

The structure-property relationship remains unresolved.
10

Stereoisomer-dependent conversion

Endo-isomer(High mobility)

Exo-isomer(Low mobility)

DNTT

Control of on-surface reactions of DNTT precursors
Sci. Rep. 2022, 12, 44448.

11

Projects1Selective control of molecular orientation✓ Sci. Rep. 2019, 9 (1), 579.

2

Understanding of crystal growth at the substrate interface✓ Appl. Phys. Express 2020, 13 (9), 095505.

3

Control and analysis of on-surface reactions✓ Sci. Rep. 2022, 12 (1), 4448.
✓ J. Phys. Chem. C 2021, 125 (4), 2437–2445.

4Porphyrin-based supramolecular organizations✓ Chem. Commun. 2022, 58 (13), 2116–2119.
✓ Cryst. Growth Des. 2021, 21 (9), 5116–5125.
✓ Chem. Eur. J. 2016, 22 (46), 16539–16546.

12

Supramolecular organizations in thin films✓ Molecular design strategy for face-on orientation
C-H/π interaction

Hydrogen bonding

C-H/N interaction

Yokoyama. D. et al. Adv. Funct. Mater.
2011, 21, 1375.

✓ Molecular design strategy for edge-on orientation

No report!
13

Control of supramolecular organizations
M2+

Fe2+Co2+

Ni2+Cu2+

Edge-onRandomFace-onFace-ond x2-y2d z2
Molecularorientation

Metal/N coordination

C–H/N interaction

Achievement of edge-on orientation of porphyrins
Chem. Commun. 2022, 58, 2116.

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