Journal Pre-proof

Comparative studies on frontier orbitals, molecular packing and optoelectronic

properties of ambipolar polymer semiconductors based on bisthiophene-fused
diketopyrrolopyrrole

Lanchao Ma, Zhengang Li, Bing Chen, Xiaojian Zheng, Haiying Xie, Chengliang Ji,
Xiaowei Zhan, Yunqi Liu, Xingguo Chen
PII: S1566-1199(23)00165-9
DOI: https://doi.org/10.1016/j.orgel.2023.106909
Reference: ORGELE 106909

To appear in: Organic Electronics

Received Date: 16 July 2023

Revised Date: 20 August 2023
Accepted Date: 20 August 2023

Please cite this article as: L. Ma, Z. Li, B. Chen, X. Zheng, H. Xie, C. Ji, X. Zhan, Y. Liu, X. Chen,
Comparative studies on frontier orbitals, molecular packing and optoelectronic properties of ambipolar
polymer semiconductors based on bisthiophene-fused diketopyrrolopyrrole, Organic Electronics (2023),
doi: https://doi.org/10.1016/j.orgel.2023.106909.

This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition
of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of
record. This version will undergo additional copyediting, typesetting and review before it is published
in its final form, but we are providing this version to give early visibility of the article. 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.

© 2023 Published by Elsevier B.V.

 All the polymer semiconductors exhibited prominent ambipolar charge transport
property. P(DPPFu-TT) displayed the best charge transport property and P(DPPFu-BT)
showed ideally balanced charge carrier mobilities for both holes and electrons.
Relationships between comonomer structure, frontier orbital energy level, orbital
delocalization index, molecular packing, film morphology and the corresponding
charge transport properties were investigated systematically.

Ambipolar polymer semiconductors based on π-expanded

diketopyrrolopyrroles in field effect transistors

f
Lanchao Ma*†, Zhengang Li†, Bing Chen‡, Xiaojian Zheng§, Haiying Xie†, Chengliang

oo
Ji†, Xiaowei Zhan§, Yunqi Liuǁ, Xingguo Chen*‡

r
-p
re
lP
na
ur
Jo
 Comparative studies on frontier orbitals, molecular packing and

optoelectronic properties of ambipolar polymer semiconductors

based on bisthiophene-fused diketopyrrolopyrrole

Lanchao Ma*†, Zhengang Li†, Bing Chen‡, Xiaojian Zheng§, Haiying Xie†, Chengliang
Ji†, Xiaowei Zhan§, Yunqi Liuǁ, Xingguo Chen*‡
E-mail: 0020150027@bipt.edu.cn (L. Ma) and xgchen@whu.edu.cn(X. Chen)

†
College of New Materials and Chemical Engineering, Beijing Key Laboratory of

f
oo
Special Elastomer Composite Materials, Beijing Institute of Petrochemical Technology,
Beijing 102617, China

r
‡ -p
Hubei Key Laboratory on Organic and Polymeric Optoelectronic Materials, College
re
of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
§
School of Materials Science and Engineering, Peking University, Beijing 100871,
lP

China
ǁ
na

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic
Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
ur
Jo
 Abstract
Ambipolar field-effect transistors based on polymer semiconductors facilitate the
convenient fabrication of low-power complementary organic circuits. However, the
species of ambipolar polymer semiconductors are limited; the design and synthesis
strategies are scarce. This work demonstrated that bisthiophene-fused
diketopyrrolopyrrole (DPPFu) was a wonderful building unit for ambipolar polymer
semiconductors. Ambipolar polymer semiconductors could be obtained by
copolymerizing DPPFu with both electron-deficient comonomers and electron-rich
comonomers. P(DPPFu-T), P(DPPFu-TT) and P(DPPFu-BT) were synthesized by

f
oo
copolymerizing DPPFu with thiophene, thienothiophene and benzothiadiazole,
respectively. The structural variation of comonomers allowed for a systematic study on

r
-p
the relationship between comonomer structure, frontier orbital energy level, orbital
delocalization index, molecular packing, film morphology and the corresponding
re
charge transport properties. Thienothiophene endowed P(DPPFu-TT) with maximum
lP

orientation of edge-on packing. The considerable delocalization extent of the lowest

na

unoccupied molecular orbitals (LUMOs) for P(DPPFu-T) and P(DPPFu-TT) resulted

in pronounced electron transport property. P(DPPFu-TT) displayed the best charge
ur

transport property with hole mobility up to about 0.1 cm2V–1s–1 and electron mobility
Jo

of 7.5×10-2 cm2V–1s–1. P(DPPFu-BT) showed ideally balanced charge carrier mobilities

for both holes and electrons of 1.6×10-2 cm2V–1s–1 and 1.7×10-2 cm2V–1s–1, respectively.
Ion/Ioff ratios of all the ambipolar polymers were above 103. The ambipolarity of
polymer semiconductors was related to not only push-pull electronic characteristics of
comonomers, but also the planarity of polymer backbones and delocalization extent of
frontier orbitals. Overall, this study provides valuable insights into the design and
synthesis of ambipolar polymer semiconductors, which is crucial for the advancement
of low-power complementary organic circuits.
Keywords: ambipolar polymer semiconductors, bisthiophene-fused
diketopyrrolopyrrole, organic field-effect transistors

1. Introduction
 Ambipolar field-effect transistors (FETs) facilitate the fabrication of
complementary logic circuits, and endow the integrated circuits with low power
dissipation, wide noise margins and high robustness.1-3 As an important component for
ambipolar FETs, the semiconductor layer could conduct both electrons and holes.
Polymer semiconductors are of versatile chemical synthesis and solution processing,
which provides opportunities for low-cost fabrication of large-area flexible devices
such as smart cards, bendable displays, and radiofrequency identification (RFID) tags.4-
7
Consequently, ambipolar polymer semiconductors are attracting more and more
research interest.

f
oo
Donor-acceptor (D-A) strategy is widely used in the design of high-performance
polymer semiconductors for FETs. D-A copolymers offer significant potential in

r
-p
achieving tunable energy levels, robust intramolecular charge transfer (ICT), and
intermolecular interactions between adjacent polymer chains. Among the most
re
commonly used donor moieties are thiophene and its derivatives; while lactam, imide
lP

and thiazole derivatives are usually adopted as the acceptor units.8

na

Charge transport property of polymer semiconductors could be readily modulated

by engineering the donor and acceptor units,9 and the majority carrier type is
ur

determined by the relative strength of donor and acceptor components.10 For example,
Jo

diketopyrrolopyrrole (DPP)-thiophenes (Ts) copolymers, such as P(DPP-nT), exhibit

varying charge carrier types and mobility based on the number of thiophenes present.
Both P(DPP-2T) and P(DPP-3T) exhibit ambipolar charge transport, with hole transport
being dominant.11-13 However, an increase in the number of thiophenes enhances donor
strength and results in unipolar hole transport with increased mobility.14-16 To enhance
electron transport property, benzothiadiazole is incorporated. The introduction of
benzothiadiazole to P(DPP-2T) endows P(DPP-2T-BT) with balanced ambipolar
charge transport property.17 The hole and electron mobilities of P(DPP-2T-BT) are 0.35
cm2V-1s-1 and 0.40 cm2V-1s-1, respectively. P(DPP-2T-bisBT), synthesized by adding
one more benzothiadiazole to P(DPP-2T-BT), exhibits electron-dominant charge
transport property and the electron mobility is about one order of magnitude higher than
the hole mobility.18
 Electron-withdrawing (or donating) ability could be enhanced by incorporating
more acceptor (donor) moieties. Except that, electron-withdrawing ability could also
be improved by incorporating more electron withdrawing groups in the acceptor unit.
Thiadiazoloquinoxaline-fused acenaphthenequinone imide (TQAI) is a highly π-
expanded and sulfur/nitrogen enriched acceptor, a strong electron deficient unit. A
conjugated copolymer containing TQAI and thiophene derivatives demonstrates
ambipolar charge transport, with electron mobility approximately 4 times higher than
hole mobility.19
The interplay between donor and acceptor strengths could tune the electronic

f
oo
structure of polymer semiconductors, thus modulating charge carrier type and transport
property. Bisthiophene-fused DPP (DPPFu), a building block comprising both DPP

r
-p
(with electron-withdrawing properties) and thiophenes (with electron-donating
properties),10, 20, 21, 22 has been utilized to construct ambipolar semiconductors. PBDTT-
re
DPPFu, consisting of benzo[1,2-b:4,5-b′]dithiophene (BDTT) as the donor and DPPFu
lP

as the acceptor unit,20 was synthesized and compared to the unfused counterpart,
PBDTT-DPP. The hole mobility of PBDTT-DPPFu was about 1.8×10-3 cm2V–1s–1,
na

which was over one order of magnitude higher than that of PBDTT-DPP, while the
ur

electron mobility of PBDTT-DPPFu was about 1.0×10-2 cm2V–1s–1, which was more
Jo

than two times that of PBDTT-DPP. The results of UV-vis spectroscopy, DFT
calculation, ESP and vdW analyses, as well as XRD implied that ring-fusion methods
provided a robust approach to enhancing interchain interaction between chain segments
in polymer semiconductors.
In the construction of optoelectronic materials, DPPFu is often employed as an
electron acceptor and copolymerized with electron donors to construct D-A
copolymers.21 However, systematic investigation of polymer semiconductors based on
DPPFu remains limited. When utilizing bisthiophene-fused DPP as a building block for
copolymer semiconductors, several issues require analysis: 1. How does the double
bond in the fused ring impact the spatial and electronic structure of the DPPFu? 2. How
does the structure of comonomers affect the spatial configuration, molecular weight of
the copolymers, and chain packing in the thin films? 3. How does the electronic
property of comonomers affect the absorption spectra, frontier orbital energy levels,
charge carrier type and carrier mobility of the copolymer semiconductors?
In this work, DPPFu was synthesized by fusing the two N atoms in the DPP unit
with two flanking thiophenes, yielding a π-expanded, planar fused-ring building
block.21, 23-25
Additionally, 2-octyldodecyl side chains were attached to the fused
benzene rings to ensure good solubility of the building block. P(DPPFu-T), P(DPPFu-
TT) and P(DPPFu-BT) were synthesized by copolymerizing DPPFu with thiophene,
thienothiophene and benzothiadiazole, respectively. The molecular weight, absorption
spectrum, energy levels, and frontier orbital distribution of the copolymer

f
oo
semiconductors were compared. The relationship between the structure of copolymer
semiconductors and their molecular packing, film morphology and charge transport

r
-p
properties was also systematically investigated.
re
2. Results and discussion
lP

2.1 Molecular weight and thermal stability

na

Scheme 1 Synthetic routes of polymer semiconductors

ur
Jo
 f
r oo
-p
re
lP
na
ur

DPPFu (bisthiophene-fused DPP dibromide) was synthesized according to the previous

Jo

references.24, 26 Thiophene ditin, thienothiophene ditin and benzothiadiazole diboric acid ester were

purchased from Derthon Optoelectronics Materials Science Technology Co Ltd.

The synthetic routes for polymer semiconductors are depicted in Scheme 1.

P(DPPFu-T) and P(DPPFu-TT) were synthesized via Stille-coupling polymerization of
DPPFu dibromide with thiophene ditin and thienothiophene ditin, respecctively;
P(DPPFu-BT) was synthesized via Suzuki-coupling of DPPFu dibromide with
benzothiadiazole diborate. The crude products were purified by Soxhlet extraction
using methanol, acetone, and hexane successively to elute low molecular weight
oligomers and other impurities. Chloroform was used as the end-product solvent for
P(DPPFu-T) and P(DPPFu-TT), whereas hexane was used for P(DPPFu-BT). The
number-average molecular weight (Mn), weight-average molecular weight (Mw) and
polydispersity index (Mw/Mn) were listed in Table S1. The molecular weight of
P(DPPFu-BT) was the lowest among these polymers due to the low reaction
temperature. The reaction temperature for P(DPPFu-T) and P(DPPFu-TT) synthesis
was 90℃, whereas it was 70℃ for P(DPPFu-BT) synthesis. Higher reaction
temperatures provide more energy for the coupling reaction, while the lower reaction
temperature used for P(DPPFu-BT) synthesis supplies less energy, thereby reducing the
probability of coupling between DPPFu dibromide and benzothiadiazole diborate,
ultimately resulting in a lower molecular weight. The Mn of polymer semiconductors

f
oo
featuring DPPFu was often smaller than that of their unfused counterparts.20, 22 The
main reason was that the DPPFu was more rigid than its unfused counterpart and caused

r
-p
larger steric hindrance in the coupling reaction. The polymer semiconductors exhibited
high thermal stability, with decomposition temperatures above 370℃.
re
lP

2.2 DFT calculation

na
ur
Jo
 f
r oo
-p
re
lP
na
ur
Jo

Figure 1 Structural formulas, optimized geometries, frontier molecular orbitals of

(a) DPPFu-T_×2, (b) DPPFu-TT_×2 and (c)DPPFu-BT_×2.

To predict how comonomers can impact the spatial and electronic features of
polymer semiconductors, theoretical calculations were performed to evaluate the
dihedral angels, frontier orbital energy and orbital delocalization index (ODI) of these
polymer semiconductors. Density function theory (DFT) was employed in these
calculations, and geometries were optimized at the B3LYP level. For computational
simplicity, models comprising two repeating units (DPPFu-T_×2, DPPFu-TT_×2 and
DPPFu-BT_×2) were used, with branched alkyl chains replaced with methyl groups
(Figure 1). The absence of bulky branched alkyl chains resulted in all backbones
exhibiting good coplanarity. The dihedral angles between DPPFu and comonomers
were roughly 0.02°, 0.008° and 0.443° for DPPFu-T_×2, DPPFu-TT_×2 and DPPFu-
BT_×2, respectively. The dihedral angle in DPPFu-BT_×2 was slightly larger than that
in DPPFu-T_×2 and DPPFu-TT_×2. Additionally, the bond length between DPPFu and
comonomers in DPPFu-BT_×2 was about 0.02 Å longer than that in DPPFu-T_×2 and
DPPFu-TT_×2. The larger dihedral angle and longer bond length in DPPFu-BT_×2
could primarily be attributed to the steric hindrance caused by benzothiadiazole. Upon
the introduction of bulky side chains, the dihedral angle between diketopyrrolopyrrole
and fused thiophenes remained stable, while the dihedral angle between DPPFu and
comonomers likely increased.

f
oo
Using geometry optimization, ODI was calculated via the Multiwfn program with
Hirshfeld method as the base.27, 28 A smaller ODI value indicates that the orbitals are

r
-p
more spatially delocalized, with the orbitals being distributed across more atoms within
the molecule.20 The ODI versus molecular orbital index of DPPFu-T_×2, DPPFu-
re
TT_×2 and DPPFu-BT_×2 (from LUMO +10 down to HOMO-10) was plotted for
lP

comparison (Figure S2). The ODI of HOMO orbitals of DPPFu-T_×2, DPPFu-TT_×2

na

and DPPFu-BT_×2 were close to each other, suggesting comparable delocalization of

HOMO orbitals. The HOMO level of all the three dimers was about -4.5 eV, with their
ur

values being very close.

Jo

Despite similar ODI of HOMO orbitals in DPPFu-T_×2, DPPFu-TT_×2, and

DPPFu-BT_×2, there was a considerable difference in the ODI of LUMO orbitals. ODI
of LUMO in DPPFu-T_×2 and DPPFu-TT_×2 was markedly lower than that in DPPFu-
BT_×2, suggesting that LUMO orbitals were more widely distributed in DPPFu-T_×2
and DPPFu-TT_×2 compared to DPPFu-BT_×2. Additionally, the LUMO orbital in
DPPFu-BT_×2 was primarily localized on the benzothiadiazole unit. Despite the
LUMO orbital in DPPFu-BT_×2 being more localized, the LUMO level of DPPFu-
BT_×2 was noticeably lower than that of DPPFu-T_×2 and DPPFu-TT_×2.
Theoretical calculations were also performed on unfused models (DPP-T_×2,
DPP-TT_×2 and DPP-BT_×2) for comparison (Figure S1). In these models, the
dihedral angle between DPP and adjoining thiophene was around 10°, contrasting with
the 0° angle between DPP and the fused thiophene in the models featuring DPPFu. The
fusion between DPP and adjoining thiophenes helped to improve the coplanarity of
organic semiconductors. The HOMO level of models based on DPP was roughly -4.7
eV, with the fusion lifting the HOMO level by approximately 0.2 eV. The HOMO ODI
of models based on DPPFu increased by varying degrees, indicating that fusion reduced
the delocalization of HOMO orbitals. The LUMO level of DPPFu-T_×2 and DPPFu-
TT_×2 was slightly higher than that of DPP-T_×2 and DPP-TT_×2; whereas the
LUMO level of DPPFu-BT_×2 was slightly lower than that of DPP-BT_×2. After
fusion, the LUMO ODI of DPPFu-T_×2 and DPPFu-TT_×2 decreased, while that of
DPPFu-BT_×2 increased. Fusion was beneficial for LUMO delocalization in DPPFu-

f
oo
T_×2 and DPPFu-TT_×2, but it was unfavorable for LUMO delocalization in DPPFu-
BT_×2. In terms of changes in the HOMO and LUMO levels, fusion decreased the

r
-p
HOMO-LUMO gap by 0.2-0.3 eV. Therefore, fusion is a feasible approach to achieving
narrow-bandgap polymer semiconductors with good planarity.
re
lP

2.3 Optical and electrochemical properties

Table 1-1 Optical properties of polymer semiconductorsa
na

Solution Film
ur

a
λmax λmax λonset Egopt
Jo

(nm) (nm) (nm) (eV)

P(DPPFu-T) 420, 854 422, 785, 875 994 1.25

P(DPPFu-TT) 420, 772 423, 764, 838 982 1.26
P(DPPFu-BT) 407, 796 418, 833 1075 1.15
a The optical bandgap was calculated according to equation: Egopt = 1240/λonset.

Table 1-2 Redox potentials and energy levels of the polymer semiconductors
a b
Polymer Eox(V) Ered(V) HOMO(eV) LUMO(eV) EgCV(eV)

P(DPPFu-T) 0.72 -0.83 -4.98 -3.43 1.55

P(DPPFu-TT) 0.68 -0.97 -4.94 -3.29 1.65
P(DPPFu-BT) 0.75 -0.73 -5.01 -3.53 1.48
a Eox is the onset potential corresponding to oxidation, b Ered is the onset potential corresponding to reduction.

HOMO is short for highest occupied molecular orbital and LUMO is short for lowest unoccupied molecular orbital.

LUMO levels and HOMO levels are estimated from the onset reduction and oxidation potentials, respectively.

(EHOMO/LUMO = -(4.8 + 𝐸ox/red - 𝐸(Fc/Fc+)) eV)

f
r oo
-p
re
Figure 2 (a) UV-vis-NIR absorption spectra of polymer semiconductors in thin
films; (b) cyclic voltammogram (CV) curves of polymer semiconductors.
lP
na

UV-vis-NIR absorption spectra for solutions and thin films of P(DPPFu-T),

P(DPPFu-TT) and P(DPPFu-BT) were presented in Figure 2 and Figure S4. The
ur

absorption spectrum of P(DPPFu-T) and P(DPPFu-TT) solutions showed a broad

Jo

absorption range from 350 nm to 1000 nm. The absorption onset of P(DPPFu-BT)
solution reached 1100 nm, indicating efficient intramolecular charge transfer
originating from D-A structure along the backbone. The extensional absorption of
P(DPPFu-BT) solution was attributed to the introduction of benzothiadiazole with
strong electron-withdrawing ability, which endowed the polymer with strong electron
pull-push characteristics.
Comparing with the absorption of solutions, the absorption peaks of the
corresponding thin films all red-shifted. The shoulder peak was very apparent for the
absorption spectrum of P(DPPFu-TT) thin film; there was a tendency to form a shoulder
peak in the absorption spectrum of P(DPPFu-T) thin film; and the shoulder peak was
absent in the absorption spectrum of P(DPPFu-BT) thin film. The shoulder peak was
greatly related to the chain interactions through π-π stacking induced aggregation.
Among the comonomers of thiophene, thienothiophene and benzothiadiazole,
thienothiophene was the most beneficial for forming strong π-π interactions in
P(DPPFu-TT); and benzothiadiazole hindered the formation of strong π-π interactions
in P(DPPFu-BT).
The structural formula of polymer semiconductors made it clear that the adjacent
branched alkyl chains were in close proximity, causing significant steric hindrance, and
leading to torsion of polymer backbone, which was detrimental to molecular
organization in thin films (Scheme 1). In contrast, reducing steric hindrance could

f
oo
enhance molecular organization as exemplified by PDPP7T, where the branched alkyl
chains on DPP were spaced by septetthiophene. The sharp and intense shoulder peak in

r
-p
the absorption spectrum of PDPP7T confirmed its excellent molecular organization.16
Cyclic voltammetry (CV) curves were measured to quantitatively investigate the
re
effect of different comonomers on the redox potential and frontier orbital energy levels
lP

for these polymers (Figure 2).12 The frontier orbital energy was calculated according to
na

the equation of -(4.8 + 𝐸ox/red - 𝐸(Fc/Fc+)) eV. The introduction of an electron-

withdrawing group lowered both the LUMO and HOMO levels.29 The electron-
ur

withdrawing ability was in the order of benzothiadiazole thiophene thienothiophene.

Jo

Among the polymers studied, P(DPPFu-BT) exhibited the lowest LUMO and HOMO
energy levels and the smallest electrochemical gap.

2.4 Thin film morphology

Thin film morphology was characterized by atomic force microscopy (AFM)
(Figure S5). All the thin films were prepared by spin coating and exhibited fine film-
forming properties. The root-mean-square (RMS) roughness of all the thin films was
about 1 nm (Table S2).
All the as-prepared films displayed a granule-like morphology, indicating that
P(DPPFu-T), P(DPPFu-TT) and P(DPPFu-BT) had a tendency to self-aggregate in the
films. Upon thermal annealing, more connections between granules were formed.
Additionally, the granules in P(DPPFu-TT) film grew long and thin; whereas those in
P(DPPFu-BT) grew larger.

2.5 Molecular packing

f
r oo
-p
Figure 3 Grazing incidence X-ray diffraction (GIXRD) of polymer semiconductor
re
films. 2D GIXRD patterns of (a) P(DPPFu-T), (b) P(DPPFu-TT) and (c) P(DPPFu-BT)
lP

thin films after thermal annealing at 200℃. Schematic illustrations for stacking
orientations of (d) P(DPPFu-T), (e) P(DPPFu-TT) and (f) P(DPPFu-BT).
na
ur
Jo

Figure 4 GIXRD of polymer semiconductor films. Diffraction patterns along (a)

out-of-plane and (b) in-plane directions for polymer semiconductor films after thermal
annealing at 200℃.

The impact of comonomer structures on interchain packing in thin films of

P(DPPFu-T), P(DPPFu-TT), and P(DPPFu-BT) was thoroughly investigated using
grazing incidence X-ray diffraction (GIXRD).30 Figure 3 displayed the 2D diffraction
patterns of the thin films and Figure 4 presented 1D intensity profiles. In Table S4, the
position of diffraction peaks for lamellar stacking of interdigitated alkyl chains and
interchain π-π stacking, the corresponding distance of lamellar stacking and π-π
stacking, as well as the crystalline size, were summarized. The crystal size
perpendicular to the diffraction direction was calculated based on the full width at half-
maximum (fwhm) of (100) diffraction signals.
The 2D GIXRD analysis revealed distinct packing modes in the polymer films
(Figure 3). The thin film of P(DPPFu-T) predominantly exhibited a face-on packing

f
oo
mode; while the thin films of P (DPPFu-TT) and P(DPPFu-BT) primarily showed an
edge-on packing mode. All the thin films exhibited multiple diffraction orders. Based

r
-p
on Figures 3 and 4, P(DPPFu-T) displayed anisotropic diffraction along the in-plane
direction up to the (300) diffraction peak; P(DPPFu-TT) displayed anisotropic
re
diffraction along the out-of-plane direction up to the (400) diffraction peak; and
lP

P(DPPFu-BT) showed diffraction along the out-of-plane direction up to the (300)

na

diffraction peak.
A pole figure analysis of the 2D GIXRD patterns was conducted to quantitatively
ur

investigate the stacking orientation influenced by the comonomer unit structure (Figure
Jo

S7). Pole figures were extracted from the (100) lamellar diffraction peaks in 2D GIXRD
patterns, which were then integrated with polar angles of 0-45° and 135-180° (Axy)
representing face-on crystallites, and 45-135° (Az) representing edge-on crystallites,
respectively. The integrated area of Az and Axy for these thin films were presented in Table
S3.31, 32 The Az/Axy ratios were calculated as 34.4/65.6, 96.0/4.0 and 69.7/30.3 for the
as-prepared films of P(DPPFu-T), P(DPPFu-TT) and P(DPPFu-BT), respectively. After
thermal annealing at 200℃, these ratios changed to 25.3/74.7, 96.5/3.5 and 72.1/27.9.
These data implied that thermal annealing increased the packing orientation in all thin
films, enhancing the face-on content in P(DPPFu-T) and the edge-on content in
P(DPPFu-TT) and P(DPPFu-BT) thin films.33
It is worth noting that the structural changes of comonomers from P(DPPFu-T) to
P(DPPFu-TT) and P(DPPFu-BT) resulted in polymer semiconductors with distinct
backbone orientation.34 This variation in orientation is likely attributed to changes in
the surface energy of polymers and their interactions with the substrate.
d-spacing and π-π stacking distance could also be obtained from 1D GIXRD
patterns (Table S4). The d-spacing values ranged from 2.32 nm to 2.67 nm,
corresponding to diffraction peaks spanning from 3.3° to 3.8°. The d-spacing strongly
depended on the bisthiophene-fused DPP with branched alkyl chains, the fully extended
length of which was 3.68 nm, and the branched alkyl chains were interdigitated in the
thin films.
Among all the d-spacing values, the out-of-plane d-spacing in P(DPPFu-TT) was

f
oo
the shortest. This can be attributed to the fact that the horizontal length of
thienothiophene was longer than that of thiophene and benzothiadiazole, resulting in

r
-p
reduced spatial hindrance and a higher degree of interdigitation.
d-spacing was also related to the packing direction, which was very obvious for
re
P(DPPFu-BT) thin films. In this case, the in-plane d-spacing was larger than the out-
lP

of-plane d-spacing. The π-π stacking distance for all the polymer semiconductors was
na

between 0.34 nm and 0.35 nm, which was comparable with that for high-performance
polymer semiconductors based on DPP.4, 6, 35
ur

As face-on was the dominant packing mode in P(DPPFu-T) thin film, (100)
Jo

diffraction was mainly along the in-plane direction and crystal size was extracted along
out-of-plane direction; edge-on packing mode was dominant in P(DPPFu-TT) and
P(DPPFu-BT) thin films, (100) was mainly along the out-of-plane direction and crystal
size was extracted along the in-plane direction. Crystalline domain sizes in the
semiconductor films were evaluated using Scherrer equation. Crystalline domain sizes
of all the polymer semiconductors in the as-spun films were only a few nanometers.
Among them, the crystalline domain size of P(DPPFu-TT) was the largest. This could
be attributed to the longer horizontal length of thienothiophene, which reduced steric
hindrance and facilitated better packing of segments. After thermal annealing, the
crystalline domain sizes of all the polymer semiconductors increased to about a dozen
nanometers, which indicated improved microstructural ordering. Therefore, thermal
annealing resulted in improved carrier transport properties of OTFTs.
 2.6 Organic field-effect transistors

f
r oo
-p
re
lP
na
ur

Figure 5 Output and transfer curves of OFETs based on P(DPPFu-T) (a, b),
Jo

P(DPPFu-TT) (c, d) and P(DPPFu-BT) (e, f).

Table 2 Performance parameters of bottom-gate/bottom-contact (BGBC) OFETs

based on P(DPPFu-T), P(DPPFu-TT) and P(DPPFu-BT).
p-channel n-channel
μe /μh
–1 –1 –1 –1
μh (cm V s )
2
Ion/Ioff VT (V) μe (cm V s )
2
Ion/Ioff VT (V)
as prepared 2.6×10-3 2.6×103 8 2.7×10-4 4.7×10 62 0.11
P(DPPFu-T)
thermal annealing 2.4×10-3 5.7×103 -12 6.7×10-3 3.4×104 58 2.79
as prepared 6.3×10-2 3.1×102 13 8.4×10-3 3.3×10 85 0.13
P(DPPFu-TT)
thermal annealing 9.8×10-2 3.2×103 -27 7.5×10-2 1.4×103 55 0.76
-4 3 -5
as prepared 1.5×10 1.4×10 3 5.0×10 5.4×10 45 0.33
P(DPPFu-BT)
thermal annealing 1.6×10-2 1.6×104 -27 1.7×10-2 7.7×103 51 1.06

The parameters were extracted from the devices with performance of medium level among at least 5 devices
 Charge transport properties of these polymer semiconductors were evaluated using
bottom-gate/bottom-contact (BGBC) OFETs. All the OFETs exhibited ambipolar
charge transport property in the N2 atmosphere. The charge mobility (μh and μe), on/off
current ratio (Ion/Ioff) and threshold voltage (VT) were measured and compared for
OTFTs based on both as-prepared films and thermally annealed films (Table 2).
OTFTs based on as-prepared films exhibited hole-dominated charge transport
property, with the hole mobility being approximately 3-10 times higher than the
electron mobility. After thermal annealing at 200℃, the electron transport properties of
all the polymer semiconductors were significantly improved. As a result, all the OFETs

f
oo
exhibited clear ambipolar charge transport characteristics (Figure 5).
Au was utilized as source and drain electrodes, the Fermi level of which was well-

r
-p
matched with the HOMO level of polymer semiconductors. However, there was a
significant energy difference between LUMO level of these polymer semiconductors
re
and the Fermi level of Au. Thermal annealing made the contact between
lP

semiconductors and electrodes more compact, which facilitated the tunneling injection
na

of electrons from electrodes to semiconductors. As a result, the thermal annealing

process contributed to the improved performance and charge transport properties of
ur

OFETs in this study.

Jo

Electron transport of polymer semiconductors was also favorable. LUMO ODI

values of all the model compounds (Figure 1) were small, indicating well delocalized
LUMO orbitals. LUMO ODI values were even smaller than HOMO ODI values for
DPPFu-T_×2 and DPPFu-TT_×2. The delocalization not only facilitated charge
transport along polymer chains, but also promoted charge hopping between polymer
chains through favorable intermolecular coupling.
The electron and hole mobilities of P(DPPFu-T) were on the order of 10-3 cm2V–
1 –1
s , and those of P(DPPFu-TT) and P(DPPFu-BT) were on the order of 10-2 cm2V–1s–
1
magnitude. P(DPPFu-T) exhibited electron-dominated transport, while P(DPPFu-TT)
and P(DPPFu-BT) showed a balanced electron and hole transport property. Especially,
P(DPPFu-BT) demonstrated ideally balanced charge carrier mobilities for both
electrons and holes. DPPFu proved to be a suitable building block for the preparation
of copolymer semiconductors with ambipolar charge transport capabilities.
It is worth mentioning that charge transport performance of these polymer
semiconductors was inferior when compared to prevailing high-performance
semiconductors. The primary reason for this limitation was the bulky side chains, which
caused significant spatial hindrance. This hindrance reduced the planarity of the
polymer backbones and hindered the orderly packing of polymer chains, leading to
compromised charge transport properties.

Conclusion

f
oo
A series of polymer semiconductors, namely P(DPPFu-T), P(DPPFu-TT) and
P(DPPFu-BT), were successfully synthesized. These polymer semiconductors

r
-p
displayed remarkable thermal stability, broad absorption in the UV-Vis-NIR range, and
exhibited ambipolar charge transport properties.
re
Among the three polymer semiconductors, P(DPPFu-TT) exhibited the highest
lP

Mn, reaching 56.0 kg/mol. The HOMO and LUMO were the most delocalized in the
na

model DPPFu-TT_×2. Thin films of P(DPPFu-TT) predominantly adopted an edge-on

packing mode, with an edge-on/face-on ratio of 96.5/3.5. Charge transport properties
ur

of P(DPPFu-TT) were superior to the other two polymer semiconductors, owing to its
Jo

high molecular weight, delocalized frontier orbitals and the organized arrangement of
polymer chains. The hole and electron mobilities of P(DPPFu-TT) were 9.8×10-2 and
7.5×10-2 cm2V–1s–1, respectively.
In contrast, the Mn value of P(DPPFu-BT) was the lowest. Unlike DPPFu-T_×2
and DPPFu-TT_×2, the LUMO level in DPPFu-BT_×2 was more localized than the
HOMO level. Thin films of P(DPPFu-BT) predominantly exhibited an edge-on
packing mode, with an edge-on/face-on ratio of 72.1/27.9. P(DPPFu-BT)
demonstrated ideally balanced charge transport properties, with hole and electron
mobilities measured at 1.6×10-2 cm2V–1s–1 and 1.7×10-2 cm2V–1s–1, respectively.
Distinctly, thin film of P(DPPFu-T) mainly adopted a face-on packing mode,
with an edge-on/face-on ratio of 25.3/74.7, differing from P(DPPFu-TT) and
P(DPPFu-BT) thin films. P(DPPFu-T) displayed electron-dominated charge transport
properties, with the electron mobility approximately two times higher than hole
mobility. This suggests that the face-on packing mode potentially favors electron
transport.

Acknowledgements
This work was supported by Beijing Municipal Science and Technology Project
(KM201910017003), the Project of Cultivation for young top-notch Talents of Beijing
Municipal Institutions (BPHR202203093), Young Elite Scientists Sponsorship

f
oo
Program by BAST (BYESS2023089) and Beijing Natural Science Foundation
(2174074) and URT (2019J00031 and 2023J00074) program.

r
-p
The GIXRD data were obtained at BSRF-1W1A. The authors gratefully
acknowledge the cooperation of the beamline scientists at BSRF-1W1A beamline.
re
lP

Reference
na

1. Wang, H.; Wang, Y.; Ni, Z.; Turetta, N.; Gali, S. M.; Peng, H.; Yao, Y.; Chen, Y.; Janica, I.; Beljonne,
D.; Hu, W.; Ciesielski, A.; Samorì, P., 2D MXene–molecular hybrid additive for high‐performance
ur

ambipolar polymer field‐effect transistors and logic gates. Advanced Materials 2021, 33, 2008215.
Jo

2. Zhang, Y. H.; Wang, Y. S.; Gao, C.; Ni, Z. J.; Zhang, X. T.; Hu, W. P.; Dong, H. L., Recent advances
in n-type and ambipolar organic semiconductors and their multi-functional applications. Chemical
Society Reviews 2023, 52, 1331-1381.
3. Gamez-Valenzuela, S.; Comi, M.; Gonzalez, S. R.; Delgado, M. C. R.; Al-Hashimi, M.; Ortiz, R.
P., The fluorination effect: the importance of backbone planarity in achieving high performance
ambipolar field effect transistors. Journal of Materials Chemistry C 2023, 11, 8027-8036.
4. Liu, Q.; Bottle, S. E.; Sonar, P., Developments of diketopyrrolopyrrole‐dye‐based organic
semiconductors for a wide range of applications in electronics. Advanced Materials 2020, 32,
1903882.
5. Park, K. H.; Go, J.-Y.; Lim, B.; Noh, Y.-Y., Recent progress in lactam-based polymer
semiconductors for organic electronic devices. Journal of Polymer Science 2021, 60, 429-485.
6. Zhou, Y.; Zhang, W.; Yu, G., Recent structural evolution of lactam- and imide-functionalized
polymers applied in organic field-effect transistors and organic solar cells. Chemical Science 2021,
12, 6844-6878.
7. Shen, T.; Li, W. H.; Zhao, Y.; Liu, Y. Q.; Wang, Y., An all-C-H-activation strategy to rapidly
synthesize high-mobility well-balanced ambipolar semiconducting polymers. Matter 2022, 5,
1953-1968.
8. Wang, Z. L.; Shi, Y. B.; Deng, Y. F.; Han, Y.; Geng, Y. H., Toward high mobility green solvent-
processable conjugated polymers: A systematic study on chalcogen effect in
poly(diketopyrrolopyrrole-alt-terchalcogenophene)s. Advanced Functional Materials 2021, 31,
2104881.
9. Ashraf, R. S.; Meager, I.; Nikolka, M.; Kirkus, M.; Planells, M.; Schroeder, B. C.; Holliday, S.;
Hurhangee, M.; Nielsen, C. B.; Sirringhaus, H.; McCulloch, I., Chalcogenophene comonomer
comparison in small band gap diketopyrrolopyrrole-based conjugated polymers for high-
performing field-effect transistors and organic solar cells. Journal of the American Chemical
Society 2015, 137, 1314-1321.
10. Alonso-Navarro, M. J.; Harbuzaru, A.; de Echegaray, P.; Arrechea-Marcos, I.; Harillo-Banos,
A.; de la Pena, A.; Ramos, M. M.; Lopez Navarrete, J. T.; Campoy-Quiles, M.; Ponce Ortiz, R.; Segura,
J. L., Effective interplay of donor and acceptor groups for tuning optoelectronic properties in
oligothiophene-naphthalimide assemblies. Journal of Materials Chemistry C 2020, 8, 15277-15289.

f
11. Zoombelt, A. P.; Mathijssen, S. G. J.; Turbiez, M. G. R.; Wienk, M. M.; Janssen, R. A. J., Small

oo
band gap polymers based on diketopyrrolopyrrole. Journal of Materials Chemistry 2010, 20, 2240-
2246.

r
12. Lee, J. S.; Son, S. K.; Song, S.; Kim, H.; Lee, D. R.; Kim, K.; Ko, M. J.; Choi, D. H.; Kim, B.; Cho, J.
-p
H., Importance of solubilizing group and backbone planarity in low band gap polymers for high
performance ambipolar field-effect transistors. Chemistry of Materials 2012, 24, 1316-1323.
re
13. Bijleveld, J. C.; Zoombelt, A. P.; Mathijssen, S. G. J.; Wienk, M. M.; Turbiez, M.; de Leeuw, D. M.;
lP

Janssen, R. A. J., Poly(diketopyrrolopyrrole−terthiophene) for ambipolar logic and photovoltaics.

Journal of the American Chemical Society 2009, 131, 16616-16617.

na

14. Li, Y. N.; Sonar, P.; Singh, S. P.; Soh, M. S.; van Meurs, M.; Tan, J., Annealing-free high-mobility
diketopyrrolopyrrole-quaterthiophene copolymer for solution-processed organic thin film
transistors. Journal of the American Chemical Society 2011, 133, 2198-2204.
ur

15. Yi, Z. R.; Sun, X. N.; Zhao, Y.; Guo, Y. L.; Chen, X. G.; Qin, J. G.; Yu, G.; Liu, Y. Q.,
Jo

Diketopyrrolopyrrole-based π-conjugated copolymer containing β-unsubstituted

quintetthiophene unit: a promising material exhibiting high hole-mobility for organic thin-film
transistors. Chemistry of Materials 2012, 24, 4350-4356.
16. Yi, Z. R.; Ma, L. C.; Chen, B.; Chen, D. G.; Chen, X. G.; Qin, J. G.; Zhan, X. W.; Liu, Y. Q.; Ong, W.
J.; Li, J., Effect of the longer β-unsubstituted oliogothiophene unit (6T and 7T) on the organic thin-
film transistor performances of diketopyrrolopyrrole-oliogothiophene copolymers. Chemistry of
Materials 2013, 25, 4290-4296.
17. Sonar, P.; Singh, S. P.; Li, Y.; Soh, M. S.; Dodabalapur, A., A low-bandgap diketopyrrolopyrrole-
benzothiadiazole-based copolymer for high-mobility ambipolar organic thin-film transistors.
Advanced Materials 2010, 22, 5409-5413.
18. Lee, J.; Cho, S.; Seo, J. H.; Anant, P.; Jacob, J.; Yang, C., Swapping field-effect transistor
characteristics in polymeric diketopyrrolopyrrole semiconductors: Debut of an electron dominant
transporting polymer. Journal of Materials Chemistry 2012, 22, 1504-1510.
19. Yang, J.; Zhao, L.; Yin, Z.; Wang, J.; Zhao, Y.; Chen, H.; Liu, Y., Thiadiazoloquinoxaline-fused
acenaphthenequinone imide: A highly electron-withdrawing acceptor for ambipolar
semiconducting polymers with strong near-infrared absorption. Macromolecules 2021, 54, 3120-
3129.
20. Zhuang, W.; Wang, S.; Tao, Q.; Ma, W.; Berggren, M.; Fabiano, S.; Zhu, W.; Wang, E., Synthesis
and electronic properties of diketopyrrolopyrrole-based polymers with and without ring-fusion.
Macromolecules 2021, 54, 970-980.
21. Trilling, F.; Sachnik, O.; Scherf, U., π-Expanded diketopyrrolopyrroles as acceptor building
blocks for the formation of novel donor-acceptor copolymers. Polymer Chemistry 2019, 10, 627-
632.
22. Shi, D. D.; Liu, Z. T.; Ma, J.; Zhao, Z. Y.; Tan, L. X.; Lin, G. B.; Tian, J. W.; Zhang, X. S.; Zhang, G.
X.; Zhang, D. Q., Half-fused diketopyrrolopyrrole-based conjugated donor-acceptor polymer for
ambipolar field-effect transistors. Advanced Functional Materials 2020, 30, 1910235.
23. Jiang, W.; Liu, Z.; Zhu, D.; Zheng, W.; Chen, L.; Zhang, X.; Zhang, G.; Yi, Y.; Jiang, L.; Zhang, D.,
New synthetic approaches to N-aryl and π-expanded diketopyrrolopyrroles as new building
blocks for organic optoelectronic materials. Angewandte Chemie-International Edition 2021, 60,
10700-10708.

f
24. Chen, B.; Yang, Y.; Cheng, P.; Chen, X. G.; Zhan, X. W.; Qin, J. G., Designing a thiophene-fused

oo
DPP unit to build an A-D-A molecule for solution-processed solar cells. Journal of Materials
Chemistry A 2015, 3, 6894-6900.

r
25. Skonieczny, K.; Papadopoulos, I.; Thiel, D.; Gutkowski, K.; Haines, P.; McCosker, P. M.; Laurent,
-p
A. D.; Keller, P. A.; Clark, T.; Jacquemin, D.; Guldi, D. M.; Gryko, D. T., How to make nitroaromatic
compounds glow: Next-generation large X-shaped, centrosymmetric diketopyrrolopyrroles.
re
Angewandte Chemie-International Edition 2020, 59, 16104-16113.
26. Ma, L.; Chen, B.; Guo, Y.; Liang, Y.; Zeng, D.; Zhan, X.; Liu, Y.; Chen, X., NIR polymers and
lP

phototransistors. Journal of Materials Chemistry C 2018, 6, 13049-13058.

27. Lu, T.; Chen, F., Multiwfn: A multifunctional wavefunction analyzer. Journal of Computational
na

Chemistry 2012, 33, 580-592.

28. Lu, T.; Chen, F., Calculation of molecular orbital composition. Acta Chimica Sinica 2011, 69,
2393-2406.
ur

29. Ma, L. C.; Li, Z. G.; Chen, B.; Xue, P. Y.; Wang, Z. M.; Wu, Y. B.; Zhan, X. W.; Liu, Y. Q.; Chen, X.
Jo

G., The impact of benzothiadiazole on the optoelectronic performance of polymer/PC71BM blend

films and their application in nir phototransistors. Advanced Electronic Materials 2022, 8, 2101297.
30. Chabinyc, M. L.; Toney, M. F.; Kline, R. J.; McCulloch, I.; Heeney, M., X-ray scattering study of
thin films of poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene). Journal of the American
Chemical Society 2007, 129, 3226-3237.
31. Lan, S.; Yan, Y.; Yang, H.; Zhang, G.; Ye, Y.; Li, F.; Chen, H.; Guo, T., Improving device
performance of n-type organic field-effect transistors via doping with a p-type organic
semiconductor. Journal of Materials Chemistry C 2019, 7, 4543-4550.
32. Wang, Z. J.; Liu, Z. T.; Ning, L.; Xiao, M. F.; Yi, Y. P.; Cai, Z. X.; Sadhanala, A.; Zhang, G. X.; Chen,
W.; Sirringhaus, H.; Zhang, D. Q., Charge mobility enhancement for conjugated DPP-selenophene
polymer by simply replacing one bulky branching alkyl chain with linear one at each DPP unit.
Chemistry of Materials 2018, 30, 3090-3100.
33. Zhang, X.; Richter, L. J.; DeLongchamp, D. M.; Kline, R. J.; Hammond, M. R.; McCulloch, I.;
Heeney, M.; Ashraf, R. S.; Smith, J. N.; Anthopoulos, T. D.; Schroeder, B.; Geerts, Y. H.; Fischer, D. A.;
Toney, M. F., Molecular packing of high-mobility diketo pyrrolo-pyrrole polymer semiconductors
with branched alkyl side chains. Journal of the American Chemical Society 2011, 133, 15073-15084.
34. Chen, J.; Zhang, X.; Wang, G.; Uddin, M. A.; Tang, Y.; Wang, Y.; Liao, Q.; Facchetti, A.; Marks,
T. J.; Guo, X., Dithienylbenzodiimide: A new electron-deficient unit for n-type polymer
semiconductors. Journal of Materials Chemistry C 2017, 5, 9559-9569.
35. Luo, L.; Huang, W.; Yang, C.; Zhang, J.; Zhang, Q., Recent advances on π-conjugated polymers
as active elements in high performance organic field-effect transistors. Frontiers of Physics 2021,
16, 33500.

f
r oo
-p
re
lP
na
ur
Jo
 P(DPPFu-T), P(DPPFu-TT) and P(DPPFu-BT) were designed and successfully
synthesized by copolymerizing DPPFu with thiophene, thienothiophene and
benzothiadiazole, respectively.
All the polymer semiconductors exhibited prominent ambipolar charge transport
property. P(DPPFu-TT) displayed the best charge transport property with hole mobility
up to about 0.1 cm2V–1s–1 and electron mobility of 7.5×10-2 cm2V–1s–1.
Relationships between comonomer structure, frontier orbital energy level, orbital
delocalization index, molecular packing, film morphology and the corresponding
charge transport properties were investigated systematically.

f
r oo
-p
re
lP
na
ur
Jo
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐ The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

of
ro
-p
re
lP
na
ur
Jo