N -Annulated perylene diimide derivatives as non-fullerene acceptors for solution-processed solar cells with an open-circuit voltage of up to 1.14 v

Article abstract of DOI:10.1039/c8nj02566e

Three different non-fullerene small molecular acceptors containing N-annulated perylene diimide, named di-PNR, TPA-PNR and EDOT-PNR, were successfully designed and synthesized for photovoltaic applications. Introducing an electron donating unit such as tr

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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N-annulated Perylene Diimide Derivatives as Non-Fullenence
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Acceptors for Solution-Processed Solar Cells with Open-Circuit
www.rsc.org/
Voltage up to 1.14 V
Fei Youa, Xingbao Zhou a, Hongyan Huang a,*, You Liua, Sizhou Liua, Jinjun Shaoa, Baomin Zhaob,*
Tianshi Qina, Wei Huanga,b,c,*
,
Three different non-fullerene small molecular acceptors containing N-annulated perylene diimide, named di-PNR,
TPA-PNR and EDOT-PNR were successfully designed and synthesized for photovoltaic applications. Introducing an
electron donating unit such as triphenylamine (TPA) or 2,3-dihydrothieno[3,4-b][1,4]dioxine (EDOT), into the N-
annulated PDI derivatives impart significant influence on the light-harvesting capabilities, energy level, the
morphology as well as the photovoltaic performance. Preliminarily, TPA-PNR and EDOT-PNR possessed lower band
gaps and higher HOMO/LUMO energy levels. Power conversion efficiencies (PCEs) of 5.29% and 4.54% were
obtained for the inverted solar cells based on the blends of PTB7-Th/di-PNR and PTB7-Th/TPA-PNR, respectively,
resulting from their smooth morphology of the blend films and the intense light absorption that increases the Jsc
and FF. Under the same optimization conditions, EDOT-PNR exhibited a low PCE of 1.6% with a remarkably high
Voc of 1.14 V because of its higher LUMO energy level, which was one of the highest Voc values reported for
organic solar cells using N-annulated PDI derivatives as the electron acceptors. Our work offers an effective
guideline for the design of non-fullerene acceptors using N-annulated PDI derivatives.
BHJ OSCs. Compared with fullerene derivatives, NFAs possess
some distinctive advantages,[10-15] e.g. adjustable chemical
structures and energy levels, inexpensive synthetic cost,
Introduction
Bulk heterojunction (BHJ) organic solar cells (OSCs)
containing fullerene acceptors have attracted extensive
research attention for their promising applications in next
generation of clean and renewable energy sources owing to
unique advantages, such as low cost, light-weight, large area
production and mechanical flexibility.[1-6] High-performance
BHJ OSCs have been reported with power conversion efficiency
(PCE) of 11%.[7] Very recently, BHJ OSCs with non-fullerene
acceptors (NFAs) have received considerable interests as a
promising alternative to fullerene BHJ OSCs and the PCE have
reached 14%,[8-9] which rewrote the PCE record for fullerene
improved light absorption in the visible regions, and enhanced
match capability with donor materials. Intensive research
interesting has been devoted to designing and synthesizing
NFAs for replacing fullerene acceptors in BHJ OSCs, a series of
high-performance NFAs have been developed and successfully
applied to high-performance BHJ OSCs, two representative
NFAs are the system of perylene diimide (PDI) and 3,9-bis(2-
methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-
tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-
b:5,6-b′]-dithiophene (ITIC) family.[16-20] The PCEs of BHJ OSCs
based on the family of ITIC acceptors have exceeded 12%,[18]
while the best-performing BHJ OSCs based on PDI show a PCE
around 10%.[19] Actually, PDI derivatives show appealing
characters including excellent chemical, photochemical,
thermal stabilities, high electron mobility (10-3 ~ 101 cm2 V‒1
s‒1), strong absorption in visible region (between 400 and 650
nm), and superior electron affinity (ca. -4.0 eV). The solubility,
energy levels and optoelectronic properties could be readily
tuned.[21-24] Yet, the high planarity and strong intermolecular
stack of PDI tend to excessive aggregate, resulting in easily
forming large crystalline domains and phase separation in BHJ
films, which is not conducive to the photovoltaic performance
of BHJ OSCs.[25-29]
a.Key Laboratory of Flexible Electronics (KLOFE) and Institute of Advanced Materials
(IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials
(SICAM), Nanjing Tech University (Nanjing Tech), 30 South Puzhu Road, Nanjing
211816, iamwhuang@njtech.edu.cn
b.Key Laboratory for Organic Electronics and Information Displays &Jiangsu Key
Laboratory for Biosensors, Institute of Advanced Materials (IAM), Jiangsu
National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing
University of Posts and Telecommunications, 9 Wenyuan Road, Nanjing 210023,
China. E-mail: iambmzhao@njupt.edu.cn
c. Shaanxi Institute of Flexible Electronics (SIFE) Northwestern Polytechnical
University (NPU) Xi’an 710072 China
Electronic Supplementary Information (ESI) available: TGA spectra, NMR spectra,
MALDI-TOF MS and device optimization. See DOI:10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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Several strategies were adopted to suppress the strong
Journal of Materials Chemistry C
Bis(pinacolato)diboron and Pd(PPh3)4 were purchased from
aggregation tendency of PDI derivatives.[30-32] Constructing PDI Energy Chemical Inc. Some intermediate products, such as
dimers via introducing torsion into the conjugated backbone is tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-
an effective method to obtain highly efficient NFAs,[33] which amine and 5,7-bis(trimethylstannyl)-2,3-dihydrothieno[3,4-
can be connected a single bond,[34] π-bridge units including b][1,4]dioxine were synthesized according to the reported
oligothiophene,[35]
selenophene,[36] phenylene[37]
and procedures with optimization, and the detailed synthetic
biphenylene,[38] other fused aromatic rings were also used to procedures are described in supporting information. Toluene
construct PDI dimers, such as benzo[1,2-b:4,5-b']dithiophene and THF were freshly distilled from Na metal prior to use.
(
spirobi[9H-fluorene]
BDT),[39] indaceno [1,2-b:5,6-b']dithiophene
(
IDT)[40] and 9,9'- Other solvents and reagents were used directly without any
(
SBF).[41] Another common method treatment.
includes the substitution of the imide position, bay position or
non-bay position of the PDI units with different functional
groups to construct PDI trimmers or tetramers with three
dimensional (3D) geometry.[42-44] This method can also
General instruments
1H NMR and 13C NMR data were recorded on a Bruker Ultra
Shield Plus AV400 spectrometer in CDCl3 solution at 298 K with
tetramethylsilane (TMS; d = 0 ppm) as the internal standard (1H
NMR: 400 MHz; 13C NMR: 100 MHz). Matrix assisted laser
desorption/ionization time of-flight mass spectrometry
(MALDI-TOF MS) was conducted by a Bruker Autoflex II mass
spectrometer using anthracene-1,8,9-triol as matrix.
Thermogravimetric (TGA) analysis was performed using a
Rigaku TG-DTA 8120 thermal analyzer at a heating rate of 10 oC
min‒1 under nitrogen atmosphere. UV-vis absorption spectra
were measured on a Shimadzu UV-1700 spectrometer. CV
measurements were conducted on a CHI 620C electrochemical
effectively reduce molecular aggregation of PDIs. In addition to
[46]
this, incorporating heteroatoms such as S,[45] Se,
or N[47] in
the bay positions of the PDI framework is considered as a more
effective way to reduce intermolecular aggregation. Typically,
SdiPDI-S containing S-annulation in PDI framework was
reported by Wang's group and used for OSCs showing a PCE
over 7%[45]
. Meanwhile, Z. H. Wang and his coworkers
developed Se-annulated PDI dimer SdiPDI-Se with admirable
PCE.[46] The ternary organic solar cell based on SdiPDI-Se as the
electron acceptor yielded a PCE of 10.3%.[47] N-annulated PDI
dimer was exploited by Welch's group and realized a PCE of
7.55% when it was blended with P3TEA.[48] They futher
designed some N-annulated PDI derivates as the acceptors and
successfully applied to BHJ OSCs.[49-51] However, few works has
reported to construct N-annulated PDI based A-D-A NFAs as
previously done to other PDI derivatives.
analyzer with
a
three-electrode system containing
tetrabutylammonium phosphorus hexafluoride (Bu4NPF6, 0.1
M) as an electrolyte in anhydrous dichloromethane at a scan
rate of 50 mV s‒1. Surface roughness and morphologies of thin
flms were characterized by atomic force microscopy (AFM)
(Thermo. Auto Probe
C P Res.). Transmission electron
microscope (TEM) measurements were carried out via a JEOL
JEM-1011 transmission electron microscope operated at an
acceleration voltage of 100 kV.
In this work, considering excellent photovoltaic
performance of N-annulated PDI dimer, we designed and
synthesized three different non-fullerene small molecule
acceptors containing N-annulated PDI, named di-PNR, TPA-PNR
and EDOT-PNR (Fig. 1). Longer branched alkyl chains were
introduced to N-annulated PDI to improve the solubility. The
electron donating unit such as TPA or EDOT was introduced to
N-annulated PDI derivatives, which influenced the light-
harvesting capabilities, energy level, the morphology as well as
the photovoltaic performance. The energy band gaps and
HOMO/LUMO levels were compared according to the cyclic
voltammetry (CV) measurements and theoretical simulations.
As a preliminary result, the device based on PTB7-Th/di-PNR
and PTB7-Th/TPA-PNR yielded a PCE of 5.29% and 4.54%,
respectively. Their smooth morphology of the blend films and
the intense light absorption that increases the Jsc and FF.
Although solar cells using EDOT-PNR as the electron acceptor
exhibited poor device performance (1.60%), the device
delivered an impressively high Voc up to 1.14 V, which is one of
the highest Voc values reported for organic solar cells using N-
annulated PDI derivatives as the electron acceptors.
Fabrication and characterization of inverted solar cells
Solution-processed non-fullerene BHJ organic solar cells
were fabricated with an inverted configuration of
ITO/ZnO/active layer/MoO3/Ag. ITO glass substrates were
cleaned sequentially with deionized water, alcohol and acetone
for 15 min each by sonication, and then treated in an UV ozone
generator for 15 min. A thin layer of sol-gel ZnO was spin
coated onto precleaned ITO glass substrates and then annealed
o
at 180 C for 15 min.[52] Following, the active layer films were
prepared by spin-coating PTB7-Th: acceptor (di-PNR, TPA-PNR
or EDOT-PNR) solutions. The thickness of the active layer was
determined to be ca 100 nm by a Dektak 150 profilometer.
Lastly, MoO3 and Ag were thermally evaporated under a
vacuum of 2 × 104 Pa on top of the active layer. The
photovoltaic performance was measured by a computer-
programmed Keithley 4200 source meter under illumination at
100 mW cm‒2 AM 1.5G irradiation. The external quantum
efficiency (EQE) of organic solar cells were measured with a
source meter, silicon photodiode and a computer controlled
light source-monochromator-lock-in system.
Experimental section
Materials
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Fig. 1 Chemical structures of di-PNR, TPA-PNR, EDOT-PNR and PTB7-Th.
Scheme 1 The synthesis routes of the three compounds di-PNR, TPA-PNR and EDOT-PNR: (i) Zn(OAC)2, NH(C5H11)2, iminazole, 200 oC, 5
h; (ii) conc.HNO3, dichloromethane, 0 oC, 3 h; (iii) PPh3, chlorobenzene, 135 oC, 12 h; (vi) K2CO3, KI, DMF, 70 oC, 12 h; (v) HOAc, Br2,
chloroform, 25 oC, 6 hr.
Synthesis
Compound (1) In a 250 mL round bottom flask (RBF), 3, 4, 9,
filtered and dried in vacuum. The crude product was purified
by column chromatography (chloroform/hexane as an eluent)
to obtain compound 1 with a yield of 81%. H NMR (400 MHz,
1
CDCl3) δ 8.67 – 8.62 (m, 8H), 5.21 – 5.15 (m, 2H), 2.27 – 2.19
(m, 4H), 1.89 – 1.83 (m, 4H), 1.33 – 1.23 (m, 24H), 0.85 – 0.81
(m, 12H). 13C NMR (100 MHz, CDCl3) δ 164.51, 163.50, 134.35,
131.73, 131.05, 129.50, 126.32, 123.84, 123.17, 122.88, 54.76,
32.33, 31.74, 26.64, 22.55, 14.01. MALDI-TOF-MS m/z: [M]
calcd. for C46H54N2O4, 698.95; found, 697.22 [M+].
10-Perylenetetracarboxylic dianhydride (5 g, 12.75 mmol),
imidazole (25 g, 367.22 mmol) and zinc acetate (1.756 g, 9.56
mmol) were added. The mixture was stirred at 150 oC under N2
before injecting 1-Pentylhexylamine (13 mL). After 4 h, the
mixture was cooled to room temperature, poured into HCl (2
M, 400 mL) and stirred for 12 h. The red precipitate was
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Journal of Materials Chemistry C
Compound (2) In a two-necked RBF, compound 1 (0.5 g, 2H), 4.91 – 4.87 (m, 2H), 2.36 (m, 4H), 2.21 – 2.17 (m, 2H), 1.95
0.71 mmol) was dissolved in dichloromethane at 0 oC. Then the (s, 4H), 1.41 – 1.23 (m, 34H), 0.86 – 0.82 (m, 15H). 13C NMR
nitrating agent (the mixture of 4 mL fuming nitric acid and 8 (100 MHz, CDCl3) δ 164.78, 163.81, 134.57, 134.23, 134.01,
mL dichloromethane) was added over a period of 10 min. The 131.80, 129.91, 127.05, 126.57, 123.88, 123.23, 122.96, 122.40,
reaction solution was stirred at 0 oC for another 1 h and 121.70, 121.04, 118.35, 117.93, 117.42, 55.09, 54.94, 46.81,
quenched by adding ice water (100 mL) before being extracted 32.56, 31.88, 31.86 – 31.74, 31.65, 31.42, 29.69, 29.13, 29.08,
with dichloromethane. The crude product was collected by 27.20, 26.85, 22.66, 22.53, 14.10, 13.99. MALDI-TOF-MS m/z:
rotary evaporation and purified through column [M] calcd. for C54H68BrN3O4, 903.04; found, 901.87 [M+].
chromatography with petroleum ether/dichloromethane (v/v,
di-PNR In a 25 mL Schlenck tube, PNR-Br (1.05 g, 1.16
1:1) as an eluent to produce compound 2 as an dark red solid
mmol), acetic acid sodium salt (952 mg, 11.6 mmol) were
1
(480 mg, 90%). H NMR (400 MHz, CDCl3) δ 8.74 (m, 5H), 8.59
added in a mixture containing DMF (10 mL), toluene (3 mL) and
(s, 1H), 8.26 (d, J = 8.2 Hz, 1H), 5.16 (m, 2H), 2.27 – 2.19 (m,
water (1 mL). The mixture was degassed with N2 for 15 min
4H), 1.86 – 1.80 (m, 4H), 1.28 – 1.25 (m, 24H), 0.84 – 0.81 (m,
before
Pd(dppf)Cl2
(50
mg,
0.06
mmol)
and
12H). 13C NMR (100 MHz, CDCl3) δ 147.70, 135.48, 132.93,
129.49, 129.35, 129.11, 127.90, 127.52, 126.62, 126.46, 124.46,
124.00, 55.26, 54.97, 32.27, 32.18, 31.69, 31.66, 26.57, 26.55,
22.52, 13.99. MALDI-TOF-MS m/z: [M] calcd. for C46H53N3O6,
743.95; found, 742.29 [M+].
bis(pinacolato)diboron (147 mg, 0.58 mmol) were added under
N2 atmosphere. The reaction system was heated to 70 oC
overnight. Di-PNR was purified by column chromatography
with petroleum ether/ dichloromethane (v/v, from 2:1 to 1:1)
1
as an eluent (468 mg, 49%). H NMR (400 MHz, CDCl3) δ 9.30
Compound (3) In a 25 mL Schlenck tube, compound 2 (744 (d, J = 17.9 Hz, 2H), 9.12 (d, J = 17.5 Hz, 1H), 8.90 (d, J = 17.8 Hz,
mg, 1 mmol), chlorobenzene (10 mL) and PPh3 (787 mg, 3 2H), 8.00 – 7.92 (m, 2H), 7.71 (d, J = 9.5 Hz, 2H), 5.42 – 5.22 (m,
mmol) were added under N2 atmosphere. The mixture was 8H), 5.02 (s, 2H), 2.34 – 2.30 (m, 8H), 2.23 (m, 4H), 2.00 – 1.75
o
heated to 135 C and stirred overnight. After cooled to room (m, 8H), 1.46 – 1.13 (m, 68H), 0.88 – 0.70 (m, 30H). 13C NMR
temperature, the reaction mixture was extracted with ethyl (100 MHz, CDCl3) δ 166.51, 165.29, 164.79, 164.01, 163.39,
acetate and the organic phase was dried with anhydrous 140.91, 135.29, 135.08, 132.94, 130.85, 130.42, 130.11, 128.00,
Na2SO4. The crude product was purified by column 127.27, 126.85, 124.94, 124.71, 123.60, 122.78, 120.12, 119.85,
chromatography with petroleum ether/dichloromethane (v/v, 119.24, 119.05, 118.45, 55.10, 54.69, 47.13, 32.86, 32.65,
from 1:1 to 1:2) as an eluent to yield compound 3 (533 mg, 32.51, 32.37, 31.83, 31.74, 31.70, 31.68, 29.68, 29.25, 29.15,
1
75%). H NMR (400 MHz, CDCl3) δ 10.26 (s, 1H), 9.06 (d, J = 27.34, 26.77, 26.52, 22.58, 22.44, 14.04, 13.92. MALDI-TOF-MS
15.0 Hz, 2H), 8.92 (d, J = 7.9 Hz, 2H), 8.87 – 8.80 (m, 2H), 5.35 m/z: [M] calcd. for C108H136N6O8, 1645.04; found, 1644.87 [M+].
(s, 2H), 2.35 (m, 4H), 1.95 (m, 4H), 1.31 – 1.25 (m, 24H), 0.88 –
TPA-PNR In
a 25 mL Schlenck tube, tris(4-(4,4,5,5-
0.80 (m, 12H). 13C NMR (100 MHz, CDCl3) δ 166.44, 165.37,
165.09, 164.09, 133.43, 132.23, 128.11, 127.35, 124.27, 123.25,
122.67, 121.86, 121.11, 120.36, 119.53, 55.09, 54.94, 32.61,
31.83, 26.91, 22.59, 14.01. MALDI-TOF-MS m/z: [M] calcd. for
C46H53N3O4,711.95; found, 711.30 [M+].
tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine (63 mg, 0.1
mmol) and PNR-Br (271 mg, 0.3 mmol) was dissolved in
toluene (10 mL) and 2 M K2CO3 solution (5 mL). The mixture
was degassed with N2 flow for 20 min, then Pd(PPh3)4 (57 mg,
0.05 mmol) was added under N2 atmosphere. The mixture was
PNR In a two neck round bottomed flask, compound 3 (712 heated to reflux for 48 h. AFter that, the crude product was
mg, 1 mmol), K2CO3 (415 mg, 3mmol), KI (16.6 mg, 0.1 mmol) extracted with dichloromethane and dried over Na2SO4. The
were mixed in dry N,N-dimethylformamide (DMF, 15 mL) under crude product was obtained by rotary evaporation and
N2 atmosphere, then 1-bromooctane (2.12 g, 1.1mmol) was purified by column chromatography with the mixture of
injected. The reaction mixture was heated to 100 oC for 6 h, petroleum ether/dichloromethane (v/v, 2:1) as an eluent to
1
followed by being extracted with ethyl acetate. The organic give the target product TPA-PNR (111 mg, 41%). H NMR (400
layer was dried with anhydrous Na2SO4 and evaporated under MHz, CDCl3) δ 9.11 – 9.04 (t, J = 14.2 Hz, 6H), 8.87 (d, J = 27.0
reduced pressure. Pure product of PNR was obtained by Hz, 3H), 8.63 – 8.56 (m, 3H), 8.39 (s, 3H), 7.79 (s, 12H), 5.36 –
column
chromatography
with
petroleum 5.21 (m, 6H), 4.95 (s, 6H), 2.38 (m, 6H), 2.27 – 2.24 (m, 12H),
ether/dichloromethane as an eluent (v/v, 2:1) (741 mg, 90%). 1.91 – 1.80 (m, 12H), 1.38 – 1.19 (m, 102H), 0.86 – 0.73 (m,
1H NMR (400 MHz, CDCl3) δ 9.02 – 8.98 (m, 4H), 8.89 – 8.82 (dd, 45H). 13C NMR (100 MHz, CDCl3) δ 166.75, 166.68, 165.58,
J = 20.0, 9.5 Hz, 2H), 5.35 (s, 2H), 4.89 (m, 2H), 2.39 – 2.30 (m, 165.29, 165.16, 164.24, 164.13, 147.87, 142.47, 136.90,
4H), 2.22 – 2.18 (m, 2H), 1.93 (m, 4H), 1.38 – 1.23 (m, 34H), 135.17, 134.79, 133.84, 131.99, 131.32, 130.50, 130.26,
0.85 – 0.81 (m, 15H). MALDI-TOF-MS m/z: [M] calcd. for 127.94, 127.11, 125.69, 124.85, 124.09, 123.25, 123.16,
C54H69N3O4, 823.53; found, 822.47 for [M]+.
122.77, 122.02, 121.89, 121.09, 120.07, 119.01, 118.74,
118.21, 117.93, 54.89, 54.78, 54.70, 54.63, 46.91, 34.88, 34.54,
33.84, 32.66, 32.54, 31.94, 31.86, 31.75, 31.71, 31.58, 31.45,
30.20, 29.71, 29.38, 29.23, 29.15, 27.27, 26.71, 26.62, 22.61,
22.58, 22.52, 14.14, 14.09, 14.05, 14.00. MALDI-TOF-MS m/z:
PNR-Br In a 50 mL two-necked RBF, PNR (824 mg, 1 mmol),
acetic acid sodium salt (164 mg, 2 mmol), CHCl3 (8 mL) and
HAC (8 mL) were mixed at 0 oC. The liquid bromine (1.87g,
11.6mmol) was slowly added over 10 min. The solution was
[M] calcd. for C180H216N10O12, 2711.77; found, 2711.68 [M+]
EDOT-PNR In a 25 mL Schlenck tube, 5,7-
.
o
allowed to stir at 0 C for 4h. The reaction was quenched by
adding saturated Na2S2O3 solution before extracted with
dichloromethane. Pure PNR-Br was obtained by column
chromatography with petroleum ether/dichloromethane (v/v,
bis(trimethylstannyl)-EDOT (72 mg, 0.1 mmol), PNR-Br (217
mg, 0.24 mmol), and Pd(PPh3)4 (57 mg, 0.05 mmol) were
added in dry toluene (15 mL). The mixture was heated to 100
oC and stirred for 24 h. After cooled to room temperature, the
1
5:2) (802 mg, 88%). H NMR (400 MHz, CDCl3) δ 10.18 (d, J =
9.8 Hz, 1H), 9.04 – 9.01 (m, 3H), 8.90 – 8.82 (m, 1H), 5.33 (s,
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mixture was extracted with ethyl acetate. The organic phase and 68.2° between each benzene ring and PNR subunits,
was dried with anhydrous Na2SO4. The target product EDOT- respectively. Clearly, these molecules displayed twisted
PNR was obtained by column chromatography with petroleum structure, which could be beneficial to astrict aggregation
ether/dichloromethane as an eluent (v/v, 3:1) (129 mg, 72%). among the PDI molecules.[54] Additionally, the distributions of
1H NMR (400 MHz, CDCl3) δ 9.15 – 9.09 (m, 6H), 8.89 – 8.67 (m, the electron density were also calculated for the three
4H), 5.37 (s, 4H), 4.96 (s, 4H), 4.19 (s, 4H), 2.39 – 2.22 (m, 12H), molecules. For TPA-PNR, the lowest unoccupied molecular
1.95 – 1.90 (m, 8H), 1.42 – 1.22 (m, 68H), 0.89 – 0.82 (m, 30H). orbital (LUMO) levels mainly locate at three PNR subunits, the
13C NMR (100 MHz, CDCl3) δ 166.70, 166.64, 165.60, 165.52, highest occupied molecular orbital (HOMO) levels localize on
165.13, 164.09, 164.06, 139.19, 135.15, 135.02, 133.69, the core unit, suggesting a significant charge polarization in
132.96, 132.33, 132.23, 131.99, 131.50, 130.31, 128.57, the exited state. the LUMO energy levels of EDOT-PNR focus
128.46, 128.13, 127.41, 127.12, 124.87, 124.69, 123.32, on the two PNR subunits, however, the HOMO energy levels
123.16, 123.00, 122.61, 122.41, 122.08, 121.83, 121.31, localize on along the whole molecule. The calculated HOMO
119.93, 119.23, 119.06, 118.44, 118.26, 117.53, 64.96, 54.91, and LUMO energy levels of di-PNR, TPA-PNR, EDOT-PNR are –
46.89, 32.66, 32.59, 31.88, 31.72, 31.62, 31.45, 30.20, 29.78, 5.95/–3.19 eV, –5.45/–3.17 eV and –5.69/–3.21 eV,
29.23, 29.16, 27.28, 26.77, 22.62, 22.59, 14.10, 14.06. MALDI- respectively. Obviously, by construting A-D-A type NFAs with
TOF-MS m/z: [M] calcd. for C114H140N6O10S, 178
1784.13 [M+].
5.04; found, PNR and electron donating units, the energy levels and
Results and discussion
Material synthesis and Thermal properties
Fig.1 shows the molecular structures of the target
compounds di-PNR, TPA-PNR and EDOT-PNR. Scheme 1 depicts
their synthetic routes. Firstly, PNR, was synthesized following
modified procedures.[47] di-PNR, as the homocoupled PNR, was
obtained under Pd(dppf)Cl2 as the catalyst and DMF/H2O as the
solvent under alkaline condition. TPA-PNR and EDOT-PNR were
synthesized by Suzuki and Stille coupling reaction,[53-55]
respectively. The chemical structures of di-PNR, TPA-PNR and
EDOT-PNR were unambiguously confirmed ultilizing 1H NMR
and MALDI-TOF MS measurements (see supporting
information). As expected, each of di-PNR, TPA-PNR and EDOT-
PNR exhibited excellent solubility in common organic solvents,
such as dichloromethane, chloroform, toluene, chlorobenzene,
o-dichlorobenzene and etc. Their excellent solubility can
guarantee solution-processed technique in the fabrication of
organic solar cells. Thermal properties of di-PNR, TPA-PNR and
EDOT-PNR were measured by Thermogravimetry analysis (TGA).
As shown in Fig. S1 and Table 1, the decomposition
temperature (Td) at 5 wt % under N2 atmosphere are over
390 °C, which is high enough for organic solar cells or other
optoelectronic applications.
Fig.
2 Simulated molecular geometries obtained by DFT
calculations for simplified molecules of di-PNR, TPA-PNR and
EDOT-PNR.
bandgaps both can be tuned.
Optical properties
The UV–vis absorption spectra of diPNR, TriPNR and EDOT-
PNR in dilute dichloromethane solutions (~ 10‒5 M) and solid
films (prepared by spin-coating on quartz) were measured and
shown in Fig.3a and 3b. The major data were summarized in
Table 1. In the dilute dichloromethane solution, di-PNR, TPA-
PNR and EDOT-PNR displayed similar absorption features with
a broad absorption peak ranging from 400 to 570 nm as
previously reported results.[30] The maximum extinction
Theoretical analysis
Density functional theory (DFT) theoretical calculation
with the B3LYP-6-31G(d) basis set was used to understand the
molecular geometry of the three compounds di-PNR, TPA-PNR
and EDOT-PNR. The alkyl side chains attached on the PNR
skeleton were replaced with methyl groups to simplify the
calculations and save the calculation power. The calculated
HOMO and LUMO energy levels as well as electronic-density
distribution were showed in Fig. 2. Compound di-PNR exhibits
a dihedral angle of 91.7° between the two PNR subunits owing
to intrinsic steric hindrance. In contrast to di-PNR, the torsion
angles between PNR subunits and EDOT unit increased to
55.5°. For TPA-PNR, the torsion angles are about 67.2°, 67.9°
coefficients were 2.36
0.75
105 M-1 cm-1, respectively. The relatively high extinction
╳ ╳
105 M-1 cm-1, 1.97 105 M-1 cm-1 and
╳
coefficients may be beneficial to improve the ability of light
absorption and Jsc as well as the photovoltaic performance.
The absorption peak of the three compounds in thin films
showed no obvious red-shift in comparison to those of
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Fig. 3 (a) Absorption spectra of di-PNR, TPA-PNR and EDOT-PNR in solution, (b) Absorption spectra of di-PNR, TPA-PNR and EDOT-PNR
in thin films, (c) Absorption spectra of the blend films (The D:A ratios of PTB7-Th:acceptor are 1:1), (d) Cyclic voltammograms of di-PNR,
TPA-PNR and EDOT-PNR recorded from solution at a scan rate of 50 mV s-1.
Table 1 Optical and electrochemical properties of di-PNR, TPA-PNR and EDOT-PNR
Solutionb
ε M–1 cm–1
2.36 × 105
1.97 × 105
0.75 × 105
Filmc
HOMO(eV)
Compound
di-PNR
Tda (oC)
406
λmax (nm)
494, 533
494, 527
501, 535
λmax (nm) λedge (nm) Eogpt (eV)d
LUMO(eV)
–3.75
495, 534
501, 526
496, 532
608
663
620
2.04
1.87
2.00
–5.97
–5.45
–5.75
TPA-PNR
EDOT-PNR
394
–3.65
388
–3.68
a The 5% weight-loss temperatures under nitrogen atmosphere. b Measured in dilute dichloromethane solution.c Cast from
dichloromethane solution.d Bandgap estimated from the onset wavelength (λedge) of the optical absorption: Eogpt = 1240/λedge
.
solution, disclosing that the aggregation of the three blend films PTB7-Th:TPA-PNR, especially for PTB7-Th:di-PNR
molecules in thin films may be suppressed owing to the torsion exhibited stronger absorption than PTB7-Th:EDOT-PNR, which
is essential for achieving a higher Jsc in organic solar cells.
existing in each compound. Note that TPA-PNR and EDOT-PNR
showed a slightly wider absorption than di-PNR. Accordingly, Electrochemical properties
the optical band gaps (Eogpt ) of di-PNR, TPA-PNR and EDOT-PNR
CV measurements with Ag/AgCl as a reference electrode
were carried out to investigate the electrochemical properties
of di-PNR, TPA-PNR and EDOT-PNR in 0.1 M Bu4NPF6 anhydrous
dichloromethane. HOMO and LUMO energy levels were
estimated from the onset oxidation potential (Eox) and
reduction potential (Ered), respectively. The CV curves of the
three molecules were shown in Fig. 3d and the related
electrochemical data were shown in Table 1. The HOMO
calculated from the absorption edges of thin films are 2.04,
1.87 and 2.00 eV, respectively. These results manifest that the
incorporation of TPA and EDOT imparts significant influence on
the light harvesting ability and the optical band gaps of the
target NAFs. Fig. 3c shows the absorption spectra of blended
films. Obviously, the spectral features of the three compounds
exhibit good complementary with the absorption of PTB7-Th
(as the donor material in the blended films). Moreover, the
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energy levels of di-PNR, TPA-PNR and EDOT-PNR are –5.97, –
For di-PNR, the devices based on di-PNR:PTB7-Th display a
5.45, and –5.75 eV, respectively, while the LUMO energy levels Jsc of 11.67 mA cm–2, a Voc of 1.03 V, a FF of 44.0% and a best
are –3.75, –3.65, and –3.68 eV, respectively. Their HOMO and PCE of 5.29% with 0.25 v/v % DIO as the solvent additive,
LUMO energy levels were obviously lower than the polymer which is higher than the devce performance based on S(TPA-
donor material PTB7-Th (HOMO/LUMO: –5.12 eV/–3.60 eV).[56] PDI) as the electron acceptor.[42] TPA-PNR and EDOT-PNR
TPA-PNR and EDOT-PNR exhibit slightly higher HOMO and yielded the inferior PCE of 4.54% and 1.60% owing to the
LUMO energy levels in comparison with those of di-PNR, lower Jsc and FF under the same conditions, which may be
demonstrating that the introduction of the electron donating stemed from the weaker absorption intensity. Note that the
unit could raise HOMO and LUMO energy levels, which is devices using TPA-PNR and EDOT-PNR as the acceptors
attributed to the electron-donating properties of TPA and exhibited relatively higher Voc because of their slightly higher
EDOT units. It is well known that Voc is proportional to the LUMO energy levels, especially for EDOT-PNR, the device
difference between the HOMO of the donor material and the delivered an impressively high Voc up to 1.14 V, which is one
LUMO of the acceptor material,[57] thus, the slightly higher of the highest Voc values reported for organic solar cells using
LUMO of TPA-PNR and EDOT-PNR may lead to improved Voc in N-annulated PDI derivatives as the acceptors.[48-51] Especially,
organic solar cells. The experimental results of CV is in good TPA-PNR based OSC devices displayed a PCE of 4.54% which is
agreement with the absorption spectra and the theoretical 37% higher than that of S(TPA-PDI) (PCE
=
3.32%).[41]
calculations. Given the above, introducing the electron Meanwhile, the Voc of TPA-PNR based devices is around 1.08
donating units into the N-annulated PDI derivatives can V which is also higher than that of S(TPA-PDI) based devices
effectively tune the band gaps as well as the energy levels of (Voc = 0.88 V). These results suggest that PNR is a superior
the target NFAs.
building block for constructing A-D-A type NFAs. The External
quantum efficiency (EQE) spectra of the optimized devices
based on polymer donor:acceptors blend films are shown in
Fig. 5b. The devices based on di-PNR and TPA-PNR exhibited
photo-to-current responses from 350 to 800 nm with the
maximum EQE values reaching 49% and 41%, respectively. The
calculated Jsc integrated from EQE for optimum devices are
Solar cell fabrication and characterizations
To explore the photovoltaic properties of the three NFAs,
BHJ OSC devices were fabricated with an inverted
configuration of ITO/ZnO/donor polymer:acceptor/MoO3/Ag.
The commercially available PTB7-Th was chosen as the donor
material owing to the complementary absorption (Fig. 3c) and
suitable energy levels that match well with di-PNR, TPA-PNR
and EDOT-PNR (Fig. 4). The device fabrication conditions, such
as different D/A weight ratios (1:1.5, 1:1 and 1:0.8) and solvent
additive 1,8-diiodooctane (DIO) were used to optimize the
device performance. Fig. 5a shows the typical current density–
voltage (J–V) curves of OSCs under AM 1.5 solar illumination at
100 mW cm–2. Table
2 summarizes the related device
Fig. 4 Energy level diagram of inverted device with an inverted
non-fullerene sequential layer of ITO/ZnO/donor
polymer:acceptors/MoO3/Ag.
parameters. The blend films of donor polymer:acceptor as the
active layer were spin-coated from chlorobenzene solution
and the optimized weight ratio of donor to acceptor was 1:1.
Fig. 5 (a) J−V characteristics based on PTB7-Th:acceptors (1 : 3,
w/w) with DIO as the solvent additive, (b) EQE curves of solar
cells based on PTB7-Th:acceptors with 0.25 v/v % DIO as the
solvent additive under standard solar illumination conditions.
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Table 2 Photovoltaic performance of di-PNR, TPA-PNR and EDOT-PNR based on inverted solar cells under optimal conditions
Jsc
Voc
FF
PCE
(%)
Blenda
(mA/cm2)
(V)
(%)
PTB7-Th:di-PNR
PTB7-Th:di-PNRb
11.15
11.69(11.56)c
9.02
1.03
1.03
1.08
1.09
1.14
1.13
42.0
44.0
43.0
42.0
26.0
27.0
4.96
5.29
4.19
4.54
1.54
1.60
PTB7-Th:TPA-PNR
PTB7-Th:TPA-PNRb
PTB7-Th:EDOT-PNR
PTB7-Th:EDOT-PNRb
9.92(9.87)c
5.19
5.25
a: D:A ratio is 1:1 b: 0.25 v/v % DIO additive. c: Integrated from EQE curve.
11.56 mA cm-2 for di-PNR and 9.87 mA cm-2 for TPA-PNR, exhibited uniform surface morphology with appropriate
respectively, which are pretty close to the Jsc obtained from domain size, resulting in the exciton dissociation and charge
the J–V measurements.
transport and hence the better photovoltaic performance.
The surface morphology of the active layer is an important
The hole and electron mobilities of the devices were
factor of the device performance. Tapping-mode atomic force measured by the space-charge-limited current (SCLC) method
microscopy (AFM) and transmission electron microscopy (TEM) to investigate the charge-transporting behavior of the active
s
were employed to research the surface morphologies of the layer. Under the optimized conditions, the devices based on di-
blend films with DIO as the solvent additive. As shown in Fig. PNR/PTB7-Th exhibited the higher hole and electron mobility
6a-6c, Root mean square (RMS) values are 0.8 nm, 1.02 nm, of 1.6 × 10‒4 and 3.4 × 10‒5 cm2 V‒1 s‒1, respectively, which is
1.34 nm for PTB7-Th/di-PNR, PTB7-Th/TPA-PNR and PTB7- slightly higher than the hole (1.3 × 10‒4 cm2 V‒1 s‒1) and
Th/EDOT-PNR under the same conditions. The difference of electron (3.1 × 10‒5 cm2 V‒1 s‒1) mobility of TPA-PNR/PTB7-Th.
the surface morphologies may result from the the different The device based on EDOT-PNR/PTB7-Th showed the lower
aggregation behaviors of di-PNR, TPA-PNR and EDOT-PNR. hole (6.7 × 10‒5 cm2 V‒1 s‒1) and electron (8 × 10‒6 cm2 V‒1 s‒1)
Additionally, the smoother morphologies of PTB7-Th/di-PNR, mobility compared to the di-PNR/PTB7-Th and TPA-PNR/PTB7-
PTB7-Th/TPA-PNR indicated the excellent miscibility between Th devices. Obviously, these results indicate that the higher
the donor and the acceptor materials, which could lead to the h/e mobilities result in the higher JSC and PCE values in OPV
formation of the bicontinuous interpenetrating networks. The devices. Moreover, the unbalanced hole and electron mobility
results of TEM are consistent with the AFM observations as may be responsible for the relatively low photovoltaic
shown in Fig. 6d-6f. The blend films of di-PNR and TPA-PNR performance and the mobility data are consistent with the
trend in the photovoltaic performance.
Conclusions
In summary, three small molecular NFAs of di-PNR, TPA-
PNR and EDOT-PNR were synthesized and characterized,
respectively. Introducing the electron donating units into N-
annulated PDI derivatives influences their light-harvesting
capabilities, energy level, the morphology as well as their
photovoltaic performance. Compared to di-PNR, TPA-PNR and
EDOT-PNR possessed lower band gaps and higher
HOMO/LUMO energy levels. By blending with PTB7-Th, the
device based on di-PNR and TPA-PNR yielded a PCE of 5.29%
and 4.54%, respectively, resulting from their smooth and
uniform morphology of blend films and the intense light
absorption that increases the Jsc and FF. Although solar cells
Fig. 6 AFM height (a, b, c) and TEM (d, e, f) images of blend films
with 0.25% v/v DIO as the solvent additive: (a, d) PTB7-Th/di-
PNR; (b, e) PTB7-Th/TPA-PNR; (c, f) PTB7-Th/EDOT-PNR.
8 | J. Name., 2016, 00, 1-3
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15 Y. Z. Lin, T. F. Li, F. W. Zhao, L. Han, Z. Y. Wang, Y. Wu, Q. He, J.
Y. Wang, L. J. Huo, Y. M. Sun, C. R. Wang, W. Ma and X. W. Zhan,
Adv. Energy Mater., 2016, 6, 1600854.
using EDOT-PNR as the electron acceptor exhibited poor
device performance (1.60%), the device delivered an
impressively high Voc up to 1.14 V, which is one of the highest
Voc values reported for organic solar cells using N-annulated
PDI derivatives as the electron acceptors. The preliminary
results offer an effective strategy to design small molecular
NFAs based on N-annulated PDI derivatives, especially for
tuning the corresponding HOMO/LUMO energy levels. We
believe that higher performance OPV devices containing N-
annulated PDI derivatives as the electron acceptors may be
obtained through further delicate chemical structure design
and device optimization in the near future.
16 P. Cheng, G. Li, X. W. Zhan and Y. Yang, Nat Photonics., 2018,
12, 131-142.
17 C. Q. Yan, S. Barlow, Z. H. Wang, H. Yan, A. K.-Y. Jen, S. R.
Marder and X. W. Zhan, Nat. Rev. Mater., 2018, 3, 18003.
18 S. S. Li, L. Ye, W. C. Zhao, S. Q. Zhang, S. Mukherjee, H. Ade and
J. H. Hou, Adv. Mater., 2016, 28, 9423-9429.
19 S. S. Chen, G. Y. Zhang, J. Liu, H. T. Yao, J. Q. Zhang, T. X. Ma, Z.
K. Li and H. Yan, Adv. Mater., 2017, 29, 1604231.
20 Y. Z. Lin, J. Y. Wang, Z. G. Zhang, H. T. Bai, Y. F. Li, D. B. Zhu and
X. W. Zhan, Adv. Mater., 2015, 27, 1170-1174.
21 C. Li and H. Wonneberger, Adv. Mater., 2012, 24, 613-636.
22 X. G. Guo, A. Facchetti and T. J. Marks, Chem. Rev., 2014, 114,
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Acknowledgements
Fei You and Xingbao Zhou contributed equally to this work.
This work was financially supported by the National Basic
Research Program of China-Fundamental Studies of Perovskite
Solar Cells (2015CB932200), the National Synergistic
Innovation Center for Advanced Materials (SICAM), the Sci-
tech Support Plan of Jiangsu Province (BE2014719), the Priority
Academic Program Development of Jiangsu Higher Education
Institutions (PAPD) and Program for Changjiang Scholars and
Innovative Research Team in University (IRT-15R37),
Synergetic Innovation Center for Organic Electronics and
Information Displays Specialized Research Fund for the
Doctoral Program of Higher Education (20113223110005).
23 H. Kang, W. Lee, J. Oh, T. Kim, C. Lee and B. J. Kim, Acc. Chem.
Res., 2016, 49, 2424-2434.
24 X. W. Zhan, A. Facchetti, S. Barlow, T. J. Marks, M. A. Ratner, M.
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