Foldable Semi-Ladder Polymers – Optical Properties and

Organic Light-Emitting Field-Effect Transistors

Valerii Sharapov#†, Mohammad A. Awais#†, Dafei Yuan†, Xunshan Liu†, Andriy Neshchadin†,
Wei Chen‡, Luping Yu*†
†
Department of Chemistry and the James Franck Institute, The University of Chicago, 929
th
E57 Street, Chicago, Illinois, 60637, USA
‡
Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue, Lemont,
Illinois 60439, USA

Since the first demonstration of OLETs in 2003,11 different types of light-emitting

materials were explored, such as normal LED materials, phosphorescent LED materials as
well as thermally activated delayed fluorescent (TADF) materials.12-14 However, there is
only modest progress being made so far in this field. There is a dilemma in balancing
optical and electrical properties in a single material. On the one hand, dense crystalline
structures with tightly packed conjugated molecules are required to exhibit the highest
electronic coupling and thus the best charge transport. On the other hand, the tight π-π
stacking of conjugated molecules is detrimental to their photoluminescence properties,
which may facilitate a cascade of quenching processes, including exciplex (excimer)
formation, energy and electron transfer processes, resulting in non-radiative decay. In this
paper, we describe discovery of semi-ladder-foldamer as a strategy to balance the trade-off
between charge transport and light emission.18-20 The materials are cross-conjugated co-
polymers of carbazole/fluorene derivatives and ladder oligomers, TPTQ/TPTQF. Results
indicated that the foldable polymers performed much better than fully conjugated
polymers with extended polymer chains. OLET devices with TPTQF-C showed the highest
EQE of 3.5%.
In the past two decades, efforts in the interconversion of light and electricity have dominated
the research trends in the area of organic conjugated polymers.1 The functionality involving
conversion of photons to electrons takes place in photovoltaic devices and photodetectors.2-5 The
reverse process, converting electrons to photons, occurs in organic light-emitting diodes
(OLED). The OLED devices are nowadays widely used in lighting and display applications. The
organic photovoltaic (OPV) solar cells are actively pursued.[1]
Accompanied with the development of OLED, organic light-emitting field-effect transistors
(OLET) emerged as a class of organic optoelectronic devices, which combine both the electrical
switching function of OFETs and the light-generation capability of OLEDs in a single device.6-10
These transistors have the potential for digital displays and on-chip optical interconnection,
leading to simplification of circuit design in electroluminescent display.
There are several desired characteristics of semiconducting polymers for OLET application,
including balanced electron and hole mobility, high emission quantum yield, suitable light
emitting spectrum, the controllable location of the light-emission zone and the emission
brightness. The light emitting region should be controlled so that the exciton/charge interaction
and exciton/metal electrode interaction can be minimized, both of which cause non-radiative
exciton decay. It is therefore preferred that devices are capable of ambipolar hole/electron
injection from their respective source-drain electrodes.15, 16
Since OLET devices typically consist of multiple layers (interfacial layers, organic
dielectrics, emissive layers), polymers used must be soluble in orthogonal solvents to each other.
This requirement significantly limits the choice of available materials. Therefore, new emissive
polymers that meet these critical needs may significantly facilitate the progress in the field.
Despite many attempts to resolve mobility-fluorescence trade-off, there are great challenges in
developing OLET materials that have comparable efficiency with the best performing OLED.
In this work, we synthesized semi-ladder polymers based on monomers TPTQ /TPTQF and
carbazole or fluorene, which were chosen because of their superior fluorescent properties and the
possibility of side-chain modification.21-23 These polymers had good solubility in common
organic solvents that allow us to find orthogonal solvents in preparing multilayers. We
investigated their physical, optical, electronic properties and morphologies. Interesting
aggregation behaviors including self-folding were observed. It was found that folded semi-
ladder polymers are superior over fully conjugated polymers in their performances as emissive
materials in OLET devices.

RESULTS AND DISCUSSION

The polymers were synthesized according to Scheme 1 via Suzuki polymerization of TPTQ
or TPTQF dibromide with carbazole or fluorene monomers containing bis (pinacolato) diboron
(BPin) moieties.
Scheme 1. General synthesis scheme of the polymers (R1 2-butyloxtyl, R 2-ethylhexyl).

R
O N
NR1
R X
N
X
R1N n
O
PinB BPin
O X=O, TPTQF-C
NR1 X=S, TPTQ-C
O
X Br R
n NR1 R
Br X N
+n PinB BPin
N
R1N X X
O n
X = O. TPTQF R1N
X = S. TPTQ O

R R
X=O, TPTQF-CC
O X=S, TPTQ-CC
PinB BPin
NR1 R R
X X
n
R1N
O

X=O, TPTQF-F
X=S, TPTQ-F

General synthetic procedures of the polymers are summarized in the supporting information.
Polymers exhibited sizable molecular weights and generally narrow polydispersity indices (PDI),
as summarized in Table 1. All of the polymers, except TPTQ-CC, were soluble in common
organic solvents such as p-xylene or chloroform. The polymer TPTQ-CC had lower molecular
weight, due to its poor solubility even in warm solvents. This is likely caused by strong 
interchain interaction. The basic properties of the polymers are summarized in Table 1.

Table 1. Properties of fluorescent polymers

Polymer HOMO LUMO Bandgap Eg (eV) PLQY (%) Mw Mn PDI
(eV) (eV)
TPTQF-C -5.42a/-4.90b -3.04d/-1.92b 2.98b/2.38c 50 50863 28835 1.76
TPTQ-C -5.44a/-5.03b -3.19d/-2.41b 2.62b/2.25c 30 91767 32823 2.80
TPTQF-CC -5.48a/-5.06b -3.07d/-2.23b 2.83b/2.41c 73 20407 14634 1.39
TPTQ-CC -5.65a/-5.18b -3.30d/-2.41b 2.77b/2.35c 15 1861 1524 1.22
TPTQF-F -5.67a/-5.09b -3.19d/-2.32b 2.77b/2.48c 97 33651 29511 1.14
TPTQ-F -5.76a/-5.21b -3.38d/-2.46b 2.75b/2.38c 77 55172 36012 1.53
a
Measured from the cyclic voltammetry, b Bandgap Eg calculated from DFT, c Bandgap Eg calculated from the
onset of the film absorption, d LUMO energy levels are calculated as HOMO of the polymer from CV + E g from the
onset of film absorption.

HOMO energy levels of polymers TPTQF-C and TPTQ-C are very close, -5.42 eV and -5.44
eV, respectively. This is consistent with the energy levels calculated from DFT (B3LYP method,
6-31g** basis set). Due to cross-conjugated connection and twisted dihedral angle between the
monomers, both TPTQF-C and TPTQ-C exhibit coiled foldamer-like optimized geometry in
DFT. Four other polymers in the series exhibit slightly curved but linear geometry in DFT
calculations. Carbazole-containing polymers show slightly higher HOMO energy levels, likely
due to its better electron donating ability than fluorene.
In order to study bulk polymer structure in the film, we first measured GIWAXS for the
polymer films (Figures S5). It was found that most of the polymers are almost amorphous, with
slightly preferential face-on orientation. TPTQ-F exhibits the sharpest and most intense
scattering peaks, compared to the other polymers in this study, which indicates its higher
crystallinity.
 Figure 1. Concentration-dependent solution and film UV-Vis absorption spectra of a)
TPTQF-C, b) TPTQ-C, c) TPTQF-CC, d)TPTQ-CC, e)TPTQF-F, f)TPTQ-F.

Figure 2. Concentration-dependent solution and film photoluminescence spectra of a)

TPTQF-C, b) TPTQ-C, c) TPTQF-CC, d)TPTQ-CC, e)TPTQF-F, f)TPTQ-F.

The optical absorption of these polymers was investigated in detail (Figure 1). It can be seen
that polymers containing TPTQ and carbazole absorb in the spectral region of 375-600 nm, while
polymers with the TPTQF have a narrower absorption window, 375-500 nm, which is consistent
with the wider band gap of TPTQF polymers calculated from DFT. Polymers containing
fluorene have slightly blue shifted spectra, compared to carbazole analogs. Their shape of the
film absorption spectra resembles those in the solution, slightly red-shifted and broadened due to
planarization of  system. Comparison of absorption spectra of the monomers, model
compounds and the resulting polymers gives insightful results (Figure S8). TPTQ monomer
exhibits strong 0-0 transition and decreased 0-1 transition in its absorption spectrum. However, a
significant difference in spectral shape can be observed in TPTQ-C where the 0-0 transition
intensity is reduced and 0-1 transition becomes the strongest, indicating the formation of H-
aggregation. Normalized absorption spectra at different concentration showed almost no change
of the spectral shape with the decreasing concentration (Figure 1), indicating that H aggregation
exists even at the level of single molecules. This is evidence for the polymer folding as was
shown in our previous work.[14] Polymer TPTQF-C exhibits the same feature in its absorption
spectra. A common structural feature of both polymers is that they are cross-conjugated
copolymers with carbazole moiety that presents an angled connection with ladder comonomers.
DFT calculations for simplified polymer backbone (omitted long alkyl side chains in calculation)
hinted the possibility for the formation of coiled foldamers although these calculations can only
be used with caution in interpreting experimental results. To support this conclusion, we further
synthesized model compounds – dimers, containing central TPTQ or TPTQF unit connected to
the carbazole in the same way as in the polymers TPTQ-C and TPTQF-C, respectively. These
molecules do not have folded coiled structures, and they exhibit strong 0-0 transition in dilute
solutions (Figure S8 right figure), similarly to the monomer. Therefore, the UV/vis spectra for
TPTQ-C and TPTQF-C indicated the formation of H-aggregation in single polymer chains,
which is only possible in folded chains.
The opposite pattern is observed in linear polymers TPTQF-CC, TPTQ-F, TPTQF-F, in
which the 0-0 transition is dominating, similar to the monomer properties. The absorption spectra
of TPTQ-CC showed diminished 0-0 absorption band and blue-shift in film spectrum, despite
exhibiting linear geometry. This is the typical behavior of H-aggregation. TPTQ-CC
demonstrated poor solubility and thus exists in the aggregated state in solution and has strong
tendency to form H-aggregates via favored face-to-face interaction. Results on quantum yield
for light emission provide further evidence for H aggregation (Table 1). Both TPTQ-C and
TPTQ-CC exhibit low quantum yield for light emission in solution. TPTQF-C is relatively low
in emission quantum yield, but higher than TPTQ-C and TPTQ-CC due the absence of sulfur
atoms. The rest of polymers show high quantum yield for light emission in solution.
Solution fluorescence spectra under varied temperatures provide evidence for polymer
aggregation mode. The ratio of intensities of I00 peak to I01 peak will increase with the increasing
temperature for H-aggregates, and decrease for J-aggregates. As shown in Figure S9 and
summarized in Table S1, TPTQ-C exhibits slightly increased I00/I01 ratio, from 1.35 to 1.38, when
the solution temperature increases from -9 to 20 ○C, which indicates slight H-aggregation (due to
limitation in our instrument, we can only perform the measurements in this narrow temperature
range). Similar trends are observed for TPTQ-CC, TPTQF-C and TPTQF-CC. However, fluorene
containing polymers, TPTQF-F and TPTQ-F exhibit the opposite behavior - I00/I01 ratio decreases
with the increasing temperature, which indicates J-aggregation. Spano et al proposed that J
aggregates in semiconducting polymers could be due to intrachain interaction.
The film photoluminescence spectra for all the polymers show red shift in comparison with
related solution spectra. In order to understand these observations, we measured concentration-
dependent photoluminescence spectra for all the polymers and compared them to films (Figure
2). The range of concentrations used in our study was from 0.001 mg mL-1 to 0.1 mg mL-1. The
polymers show gradual red shift of fluorescence upon concentration increase. The shoulder peaks
(I01) are present even in the most dilute solution for all the polymers and their intensity increases
with the increasing concentration. These results seem to be in contradiction with characteristics
of H-aggregates, which was known to exhibit blue shift. However, as pointed out by Spano,
compounds containing quadrupole interactions could exhibit red shift in H-aggregates when the
intermolecular angle reaches certain values. A centro-symmetric chromophore TPTQ is indeed a
compound exhibiting quadrupole interactions. When TPTQ is incorporated into polymers, we
can assume this property kept intact (although the co-monomers need to align in trans-mode to
satisfy the central symmetric condition). Thus, these polymers are special cases with quadrupole
interaction. Further studies are needed to determine the overlap modes.
To gain more insight into the photophysical properties, time-resolved fluorescence decay was
measured for polymer solutions (Table S2). Fluorescence decay curves were fitted with
exponential decay equation and fluorescence lifetimes were calculated. It was found that
polymer TPTQ-C exhibits the longest fluorescence lifetime of 2.14 ns with a single exponential
decay behavior. This value seems to be consistent with folded H-aggregate, in which exciton
delocalization elongate their lifetime. TPTQ-F also exhibits a single exponential decay, however
with much shorter lifetime of 0.615 ns. All other polymers showed double exponential decay
behavior, which may indicate the presence of different relaxation pathways.
The optical studies revealed a broad spectrum of aggregation behaviors for these polymers,
which will affect the performance of light emitting field effect transistors. We prepared OLET
devices with these polymers as emissive layers and investigated their current-voltage
characteristics. We used bottom gate-top contact (BG-TC) configuration of the device with p-
doped silicon as a gate and thermally evaporated layer of gold as source-drain electrodes (Figure
3). The channel length (L) of the devices is 50 µm and channel width (W) of 18.2 mm. Silicon
nitride (Si3N4) was used as a dielectric layer because of its higher dielectric constant, which was
modified with a layer of OTS.

Figure 3. Device architecture of organic light-emitting field-effect transistors (OLET).

 Figure 4. a) Output curves, transfer curves and microscope photographs of light-emitting
devices with TPTQF-C, b) Output curves, transfer curves and microscope photographs of light-
emitting devices with TPTQ-C, c) Microscope photographs of light emitting devices with TPTQ-
F, d) Microscope photographs of light emitting devices with TPTQ-CC, e) Microscope
photographs of light emitting devices with TPTQF-CC, f) Microscope photographs of light
emitting devices with TPTQF-F.

Polymers DPP-DTT and PFN+BIm4- were used as hole-transporting and electron-transporting

layers, respectively, which do not contribute to light emission and only facilitate charge
transport. Polymer emissive layer was coated from the solvents orthogonal to those that dissolve
DPP-DTT and annealed at 100○C. Source-drain current-voltage characteristics were measured at
positive and negative gate voltages to test electron and hole transport in the device. The transfer
curves in Figure 4 for OLET devices with the structure Si 3N4/OTS/DPP-DTT/Emissive layer/Au
show that the devices exhibit ambipolar behavior. However, the transport is not balanced,
resulting in source-drain currents at negative gate voltages (hole transport) being noticeably
larger than the currents at positive gate voltages (electron transport). The transfer curves show
typical v-shape attributed to hole and electron transport. It is evident that the charge transport
occurs predominantly at the DPP-DTT/dielectric interface. The observed mobilities for
multilayer devices are several orders of magnitude larger than for single layer devices with the
emissive layer (Table S3). These FET devices contain symmetric source and drain electrodes
(i.e. electrodes made of the same metal – gold). The injection barrier for holes is much lower
than the barrier for electrons. The work function of metal gold (-5.1 eV) is better aligned with
HOMO energy levels of the polymers (-5.2 to -5.7 eV) where hole injection happens, rather than
with LUMO levels (-2.7 to -3.5 eV), participating in electron injection.
The misbalance in hole and electron mobilities results in light emission being predominately
concentrated near the minority charge carrier injecting electrode, rather than in the middle of the
channel, which we observe in our devices. Polymers TPTQ-C and TPTQF-C, shows the brightest
emission. Both polymers were shown to form folded structures. Thus, the folded structure is
beneficial to avoid emission quenching due to weak aggregation interaction. What we can see is
that folded structure offers compromise both in charge carrier’s mobility and light emission to
achieve overall optimization.

Figure 5. Film photoluminescence and electroluminescence in a) TPTQF-C, b) TPTQ-C, c)

TPTQF-CC, d)TPTQ-CC, e)TPTQF-F, f)TPTQ-F.

Detailed investigation in light emission from the OLET devices reveals that the
electroluminescence spectra of the polymers were very close to 0-0 transition band in film
photoluminescence spectrum (Figure 5), indicating the identical nature of emissive centers for
both PL and EL processes. The transfer characteristics of the OLET and the photocurrent of the
reverse-biased photodiode were simultaneously measured, by placing calibrated photodiode right
in front of the device and observing the response (Figure 6). The brightest light emission for
polymers TPTQF-C, TPTQ-C, TPTQF-CC and TPTQ-CC was observed for negative gate
voltages, where hole transport dominates, however for TPTQ-F the brightest emission was
observed in the electron dominating region.
 Figure 6. External quantum efficiencies and photodetector photocurrents for OLET devices
with a) TPTQF-C, b)TPTQ-C, c)TPTQF-CC, d)TPTQ-C, e)TPTQF-F, f)TPTQ-F.

We measured external quantum (EQE) efficiencies of OLET devices in the brightest emission
mode (gate voltage from +20V to -100 V). Device with TPTQF-C showed the highest EQE of
3.5%, while the rest of the polymers show EQE orders of magnitude smaller, around 10-3%.
Interestingly, we do not observe EQE roll-off at the brightest point and higher currents - EQE in
the device stays almost constant over a wide voltage range, which is a highly desired property in
light emitting devices.
The above results show that there are three main advantages associated with these semi-
ladder polymers.[17, 18] First, ring fusion introduces rigidity into the molecular system,
decreasing the effective vibrational modes available for non-radiative decay and improving light
emission. The high quantum yields of TPTQ-F, TPTQF-F and TPTQF-CC demonstrated this
point. Second, the ring fusion extends effective conjugation length, leading to more controllable
bandgaps, better delocalization of frontier molecular orbitals and eventually better intramolecular
charge transport. Third, the foldamer introduces weak aggregation due to structural restrain, yet
allow significant contact between chromophores for charge transport. These advantages give
foldable semi-ladder polymers excellent OLET performance. Thus, foldable polymers are an
effective solution to the dilemma in balancing charge transport and luminescent property for
OLET application.

CONCLUSIONS
Six fluorescent, semi-ladder polymers were synthesized and explored. Experimental results
reveal that the polymers TPTQ-C and TPTQF-C exhibit foldamer structure which favors
balanced electrical and light emitting properties. The EQE of OLET devices with TPTQF-C is
3.5%, which is one of the highest reported EQE. This study shows that foldamer containing
ladder-type structures are promising materials for OLET. This design strategy may pave the way
to the development of even more efficient polymers that can be used in the next generation of
high-efficiency organic light-emitting field-effect transistors.

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