Pyran-annulated perylene diimide derivatives as non-fullerene acceptors for high performance organic solar cells

Article abstract of DOI:10.1039/c8tc02823k

There has been growing interest in the effectual strategy of constructing non-fullerene acceptors for organic solar cells that may overcome the defect of traditional fullerene-based acceptors. Herein, two novel push-pull (acceptor-donor-acceptor) type sma

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Chem. C, 2018, DOI: 10.1039/C8TC02823K.
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Fine-tuning of gold nanorod dimensions and plasmonic properties using
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ARTICLE
Pyran-annulated perylene diimides derivatives as non-fullerene
acceptors for high performance organic solar cells
Received 00th January 20xx,
Accepted 00th January 20xx
‡
a
‡a
‡b
a
a
*c
d
Gang Li , Yu Zhang , Tao Liu *, Shuaihua Wang ,Dandan Li , Jiewei Li , Fengting Li , Lian-Ming
d
e
e
*b
a
a
*a
Yang , Zhenghui Luo , Chuluo Yang , He Yan , Pin Hao , Qiaoyan Shang and Bo Tang
DOI: 10.1039/x0xx00000x
There has been growing interest in the effectual strategy of constructing non-fullerene acceptors for organic solar cells
that may overcome the defect of the traditional fullerene-based acceptors. Herein, two novel push-pull (acceptor-donor-
www.rsc.org/
acceptor) type small-molecule acceptors, that is, TPA-PDI
pyran-annulated perylene diimides (Py-PDIs) as peripheryl groups are designed and synthesized for non--fullerene organic
solar cells (OSCs). After device optimization, OSCs based on TPA-PDI demonstrate good device performance with a power
conversion efficiency (PCE) as high as 5.84%, surpassing the TPA-PDI -based counterparts fabricated under identical
conditions (1.314% PCE). The high efficiency for TPA-PDI can be attributed to complementary absorption spectra with the
donor material (PBDB-T), balanced carrier transport and favorable morphologies. To the best of our knowledge, this PCE of
2 3
and TPA-PDI , with triphenylamine (TPA) as the core unit and
3
2
3
5
.84% is among the highest values based on ethynyl-functionalized TPA-shaped non-fullerene acceptors so far.
1
. Introduction
the advantages of tunable energy levels, strong absorption in
Solution-processed organic solar cells(OSCs) have been widely
investigated with great effort to convert solar energy into
electrical energy with advantages of semi-transparency,
lightweight, flexibility and large-area fabrication through low-
C
8
H
17
10 21
C H
C
10
H
21
O
8 17
C H
N
O
O
N
O
N
1
TPA-2EY
cost solution-coatingmethods. In generally, OSCs adopt a bulk
O
O
heterojunction (BHJ) active layer consisting of a blend of
2
donors and acceptors (fullerene derivatives). However, the
Pd(PPh3)4 / CuI
toluene
/
i-Pr2NH
N
C
8
H
17
TPA-PDI2
O
N
O
10
O
N
O
C
o
C
C
10
H
21
O
80
overnight
C
H
21
10 21
H
N
O
C
8
H
17
8 17
C H
intrinsic drawbacks of the fullerene acceptors, such as weak
absorption in visible region, high retail costs, inferior ambient
stability and poor morphology stability, make it a problematic
material for future practical application in OSCs. Therefore,
nonfullerene acceptors(NFAs) used in OSCs have drawn
vigorous attention from both academic and industry due to
Br
O
C
8
H
17
8 17
C H
C
10
O
H
21
O
C10H21
O
O
N
O
C
N
N
O
N
O
10 21
H
8 17
C H
TPA-3EY
O
Py-PDI-Br
N
Pd(PPh
3
)
4
/
CuI / i-Pr
2
NH
O
N
O
O
N
O
C
toluene
C
10
H
21
10
H
21
8
0 C
o
C
8
H
17
8
C H
17
overnight
O
N
10 21
C H
O
N
TPA-PDI3
8 17
C H
10 21
C H
C
8
H
17
O
O
O
2 3
Scheme 1. Synthetic routes of TPA-PDI and TPA-PDI .
the visible and even near-infrared region (vis-NIR), as well as
3
easy purification compared to their fullerene counterparts.
Up to date, series of high performance NFAs have been
-5
4
exploited, especially for the systems of3,9-bis(2-methylene-
3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-
(
tetrakis(4hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-
b:5,6-b′]-dithiophene (ITIC) and perylene diimides (PDIs). The
PCE of organic solar cells based on the ITIC acceptors have
5
h,6
exceeded 12%,
4
while the record PCE of PDIs-based OSCs is
f,5g
1
0.58%.
PDIs demonstrated several excellent properties,
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ARTICLE
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such as easy functionalization, strong electron-acceptor of PBDB-T (Fig.S17) as the donor, the highest PCE of 5.84%
2
character, finely tunable solubility, intense light absorption with an impressively high Voc of 0.91 V, a JSC of 10.27 mA/cm ,
capability,
energy
level
tunability,
and
self- a FF of 62.4%was achieved, which is 4.5 times higher than that
(1.314% PCE). The results demonstrated that Py-
7
assemblingproperties. However, despite these favorable of TPA-PDI
2
advantages, the strong tendency for π–π stacking between PDIs is a good potential for the construction of high-
PDIs molecules inclined to form excessively large crystalline performance non-fullerene acceptors.
domains, which may result in large phase separation in active
8
layers, thereby limiting the OSCs performance.
2. Results and discussion
C
8
H
17
8 17
C H
2
.1. Synthesis and characterization
C
10
H
21
O
C
10
H
21
O
N
O
N
O
The synthetic routes of the two compounds are shown in
Br
2
Br
O
O
Scheme 1 and 2.Py-PDI-Br was synthesized by bromination of
3 2 3
CHCl / K CO
compound
Py-PDI
under
chloroform
and
reflux
O
N
O
C
overnight
O
N
O
C
potassium carbonateat reflux conditions (Scheme 2).The
10
H
21
10
H
21
C
8
H
17
C
8
H
17
acetylene substituted TPA cores were synthesized according to
1
3
Py-PDI
Py-PDI-Br
the literature methods. Target product of TPA-PDI2 and TPA-
PDI3 were obtained in moderate yields by the palladium-
catalyzed Sonogashira coupling reaction. The as-synthesized
Scheme 2. Synthetic route of Py-PDI-Br
.
1
13
molecules were fully characterized by H and C NMR, Fourier
Transform infrared spectroscopy (FT-IR), matrix assisted laser
desorption ionization time of flight mass spectrometry
Therefore, many strategies have been adopted to suppress
the aggregation tendency to enhance the processability of the
materials and to form favorable BHJ domain structures.
Several groups devoted to the construction of twisted PDIs
dimers and three-dimensional structure oligomers, connected
(MALDI-TOF). Fig. S8 shows very sharp, well resolved peaks for
the dimer, but the trimer (Fig. S10) shows very broad signals.
We think the 3D molecular geometry enhanced the structural
rigidity and conformational uniformity of the TPA-PDI3
molecule, which suppressed the free rotation of the TPA and
PDIs leaded to a 3D interlocking structure. A similar
interlocking conformation has been reported recently in a 3D
9
8b
by cores such as spirobifluorene, tetraphenyletheylene,
8
a
10
benzodithiophene and porphyrin. Furthermore, S, Se and N
heteroatoms had been incorporated at the bay positions of
PDIs units to obtain more twisted structures and higher lowest
unoccupied molecular orbital (LUMO) levels, which is favorable
9
PDI-based small molecule acceptor. To verify the structure of
1
1
for achieving good device performances. Therefore, further
the target product (TPA-PDI3), we performed the MALDI-TOF
measurements. (Fig. S13) and elemental analysis. Moreover,
They show good solubility in common organic solvents, such as
dichloromethane ,chloroform, and o-dichlorobenzene (O-DCB)
at room temperature. These conjugated molecules also exhibit
excellent thermal stability with a decomposition temperature
development of novel PDIs is worthy of being studied.
o
o
(T , 5% weight loss) of 402 C for TPA-PDI2 and 428 C for TPA-
d
PDI3 in nitrogen atmosphere. Obviously, the thermal stability
of the two small molecules is adequate for their applications in
OSCs.
2
.2. Optical and electrochemical properties
Figure 1. (a)The normalized absorption spectra ofTPA-PDI
μM dichloromethane solution. (b) The normalized absorption spectra of PBDB-T:
TPA-PDI and PBDB-T: TPA-PDI blend films.
2 3
and TPA-PDI in 10
The UV–vis absorption spectra of the two compounds in
2
3
−5
dichloromethane (DCM) solution(10 M) and as the solid film
Recently, our group developed a novel pyran-annulated are presented in Fig. 1 and Fig. S1, and the corresponding data
PDIs
Py-PDIs) which exhibited an extended UV-vis absorption are summarized in Table S1. The two compounds exhibited
and relatively high LUMO energy levels. These properties similar absorption profiles. CompoundTPA-PDI
(
1
2
3
showed a
demonstrated that Py-PDIs is a promising electron-deficient strong visible absorption band in the wavelength range of 450-
unit toward high-performance n-type semiconductors for OSCs. 670 nm with a maximum molar extinction coefficient of 9.08 ×
4
−1
−1
But the usage of Py-PDIs in non-fullerene organic solar cells 10 M cm at 553 nm, which is higher than that of TPA-PDI
2
4
−1
−1
has never been reported.
Herein we reported two novel propeller-shaped small synergistic effect of π–π interactions. Neat TPA-PDI
molecule acceptor named TPA-PDI and TPA-PDI
based on PDI films display similar absorption spectra to their solution
D-structured triphenylamine as the core which were flanked ones, indicating weak intermolecular aggregation in the solid
(6.21 × 10 M cm at 557 nm) most likely due to the
1
4
2
and TPA-
2
3
3
3
opt
with acetylene unit and end-capped with Py-PDIs. By using state. The optical bandgap (E
g
) of two compounds were
TPA-PDI
3
as the acceptors and the high performance polymer estimated to be 1.69 and 1.77 eV from the absorption onset of
2
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their films. In addition, the absorption spectra of TPA-PDI
2
and isopropyl group. The LUMO and HOMO orbitals are shown in
, the LUMO orbital localize in the PDIs unit
While the HOMO electron density localizes in the TPA core
along with PDIs unit. However, inTPA-PDI , the HOMO orbital
3 2
TPA-PDI with PBDB-T are well complemented to ensure a full Fig. S2. InTPA-PDI
harvest of light in the visible spectrum (Fig. 1b).
3
concentrated in the core of TPA, implying obvious charge
polarization in the excited state. The optimized molecular
2 3 3
Figure 2. Cyclic voltammetry of TPA-PDI and TPA-PDI recorded in CH CN.
Figure 4. Optimized molecular geometries of TPA-PDI
at B3LYP/6-31G(d)
2 3
(a, c) and TPA-PDI (b, d)
.
Figure 3. (a) Device configuration of the studied OSCs.(b) Estimated energy levels
of PBDB-T TPA-PDI , and TPA-PDI from electrochemical CV.Cyclic voltammetry
of TPA-PDI and TPA-PDI thin films recorded in dry acetonitrile.
geometries of two compounds are presented in Fig.4. The
dihedral angles between PDI with benzene for TPA-PDI are
5.7 and 6.7 , respectively (Fig.4a, 4c). Another, the dihedral
,
2
3
2
2
3
o
o
1
o
angles between PDI with benzene for TPA-PDI
o
3
are 15.1 , 12.4
Cyclic voltammetry (CV) measurements were carried out to
investigate the highest occupied molecular orbital (HOMO)
o
and 0.2 , respectively (Fig.4b, 4d). These results suggest that
the introduction of the third PDI unit results in an obviously
more twisted molecular configuration, which are expected to
suppress aggregation to form favorable morphologies and
nanoscale phase separation. The LUMO/HOMO energy levels
and lowest unoccupied molecular orbital(LUMO) energy levels
+
3
in CH CN solutions using Ag/Ag+ as a reference and Fc/Fc
(0.432 V) as a standard(Fig.2 and Table S1). The LUMO energy
levels were calculated to be the onset of reduction potential,
−
2 3
ofTPA-PDI and TPA-PDI are−3.33 /−5.27 eV and −3.39 /−5.34
3
.83 and
−
3.78 eV, respectively, according to the equation
1
5
eV through DFT calculations (Table S2), respectively. The
calculated values are consistent with the values byCV
measurements.
E
LUMO
=
−
[q(Ered
–
E
Fc/Fc+) + 4.8)] eV. The highest occupied
and TPA-
5.55 eV, respectively,
molecular orbital (HOMO) energy levels for TPA-PDI
2
PDI
3
were calculated to be
−
5.52 and
−
opt
15
according to the equation EHOMO
=
−
(ELUMO + E
g
) eV. As
shown in Fig. 3b, the relatively high energy offsets of 1.5 eV
LUMO−LUMO) for TPA-PDI
and PBDB-T compared with the
counterpart of TPA-PDI andPBDB-T (1.45 eV) can produce a
high Voc for TPA-PDI -based PSCs.
(
3
2
3
2
.3. Theoretical analysis
Figure 5. (a)
w/w),PBDB-T:TPA-PDI
corresponding BHJ OSCs.
J
-
V
curves of BHJ OSCs based on PBDB-T:TPA-PDI
2
(1:1,
In order to gain a deeper insight on the geometric and
electronic properties of the two acceptor molecules, density
functional theory calculations were performed using the
3
(1:1, w/w)without additive. (b) EQE curves of the
1
6
Gaussian package B3LYP/6-31G(d). In order to facilitate the
calculation, the long alkyl chains were replaced with an
2
.4. Photovoltaic properties
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2 3
Photovoltaic properties ofTPA-PDI and TPA-PDI as acceptors
were investigated in devices with a configuration of ITO glass/
poly(3,4-ethylenedioxythiopene):poly(styrene sulphonate)
PEDOT:PSS)/ active layers /ZrAcAc/Al were prepared. PBDB-T
(
was chosen as the electron donor material because of
complementary absorption to that of the two acceptors (See
Fig. S17). The optimal conditions for preparing the devices
were obtained by choosing the spin-coating speed and
annealing temperatures carefully. The active layers were spin-
coated from a solution in o-dichlorobenzene. The optimized
weight ratio of D/A was 1:1, and the optimized thickness of the
active layer is about 95 nm. The active layer is deposited at a
spin-coating rate of 1600 rpm from their concentrated
−1
solutions (concentration, 20 mg mL ). The current density-
voltage(J–V) curves of the OSCs with optimized devices under
2
AM 1.5G, 100 mW/cm are given in Fig. 5 and the
corresponding photovoltaic parameters, V , J , FF and PCE of
oc sc
the devices are summarized in Table S3. Notably, the most Figure 6. Atomic force microscopyheight and phase imagesof PBDB-T:TPA-PDI2 (a, c,
efficient photovoltaic cells were obtained from the BHJ 1:1, w/w) and PBDB-T:TPA-PDI
3
(b, d, 1:1, w/w) blend film.
systems usingTPA-PDI3 with PBDB-T, which showed a summit
2
−
PCE of up to 5.84%with a J of 10.27 mA cm , and a V of 0.91 The unbalanced charge transport may be responsible for low
sc
oc
2
V, an FF of 0.624. In contrast, the TPA-PDI2- based OPVs EQE and FF observed for TPA-PDI .
−
2
exhibited PCEmax = 1.314% with J = 3.837
±
0.201 mA cm ,
0.004.We infer that the 2.6. Morphology characterization
obvious enhancement in PCE values probably benefits from
sc
Voc= 0.865±0.005 V, and FF= 0.368±
the improved charge transfer and superior morphology of the The morphology of the BHJ films were known to closely
active layer, which decrease energy loss from charge correlate to mobility, Jsc, and finally PCE. Atomic force
microscopy(AFM) with tapping mode was utilized to obtain the
recombination.
Fig. 5b shows the external quantum efficiencies (EQE) surface morphology of blend films. As illustrated from the
spectrum of the TPA-PDI2and TPA-PDI3 based optimized OSCs. height and phase images in Fig. 6, the root mean square (RMS)
The Jsc values obtained by integrating the EQE curves with an values of blend films of PDBT-T: TPA-PDI
AM1.5 G reference spectrum are in accord with those PDI are measured to be 1.07 and 0.92 nm, respectively. The
obtained from J−V measurements (within 5% mismatch). The lower RMS value for the PBDB-T: TPA-PDI and PBDB-T: TPA-
optimized device showed a broad photo-to-current response PDI blend films indicate that the acceptor materials TPA-PDI
from 350 to 680 nm with a maximum value of 67%and over 50% and TPA-PDI have a good miscibility with PBDB-T molecule in
across the range of 500–650 nm, indicating a relatively the blend films, and may form a finer interpenetrating network,
efficient photoelectron conversion process.
which facilitates both exciton separation and charge
2
and PDBT-T: TPA-
3
2
3
2
3
4
g
transport.
2
.5. Charge carrier mobility
2
.7. Photocurrent density and effective voltage study.
To understand the difference of Jsc and FF of the different
acceptor devices, the current–voltage (J–V) characteristics of
The exciton dissociation and charge extraction of PBDB-
2 3
blend films in space-charge-limited current (SCLC) devices T:TPA-PDI and PBDB-T:TPA-PDI based OSCs were studied by
were measured. The device structures of the electron only and measuring the photocurrent density (Jph) versus effective
hole only devices are ITO/ZnO/active layers /ZrAcAc/Al and voltage (Veff). As shown in Fig. S4 and Table S5, the Jphs of two
ITO/V
2
O
5
/
2 5
active layers /V O
/Al, respectively. The OSCs reached saturation (Jsat) at voltages approaching 3 V, and
-2 -
corresponding SCLC devices are shown in Fig. S3, and the the Jsat after annealing were 4.732 mA cm and 10.875 mA cm
2
corresponding electron/hole mobility data are listed in Table
2 3
for PBDB-T:TPA-PDI and PBDB-T:TPA-PDI based OSCs,
S4. The hole/electron mobilities for PBDB-T: TPA-PDI
2
and respectively. After annealing treatment, the probabilities of
-4
-4
2
-1 -1
PBDB-T: TPA-PDI
/ μ = 2.53) and 7.84× 10 /3.85 ×10 cm V s (μ
.03), respectively. For PBDB-T: TPA-PDI
PCE, higher and more balanced mobilities are good for were 85.8% and 53.4% for PBDB-T: TPA-PDI
effective charge transport and thus acquire excellent JSC and FF. 94.4% and 80.0% for PBDB-T: TPA-PDI
respectively. Obviously, the PBDB-T: TPA-PDI
3
blends are 5.65× 10 /2.23 ×10 cm V
s
exciton dissociation calculated from Jph/Jsat under the short
-4
-4
2
-1 -1
(μ
h
e
h
/ μ
e
=
circuit condition and probabilities of charge collection
2
3
devices with better calculated from Jph/Jsat at the maximal power output condition
based OSC, and
2
3
based OSC,
based OSC
3
showed apparently higher exciton dissociation and charge
4
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collection probabilities than those of PBDB-T: TPA-PDI
OSCs, which is beneficial for realizing a large JSC and FF.
2
based mmol) at room temperature, then heated to reflux for 12 h
and monitored by TLC. Then aq NaHSO was added to quench
excess bromine. After being extracted by CH Cl and the
3
2
2
combined organic phase was washed with brine. After removal
of solvent, the residue was purified by silica gel column
3
. Conclusions
chromatography with petroleum ether/ CH
eluent to give compound as a dark-red solid (0.4 g, 80%
yield). H NMR (300 MHz, CDCl , ppm): δ 9.85 (d, 1H), 8.73 (s,
H), 8.57 (d, 1H), 8.49 (s, 1H), 8.03 (s, 1H), 4.10 (m, 2H), 1.84 (s,
2 2
Cl (1:3)as the
4
In conclusion, two novel small molecule acceptor TPA-PDI
2
and
1
TPA-PDI consisting of triphenylamine core and pyran-
3
3
1
6
annulated perylene diimides (Py-PDIs) were designed and
synthesized. Owing to the presence of the unique TPA core,
1
3
3
H), 1.32 (m, 64H), 0.86 (m, 12H). C NMR (75 MHz, CDCl ,
ppm): δ 163.17, 162.29, 151.97, 139.46, 134.40, 128.16,
TPA-PDI
2
and TPA-PDI
3
not only feature a rigid 3D
1
2
1
23.35, 120.35, 115.46, 80.27, 44.87, 44.73 36.70, 36.62, 31.94,
+
conformation, but also presents suitable absorption properties
and high electron mobility. The fabricated BHJ OSCs on the
6.50, 22.70, 14.15. HRMS:
085.6268; found, 1085.6329.
67 2 5
C H93BrN O (M +H), calcd,
3
basis of PBDB-T: TPA-PDI show good performance with high
PCE of up to 5.84%, which is the first report of of Py-PDIs
-
4
.2.2. Synthesis of TPA-PDI
2
based non-fullerene acceptors. The result demonstrates that
Py-PDIs is a promising building block for the construction of
structurally non-planar PDIs derivatives as non-fullerene
electron acceptors for highly efficient OSCs.
Py-PDI-Br (407 mg, 0.375 mmol), TPA-2EY (50 mg, 0.17 mmol),
Pd(PPh (100 mg) and CuI (20 mg) were added to a round
bottom flask with the protection of Ar gas, then dry toluene
20 mL) and dry diisopropylamine (5 mL) were injected into it.
3 4
)
2
(
o
4
. Experimental
The reaction was stirred under 80 C overnight. The cooled
mixture was extracted with dichloromethane and water. The
residue was purified by column chromatography (eluent,
4.1. General information
2
hexane/DCM, 60:1, 1:1) yielded compound TPA-PDI as a
1
All solvents and chemicals used were purchased from Energy purple solid (123.7 mg, 31.4% yield). H NMR (400 MHz, CDCl
3
,
Chemical and used without further purification. TLC analyses ppm): δ10.08 (d, 2H), 8.45 (s, 1H), 8.20 (d, 1H), 8.15(s, 1H) ,
were carried out by using Sorbent Technologies silica gel (200 7.95 (s, 1H), 7.59 (d, 2H), 7.48 (t, 1H), 7.35-7.28 (m, 3H), 4.12-
mm) sheets. Column chromatography was performed on 4.09 (m, 4H), 1.93(m, 2H), 1.78(m, 6H), 1.40-1.18(m, 64H) ,
1
3
Sorbent silica gel 60 (40–63 mm). Solution NMR spectra were 0.85-0.79 (m, 12H). C NMR (400 MHz, CDCl
at room 163.04, 162.92, 162.63, 151.61, 148.03, 145.90, 138.11, 134.07,
3
, ppm): δ 163.35,
taken on a Bruker 400 MHz spectrometer in CDCl
3
1
13
temperature, both H and C NMR spectra were referenced to 133.13, 132.69, 132.32, 130.24, 128.14, 126.80, 126.54, 125.75,
solvent residue peaks and the spectroscopic solvents were 125.38, 125.02, 124.81, 124.60, 123.34, 123.07, 122.67, 122.30,
purchased from Cambridge Isotope Laboratories. Mass spectra 122.06, 120.75, 119.91, 116.14, 115.44, 102.15, 91.72, 80.07,
were measured on a Bruker Maxis UHR-TOF MS spectrometer. 77.33, 77.02, 76.70, 44.84, 44.69, 36.80, 36.67, 31.92, 31.91,
UV−vis absorpꢀon spectra were performed with a Beijing 31.84, 31.72, 30.13, 29.71, 29.68, 29.66, 29.38, 29.36, 27.98,
-
1
Purkinje
General
Instrument
Co.
Ltd.
TU-1901 26.64, 26.54, 22.67, 22.66, 14.10. FT-IR (KBr, cm ): 2918, 2847,
spectrophotometer. Fluorescence spectra measurements were 2177, 1695, 1690, 1584, 1485, 1428, 1267. HRMS:
+
10 (M ), calcd, 2303.5251, found 2303.5255.
performed
using
FLS-920
Edinburgh
spectrometer. All steady-state measurements were carried out Analytical calculation for C156
fluorescence
C
156
H
199
N
5
O
199 5
H N O
10: C, 81.31; H, 8.70; N,
using a quartz cuvette with a path length of 1 cm. Element 3.04;Experimental result: C, 80.78; H, 8.89;N 2.85 .
alanalyses (EA) were performed on a Flash EA 1112 elemental
analyzer. Thermogravimetric analysis (TGA) was carried out on 4.2.3. Synthesis of TPA-PDI
3
a TA Instrument TA Q50 the thermogravimetric Analyzer at a
o
heating rate of 10 C/min up to 600 C.
o
Py-PDI-Br (550 mg, 0.534 mmol), TPA-3EY (50 mg, 0.157
mmol), Pd(PPh
3
)
4
(100 mg) and CuI (60 mg) were added to a
gas, then dry
round bottom flask with the protection of Ar
2
4
.2. Materials synthesis
toluene (20 mL) and dry diisopropylamine (5 mL) were injected
o
into it. The reaction was stirred under 80 C overnight. The
PBDB-T was purchased from Organtec solar Materials Inc, M
n
:
3
2 kDa; PDI = 2.5. TPA-2EY and TPA-3EY were synthesized cooled mixture was extracted with dichloromethane and water.
1
3
according to the literature with a modified method and The residue was purified by column chromatography (eluent,
shown in ESI.
.2.1. Synthesis of Py-PDI-Br
hexane/DCM, 20:1, 1:1) yielded TPA-PDI3 as a purple solid (160
1
mg, 31% yield). H NMR (400 MHz, CDCl , ppm): δ 10.22 (s, 1H),
3
4
8.46-8.24 (m, 3H), 7.77-7.75 (m, 3H), 7.38 (d, 2H), 4.10-4.07 (m,
4
H), 1.93-1.80 (m, 8H), 1.26-1.11 (m, 64H), 0.83-0.73 (m, 12H).
1
3
To a mixture of Py-PDI (0.5 g, 0.5 mmol), CHCl
3
(50 mL) and
C NMR (400 MHz, CDCl , ppm): δ 163.33, 163.11, 162.73,
3
K
2
CO (1.0 g，7.2 mmol) was added bromine (2.0 mL
3
，
0.4 162.36, 151.59, 146.98, 134.18, 133.38, 132.79, 132.29, 126.60,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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Journal of Materials Chemistry C
Page 6 of 8
View Article Online
DOI: 10.1039/C8TC02823K
ARTICLE
Journal Name
1
1
2
2
2
25.30, 125.02, 124.54, 123.45, 122.98, 122.38, 120.55, 119.52, acknowledges the financial support from start-up grant of
15.35, 101.48, 92.21, 80.19, 31.92, 31.84, 31.69, 30.14, 30.10, Shandong Normal University and Shandong Province Natural
9.74, 29.72, 29.68, 29.66, 29.60, 29.58, 29.38, 29.30, 26.65, Science Foundation (ZR2016BM24).
-1
6.48, 22.68, 22.60, 14.11, 14.09, 14.03. FT-IR (KBr, cm ): 2913,
839, 2172, 1687, 1654, 1580, 1494, 1423, 1267, 1164. HRMS:
+
15 (M ), calcd, 3333.2290, found 3333.2343.
Notes and references
C
225
H
291
N
7
O
Analytical calculation forC225
291 7
H N O15: C, 81.06; H, 8.80; N,
2
.94; Experimental result: C, 80.88; H , 8.79; N 2.95.
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4.3. Computational method
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2
018, 118, 3447; (c) G. Li, R. Zhu and Y. Yang, Nat. Photonics,
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The geometry was optimized by density functional theory (DFT)
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H. Yan, Nat. Energy, 2016, , 15027; (b) M. Li, K. Gao, X. Wan,
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1
1G(d). Quantum chemical calculation was performed with
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3
the Gaussian09 package. The long alkyl chains were replaced
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3
Solar cells were fabricated in
a
conventional device
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substrates were treated by UV-Ozone for 20 min before use.
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onto the ITO substrates at 4000 rmp for 40s, and then dried at
1
D. Zhu and X. Zhan, Energy Environ. Sci., 2015, , 610; (d)S.
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ratio were dissolved in O-dichlorobenzene (the concentration
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spin-cast at 1600 rmp for 40 s on the top of PEDOT: PSS layer
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,
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-5
2
under vacuum of 5×10 Pa. The active area is 4.50 mm . The
2
area of each device was 3.14 mm defined by a shadow mask.
The optimal blend thickness was about 95 nm, measured on a
Bruker Dektak XT stylus profilometer. Current density-voltage
,
5
137. (l) X. Zhan, A. Facchetti, S. Barlow, T. J. Marks, M. A.
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2
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(
AM 1.5 G) solar simulator (Class AAA solar simulator, Model
-
4063A, Oriel) with an irradiation intensity of 100 mW cm ,
2
9
which was measured by a calibrated silicon solar cell and a
readout meter (Model 91150V, Newport). EQE spectra were
measured by using a QEX10 Solar Cell EQE measurement
system (PV measurements, Inc.).
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2
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There are no conflicts to declare.
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of China (No. 21390411, 21535004, 91753111). G. Li
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| J. Name., 2012, 00, 1-3
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DOI: 10.1039/C8TC02823K
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Journal of Materials Chemistry C
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DOI: 10.1039/C8TC02823K
Through the coupling of acetylene substituted triphenylamine and pyran-annulated
perylene diimides, two novel non-fullerene electron acceptors, coded as TPA-PDI2
and TPA-PDI , were designed, synthesized and applied in BHJ organic solar cells.
3