CN110194778A - A kind of multi-arm structure organic photovoltaic material and the preparation method and application thereof - Google Patents
A kind of multi-arm structure organic photovoltaic material and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention discloses a kind of multi-arm structure organic photovoltaic material and the preparation method and application thereof.The organic photovoltaic material has multi-arm structure feature, and using three thiophene of benzo as core, then one or more donor monomers are constituted as skeleton bridging unit and introducing strong electron-withdrawing group group in end.The synthetic method raw material sources are extensive, are easy to purify, and are expected to become commercialized organic photovoltaic material.The organic photovoltaic material shows stronger absorbance, good thermal stability and higher electronics, hole mobility；Based on the organic photovoltaic devices incident photon-to-electron conversion efficiency with higher of material preparation, had potential application in photovoltaic art.
Description
Technical field
The invention belongs to optoelectronic materials technologies, and in particular to a kind of multi-arm structure organic photovoltaic material and its preparation side
Method and application.
Background technique
Organic solar batteries (OSC) can prepare large area flexible hull cell device by green inexpensive printing technology
Part shows huge development potentiality.In the past few decades, electron donor material and fowler in organic solar batteries
Alkenyl electron acceptor material achieves major progress.However, the electron acceptor material based on fullerene has the shortcomings that, example
Absorption in such as visible spectral range is weak, energy level variations are limited, synthesis cost is high and blend film in morphological stability difference
Deng.In recent years, non-fullerene electron acceptor material due to its can realize wide spectrum absorb, level structure be easy to regulate and control, chemistry and
Have excellent photostability and have with the better compatibility of electron donor material etc., attract the extensive concern of people.
So far, the best non-fullerene electron acceptor material of developed performance is typically based on electron acceptor-electronics
Donor-electron acceptor (A-D-A) skeleton, containing rich electronic core and two electrophilic end groups, incident photon-to-electron conversion efficiency has been more than
15%.But there is also some shortcomings for such material, such as absorbance is weaker, thermal stability is poor etc..In order to overcome it is above-mentioned not
Foot, we, which design, has synthesized a kind of star-type multi-arm structure electrical acceptor material system.Star-type multi-arm structure can be collected effectively
Incident light, to be conducive to improve organic solar batteries device photoelectric stream.In addition, multi-arm structural molecule being capable of more preferable Horizon
The size and exciton diffusion length scale of the solid-state molecular that weighs aggregation can not only be realized by the intermolecular interaction of appropriateness
Good electronics transfer can also effectively improve the stability of active layer film.In addition, introducing the nuclear structure list of electron rich
Member will be helpful to that electron nuclear unit and the electric charge transfer of electrophilic end groups is promoted to interact, to obtain broader optics
Band gap and higher lowest unoccupied molecular orbital (LUMO)；Light is absorbed with polymer-electronics donor material it is possible to obtaining
Complementary efficent electronic acceptor material is composed, and effectively increases open-circuit voltage (Voc), there is it in organic photovoltaic field important
Application value.
Summary of the invention
Technical problem: the present invention provides a kind of multi-arm structure organic photovoltaic material and preparation method thereof, non-at present to solve
The problems such as fullerene electron acceptor open-circuit voltage is low, stability is poor, optical absorption is poor, material preparation is complicated, overcomes non-lipid
It strangles alkene electron acceptor material performance and is difficult to the problems such as Effective Regulation.
Technical solution: to solve the above problems, the invention adopts the following technical scheme:
The present invention provides a kind of multi-arm structure organic photovoltaic material, and the material is one or more using three thiophene of benzo as core
Then donor monomer is constituted and introducing strong electron-withdrawing group group in end, is had such as following formula I institute as skeleton bridging unit
The general formula structure shown:
Wherein, n1、n2、n3For the quantity of bridging unit, and the natural number for being 0~10, preferably n=1,2；A is strong suction electricity
Subbase group；D1、D2、D3For conjugated system bridging unit.
A is selected from one of following group A1-A16:
Wherein * is link position, and C is carbon atom, and H is hydrogen atom, and O is oxygen atom, and N is nitrogen-atoms, and S is sulphur atom, F
It is fluorine atom, Cl is chlorine atom.
The D1、D2、D3For conjugated structure system bridging unit, it each is selected from one of formula:
Wherein R is hydrogen atom, C1~C30Alkyl chain, C1~C30Oxyalkyl chain, C5~C30Naphthenic base, C2~C30Miscellaneous alkane
One of base chain；S is sulphur atom, and N is nitrogen-atoms, and * is link position.
Meanwhile the present invention provides a kind of preparation method of multi-arm structure organic photovoltaic material as described above, including following
Step:
Three aldehyde radical intermediate IIs and strong electrophilic end groups A are dissolved in chloroformic solution, catalysis alkali are added dropwise, in nitrogen atmosphere
Under, 80 DEG C of reaction 12-24h, after be cooled to room temperature through extraction and chromatography obtain final product I.
More specifically, method includes the following steps:
Step 1: bridging unit and n,N-Dimethylformamide, phosphorus oxychloride being dissolved in dichloroethanes, reacted in obtaining
Mesosome 1: by bridging unit (2.8mmol), n,N-Dimethylformamide (689mg, 4.5mmol) and phosphorous oxychloride (329mg,
It 2.8mmol) is placed in three-neck flask, 30mL 1 is then added, 2- dichloroethanes dissolves, and reacts 24 hours at 100 DEG C, through washing
It washs, extract, drying, obtaining intermediate 1 after purification；
Step 2: in methylene chloride by the dissolution of above-mentioned intermediate 1, the N of N- bromo-succinimide, N- dimethyl is added
Formamide solution, reaction obtain intermediate 2: intermediate 1 (0.88mmol) being placed in single port reaction flask, 5mL dichloro is added
Methane is protected from light, ice bath；N- bromo butyryl imines (187.6mg, 1.06mmol) is dissolved in n,N-Dimethylformamide simultaneously
In, and the solution is slowly dropped in reaction flask, it is stirred overnight, obtains intermediate 2 after purification；
Step 3: three tin reagents of three thiophene of intermediate 2 and benzo are dissolved in chlorobenzene, tetrakis triphenylphosphine palladium is added,
Reaction obtains intermediate 3: by intermediate 2 (0.9mmol) and three thiophene of benzo (223mg, 0.3mmol), Pd (PPh3)4(30mg,
It 0.024mmol) is dissolved in chlorobenzene (20mL), substitutes nitrogen, above-mentioned reactant is flowed back 24 hours at 120 DEG C, passed through after cooling
Extraction, obtains intermediate 3 at drying after purification；
Step 4: intermediate 3 and strong electrophilic end groups A being dissolved in chloroform, 0.1mL pyridine is instilled and stirs 80 DEG C of reactions
12-24 hours, after extracting and washing, drying, filtering and concentrating, column Chromatographic purification obtained final product.By intermediate 3
(0.09mmol) and strong electrophilic end groups A such as bis- fluoro- 3- (dicyano methylene) indigo ketone of 5,6-, 3- (dicyano methylene) indigo
Ketone (0.36mmol) is placed in reaction tube, and 0.1mL pyridine is added dropwise, above-mentioned reactant is dissolved in 4mL chloroform, is stirred at 80 DEG C
It mixes 24 hours, obtains final product after purification.
The material can be used as active layer material or addO-on therapy for organic solar batteries such as binary, polynary or laminations
Device.
The utility model has the advantages that organic photovoltaic material preparation method of the invention is simple, reaction process is easily controllable, and product is easy to point
From, high income, purity is high.Different bridging units can be used, realize the simple regulation of material photoelectric property.In addition, such material
Material shows higher open-circuit voltage in the application of organic solar batteries device and excellent thermal stability, film forming are steady
Qualitative, light absorptive, has potential application in terms of organic solar batteries.
Detailed description of the invention
Fig. 1 is BTTIDC8IC's1H NMR spectra.
Fig. 2 is BTTIDC8IC's13C NMR spectra.
Fig. 3 is the MALDI-TOF spectrogram of BTTIDC8IC.
Fig. 4 is BTTIDC8IC-F's1H NMR spectra.
Fig. 5 is BTTIDC8IC-F's13C NMR spectra.
Fig. 6 is the MALDI-TOF spectrogram of BTTIDC8IC-F.
Fig. 7 is absorption spectrum of the target molecule BTTIDIC and BTTIDC8IC-F under film.
Fig. 8 is the curve of target molecule BTTIDIC and BTTIDC8IC-F open-circuit voltage and short circuit current.
Fig. 9 is the thermogravimetic analysis (TGA) curve of target product BTTIDC8IC and BTTIDC8IC-F.
Specific embodiment
Below by way of several embodiments, the invention will be further described, but embodiment does not limit and of the invention covers model
It encloses.
The preparation of embodiment 1:BTTIDC8IC
The synthesis of intermediate 1:IDTC8CHO: by IDTC8 (2g, 2.8mmol), n,N-Dimethylformamide (689 mg,
It 4.5mmol) is placed in three-neck flask with phosphorous oxychloride (329mg, 2.8mmol), 30mL 1 is then added, 2- dichloroethanes is molten
It solves, is reacted 24 hours at 100 DEG C.It is cooled to room temperature, reaction solution is washed with water, methylene chloride extracts three times, uses MgSO4
It is dry, it is then purified by column chromatography, obtains yellow solid IDTC8CHO (1.5g), yield 72%.1H NMR(400MHz,
CDCl3)δ9.88(s,1H),9.88(s,1H),7.61(s,1H),7.40(s,1H), 7.34(d,1H),7.31(s,1H),
6.98(d,1H),2.07-1.97(m,4H),1.93-1.82(m,4H),1.10(s,36H), 0.82(d,24H).13C NMR
(101MHz,CDCl3)δ182.89(s),156.52(s),154.93(d),153.93(s), 152.77(s),144.36(s),
141.09(s),138.53(s),133.73(s),127.79(s),121.83(s),113.21(s), 54.05(s),39.04
(s),31.80(s),29.96(s),29.95-29.27(m),29.21(s),24.22(d),22.61(s),14.08 (s),
1.04(s).MALDI-TOF-MS(m/z):Calcd for C49H74OS2,Exact Mass:742.5,Found:741.6 [M+].
The synthesis of intermediate 2:BrIDTC8CHO: IDTC8CHO (720mg, 0.88mmol) is placed in single port reaction flask
In, 5mL methylene chloride is added, is protected from light, ice bath.N- bromo butyryl imines (187.6mg, 1.06 mmol) is dissolved in N simultaneously,
In dinethylformamide, and the solution is slowly dropped in reaction flask.It after being stirred overnight, is cooled to room temperature, will react
Solution is washed with water, and methylene chloride extracts three times, uses MgSO4It is dry, reaction solution is purified by column chromatography, it is solid to obtain yellow
Body BrIDTC8CHO (740mg), yield 93%.1H NMR(400MHz, CDCl3)δ9.91(s,1H),7.64(s,1H),7.41
(s,1H),7.26(s,1H),7.02(s,1H),2.08-1.95(m,4H), 1.90(d,4H),1.12(s,36H),0.84(t,
24H).13C NMR(101MHz,CDCl3)δ183.00(s),155.20 (d),152.52(d),144.57(s),141.42(s),
138.00(s),134.05(s),124.88(s),114.91(s),113.97(s), 113.13(s),54.86(s),54.09
(s), 38.97 (d), 31.81 (s), 29.93 (s), 29.28 (d), 24.20 (d, J=13.2 Hz), 22.64 (s), 14.12
(s),1.06(s).MALDI-TOF-MS(m/z):Calcd for C49H73BrOS2,Exact Mass:820.4,Found:
821.5[M+].
The synthesis of intermediate 3:BTTIDTC8CH: by three thiophene of BrIDTC8CHO (740mg, 0.9mmol) and benzo
(223mg, 0.3mmol), Pd (PPh3)4(30mg, 0.024mmol) is dissolved in chlorobenzene (20mL), substitutes nitrogen, by above-mentioned reaction
Object flows back 24 hours at 120 DEG C.After cooling reaction, it is extracted with dichloromethane, uses MgSO4It is dry, purified with column chromatography, is obtained
To yellow solid BTTIDTC8CHO (222mg), yield 65%.1H NMR(400MHz,CDCl3)δ9.91(s,3H),7.69(s,
3H),7.65(s,3H),7.45(s,3H),7.36(s,3H), 7.31(s,3H),2.05(d,12H),1.94(d,12H),1.15
(s,108H),0.82(d,72H).13C NMR(101MHz, CDCl3)δ182.89(s),157.22(s),155.21(d),
153.64(s),152.42(s),144.70(s),141.49(s), 139.53(s),137.92(d),134.38(s),132.16
(s),130.12(s),119.62(s),117.22(s),114.88(s), 113.39(s),54.42(s),54.15(s),
53.43(s),39.06(s),31.82(s),29.98(d),29.71(s), 29.53-29.02(m),24.29(d),22.63
(s),14.09(s),1.03(s),0.00(s).MALDI-TOF-MS(m/z): Calcd for C159H222O3S9,Exact
Mass:2467.5,Found:2466.6[M+].
The synthesis of final product BTTIDC8IC: by BTTIDTC8CHO (220mg, 0.09mmol) and 3- (dicyano methylene
Base) indigo ketone (70mg, 0.36mmol) is placed in reaction tube, and 0.1mL pyridine is added dropwise, above-mentioned reactant is dissolved in 4mL chloroform,
It is stirred 24 hours at 80 DEG C.It is cooled to room temperature, reaction solution is washed with water, methylene chloride extracts three times, uses MgSO4It is dry
It is dry, black solid BTTIDC8IC (215mg), yield 80% are obtained by silica gel column purification.As shown in Figure 1,1H NMR
(400MHz,CDCl3)δ8.99(s,3H),8.69(s,3H),7.92(s,3H), 7.73(d,12H),7.58(s,3H),7.35
(d, J=17.5Hz, 6H), 2.08 (s, 12H), 1.97 (s, 12H), 1.17 (s, 108H), 0.82 (s, 72H) are as shown in Figure 2
,13C NMR(101MHz,CDCl3)δ188.46(s),162.72(s), 160.95(s),158.38(s),156.76(s),
156.43(s),154.13(s),141.40(s),140.59(s),140.17-139.63 (m),138.63(s),138.18
(s),137.76(s),136.95(s),134.85(s),134.47(s),134.21(s),132.17 (s),130.40(s),
125.20(s),123.53(s),120.72(s),119.65(s),115.89(s),115.17(s),113.51(s), 67.76
(s),54.33(d),39.10(d),38.87-38.69(m),31.82(d),30.32-30.10(m),30.10-29.35(m),
29.35-29.06 (m), 24.40 (s), 22.64 (d), 14.11 (s), 1.04 (s), 0.01 (s) is as shown in figure 3, MALDI-
TOF-MS(m/z):Calcd for C195H234N6O3S2,Exact Mass:[M+]2995.58,Found: 2994.54(M+).
The preparation of embodiment 2:BTTIDC8IC-F
The synthesis of intermediate 1:IDTC8CHO: by IDTC8 (2g, 2.8mmol), n,N-Dimethylformamide (689 mg,
It 4.5mmol) is placed in three-neck flask with phosphorous oxychloride (329mg, 2.8mmol), 30mL 1 is then added, 2- dichloroethanes is molten
It solves, is reacted 24 hours at 100 DEG C.It is cooled to room temperature, reaction solution is washed with water, methylene chloride extracts three times, uses MgSO4
It is dry, it is then purified by column chromatography, obtains yellow solid IDTC8CHO (1.5g), yield 72%.1H NMR(400MHz,
CDCl3)δ9.88(s,1H),9.88(s,1H),7.61(s,1H),7.40(s,1H), 7.34(d,1H),7.31(s,1H),
6.98(d,1H),2.07-1.97(m,4H),1.93-1.82(m,4H),1.10(s,36H), 0.82(d,24H).13C NMR
(101MHz,CDCl3)δ182.89(s),156.52(s),154.93(d),153.93(s), 152.77(s),144.36(s),
141.09(s),138.53(s),133.73(s),127.79(s),121.83(s),113.21(s), 54.05(s),39.04
(s),31.80(s),29.96(s),29.95-29.27(m),29.21(s),24.22(d),22.61(s),14.08 (s),
1.04(s).MALDI-TOF-MS(m/z):Calcd for C49H74OS2,Exact Mass:742.5,Found:741.6 [M+].
The synthesis of intermediate 2:BrIDTC8CHO: IDTC8CHO (720mg, 0.88mmol) is placed in single port reaction flask
In, 5mL methylene chloride is added, is protected from light, ice bath.N- bromo butyryl imines (187.6mg, 1.06 mmol) is dissolved in N simultaneously,
In dinethylformamide, and the solution is slowly dropped in reaction flask.It after being stirred overnight, is cooled to room temperature, will react
Solution is washed with water, and methylene chloride extracts three times, uses MgSO4It is dry, reaction solution is purified by column chromatography, it is solid to obtain yellow
Body BrIDTC8CHO (740mg), yield 93%.1H NMR(400MHz, CDCl3)δ9.91(s,1H),7.64(s,1H),7.41
(s,1H),7.26(s,1H),7.02(s,1H),2.08-1.95(m,4H), 1.90(d,4H),1.12(s,36H),0.84(t,
24H).13C NMR(101MHz,CDCl3)δ183.00(s),155.20 (d),152.52(d),144.57(s),141.42(s),
138.00(s),134.05(s),124.88(s),114.91(s),113.97(s), 113.13(s),54.86(s),54.09
(s), 38.97 (d), 31.81 (s), 29.93 (s), 29.28 (d), 24.20 (d, J=13.2 Hz), 22.64 (s), 14.12
(s),1.06(s).MALDI-TOF-MS(m/z):Calcd for C49H73BrOS2,Exact Mass:820.4,Found:
821.5[M+].
The synthesis of intermediate 3:BTTIDTC8CHO: by three thiophene of BrIDTC8CHO (740mg, 0.9mmol) and benzo
(223mg, 0.3mmol), Pd (PPh3)4(30mg, 0.024mmol) is dissolved in chlorobenzene (20mL), substitutes nitrogen, by above-mentioned reaction
Object flows back 24 hours at 120 DEG C.After cooling reaction, it is extracted with dichloromethane, uses MgSO4It is dry, purified with column chromatography, is obtained
To yellow solid BTTIDTC8CHO (222mg), yield 65%.1H NMR(400MHz,CDCl3)δ9.91(s,3H),7.69(s,
3H),7.65(s,3H),7.45(s,3H),7.36(s, 3H),7.31(s,3H),2.05(d,12H),1.94(d,12H),1.15
(s,108H),0.82(d,72H).13C NMR(101 MHz,CDCl3)δ182.89(s),157.22(s),155.21(d),
153.64(s),152.42(s),144.70(s),141.49 (s),139.53(s),137.92(d),134.38(s),132.16
(s),130.12(s),119.62(s),117.22(s),114.88(s), 113.39(s),54.42(s),54.15(s),
53.43(s),39.06(s),31.82(s),29.98(d),29.71(s), 29.53-29.02(m),24.29(d),22.63
(s),14.09(s),1.03(s),0.00(s).MALDI-TOF-MS(m/z): Calcd for C159H222O3S9,Exact
Mass:2467.5,Found:2466.6[M+].
The synthesis of final product BTTIDC8IC-F: by BTTIDTC8CHO (220mg, 0.09mmol) and 5, the fluoro- 3- of 6- bis-
(dicyano methylene) indigo ketone (83mg, 0.36mmol) is placed in reaction tube, and 0.1mL pyridine is added dropwise, above-mentioned reactant is dissolved in
In 4ml chloroform, stirred 24 hours at 80 DEG C.Reaction solution is cooled to room temperature, is washed with water, methylene chloride extracts three times, uses
MgSO4It is dry, black solid BTTIDC8IC-F (212 mg), yield 78% are obtained by silica gel column purification.As shown in figure 4,1H
NMR(400MHz,CDCl3)δ8.97(s,3H),8.57-8.53(m,3H), 7.73-7.67(m,9H),7.59(s,3H),7.38
(s, 3H), 7.33 (s, 3H), 2.09 (s, 12H), 1.97 (s, 12H), 1.15 (d108H), 0.82 (d, 72H) are as shown in Figure 5
,13C NMR(101MHz,CDCl3)δ185.97(s),164.02(s), 158.56(s),157.04(s),156.64(s),
155.54(s),154.27(s),152.92(d),141.38(s),140.79(s), 140.26(s),139.96(s),138.72
(s),137.89(s),136.40(s),134.34(d),132.15(s),130.38(s), 119.75(s),117.49(s),
116.09(s),114.69(s),113.55(s),112.36(d),68.04(s),54.39(d), 39.13(d),31.85(s),
30.04 (s), 29.36 (s), 24.47 (s), 22.68 (s), 14.17 (s), 1.05 (s) are as shown in fig. 6, MALDI-TOF-MS
(m/z):Calcd.for C195H228F6N6O3S9,Exact Mass:3106.5,Found:3106.9 [M+].
The preparation of embodiment 3:BTTBIC
The synthesis of BTTBCHO: by three thiophene of BrBCHO (180mg, 0.9mmol) and benzo (223mg, 0.3 mmol), Pd
(PPh3)4(30mg, 0.024mmol) is dissolved in chlorobenzene (20mL), substitutes nitrogen, and above-mentioned reactant is flowed back 24 at 120 DEG C
Hour.After cooling reaction, it is extracted with dichloromethane, MgSO4It is dry, purified with column chromatography, obtains yellow solid BTTBCHO
(179mg), yield 62%.
The synthesis of final product BTTBIC: by BTTBCHO (98mg, 0.09mmol) and 3- (dicyano methylene) indigo ketone
(70mg, 0.36mmol) is placed in reaction tube, and 0.1mL pyridine is added dropwise, above-mentioned reactant is dissolved in 4mL chloroform, at 80 DEG C
Stirring 24 hours.After cooling reaction, it is extracted with dichloromethane, MgSO4It is dry, black solid is obtained by silica gel column purification
BTTBIC (95mg), yield 81%.
The preparation of embodiment 4:BTTBIC-F
The synthesis of final product BTTBIC-F: by BTTBCHO (98mg, 0.09mmol) and 5, (dicyano is sub- by the fluoro- 3- of 6- bis-
Methyl) indigo ketone (83mg, 0.36mmol) is placed in reaction tube, and 0.1mL pyridine is added dropwise, above-mentioned reactant is dissolved in 4mL chloroform
In, it is stirred 24 hours at 80 DEG C.After cooling reaction, it is extracted with dichloromethane, MgSO4It is dry, it is obtained by silica gel column purification
Black solid BTTBIC (95mg), yield 81%.
The preparation of embodiment 5:BTTFIC
The synthesis of BTTFCHO: by three thiophene of BrFCHO (390mg, 0.9mmol) and benzo (223mg, 0.3 mmol), Pd
(PPh3)4(30mg, 0.024mmol) is dissolved in chlorobenzene (20mL), substitutes nitrogen, and above-mentioned reactant is flowed back 24 at 120 DEG C
Hour.After cooling reaction, it is extracted with dichloromethane, uses MgSO4It is dry, purified with column chromatography, obtains yellow solid BTTFCHO
(420mg), yield 65%.
The synthesis of final product BTTFIC: by BTTFCHO (201mg, 0.09mmol) and 3- (dicyano methylene) indigo ketone
(70mg, 0.36mmol) is placed in reaction tube, and 0.1mL pyridine is added dropwise, above-mentioned reactant is dissolved in 4mL chloroform, at 80 DEG C
Stirring 24 hours.After cooling reaction, it is extracted with dichloromethane, MgSO4It is dry, black solid is obtained by silica gel column purification
BTTFIC (160mg), yield 80%.
The preparation of embodiment 6:BTTFIC-F
The synthesis of final product BTTFIC-F: by BTTFCHO (98mg, 0.09mmol) and 5, (dicyano is sub- by the fluoro- 3- of 6- bis-
Methyl) indigo ketone (83mg, 0.36mmol) is placed in reaction tube, and 0.1mL pyridine is added dropwise, above-mentioned reactant is dissolved in 4mL chloroform
In, it is stirred 24 hours at 80 DEG C.After cooling reaction, it is extracted with dichloromethane, MgSO4It is dry, it is obtained by silica gel column purification
Black solid BTTFIC-F (176mg), yield 86%.
Embodiment 7: the product BTTIDC8IC in embodiment 1 is applied to organic photovoltaic devices, device fabrication process are as follows:
The ito glass substrate that will be patterned into first continuous ultrasonic processing in detergent, deionized water, acetone and isopropanol is pre- clear
It is clean, and by high pressure air flow drying substrates, then further exposure treatment 30 minutes in ozone chamber.Secondly by ZnO precursor
Solution (solution of the 2M diethyl zinc in toluene is diluted to 0.2M with anhydrous tetrahydro furan, is then filtered with filter) is in drying
It is spun onto ITO substrate in air with the speed of rotation of 6000rpm, 30s, is then annealed 30 points on 150 DEG C of hot plate
Clock is to form thin ZnO layer (about 30nm).The substrate of coating is moved into the glove box full of argon gas.Before rotation, photosensitive layer
Precursor be stirred overnight at 90 DEG C.For donor (PBDB-T): receptor, the total concentration of optimization are 20mg mL-1, charge ratio is
(1:1.2 w/w).Rotation speed is 2000rpm, and corresponding thickness is about 100nm.After annealing, substrate moves into evaporator immediately.
Under a high vacuum, by shadow mask by molybdenum trioxide middle layer (MoO3, 10nm) and Ag layers (100nm) deposit to active layer
Surface on.The area of each device is 0.1 square centimeter.Device parameters are as follows:
From experimental result we it can be found that based on product BTTIDC8IC obtained in embodiment 1 as electronics by
Body incident photon-to-electron conversion efficiency in binary organic photovoltaic devices has reached 6.26%.In addition, during preparing active layer film
It does not need to add any additive, to simplify filming technology, is conducive to prepare large area organic photovoltaic devices, and the material
Material synthetic method raw material is easy to get, is low in cost, being easy to purify, and it is commercialized to show that the material has in organic photovoltaic devices
Future.
Embodiment 8: the product BTTIDC8IC-F in embodiment 2 is applied to organic photovoltaic devices, device fabrication process
Are as follows: the ito glass substrate that will be patterned into first continuous ultrasonic processing in detergent, deionized water, acetone and isopropanol is pre-
Cleaning, and by high pressure air flow drying substrates, then further exposure treatment 30 minutes in ozone chamber.It secondly will be before ZnO
Liquid solution (solution of the 2M diethyl zinc in toluene is diluted to 0.2M with anhydrous tetrahydro furan, is then filtered with filter) is dry
It is spun onto ITO substrate in dry air with the speed of rotation of 6000rpm, 30s, then anneals 30 on 150 DEG C of hot plate
Minute is to form thin ZnO layer (about 30nm).The substrate of coating is moved into the glove box full of argon gas.Before rotation, photosensitive
The precursor of layer is stirred overnight at 90 DEG C.For donor (PBDB-T): receptor, the total concentration of optimization are 20mg mL-1, charge ratio
For 1:1 (w/w).Rotation speed is 2000rpm, and corresponding thickness is about 100nm.After annealing, substrate moves into evaporator immediately.
Under a high vacuum, by shadow mask by molybdenum trioxide middle layer (MoO3, 10nm) and Ag layers (100nm) deposit to active layer
Surface on.The area of each device is 0.1 square centimeter.Device parameters are as follows:
We are it can be found that based on product BTTIDC8IC-F obtained in embodiment 2 as electronics from experimental result
Receptor incident photon-to-electron conversion efficiency in binary organic photovoltaic devices has reached 8.24%.In addition, in the process for preparing active layer film
In do not need to add any additive, to simplify filming technology, be conducive to prepare large area organic photovoltaic devices, and should
Material synthesis method raw material is easy to get, is low in cost, being easy to purify, and shows that the material has commercialization in organic photovoltaic devices
Future.
Fig. 7 is the abosrption spectrogram of target product BTTIDC8IC and BTTIDC8IC-F thin-film state, molar extinction coefficient point
It Wei 1.81 × 105M-1cm-1、2.22×105M-1cm-1, show that material has efficient extinction effect, so as to effective
Promote the photoelectric current in organic photovoltaic devices.
Fig. 8 is the organic photovoltaic devices prepared using target product BTTIDC8IC and BTTIDC8IC-F as electron acceptor
Voltage-current density curve graph, show that material achieves good effect as electron acceptor in organic photovoltaic devices.
Fig. 9 is the thermogravimetic analysis (TGA) curve of target product BTTIDC8IC and BTTIDC8IC-F.As shown, material from
380 DEG C or so just start slowly to decompose, and illustrate that the material has good thermal stability.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other any without departing from the modifications and variations done under the principle of the present invention, it should be equivalent substitute mode, all
It is included within the scope of the present invention.
Claims (9)
1. a kind of multi-arm structure organic photovoltaic material, which is characterized in that the material is one or more to give using three thiophene of benzo as core
Then body unit is constituted and introducing strong electron-withdrawing group group in end, is had as shown in following formula I as skeleton bridging unit
General formula structure:
Wherein, n1、n2、n3For the quantity of bridging unit, and the natural number for being 0~10；A is strong electron-withdrawing group group；D1、D2、D3For
Conjugated system bridging unit.
2. a kind of multi-arm structure organic photovoltaic material according to claim 1, which is characterized in that the A unit is selected from
One of following formula A1-A16 structure:
Wherein * is link position, and C is carbon atom, and H is hydrogen atom, and O is oxygen atom, and N is nitrogen-atoms, and S is sulphur atom, and F is fluorine original
Son, Cl are chlorine atoms.
3. a kind of multi-arm structure organic photovoltaic material according to claim 1, which is characterized in that the D1、D2、D3For
Conjugated structure system bridging unit, each is selected from one of formula:
Wherein, R is hydrogen atom, C1~C30Alkyl chain, C1~C30Oxyalkyl chain, C5~C30Naphthenic base, C2~C30Miscellaneous alkyl chain
One of；S is sulphur atom, and N is nitrogen-atoms, and * is link position.
4. a kind of multi-arm structure organic photovoltaic material according to claim 1, which is characterized in that the n1、n2、n3For
The quantity of bridging unit, value are 1 or 2.
5. a kind of preparation method of multi-arm structure organic photovoltaic material as described in claim 1, which is characterized in that its synthesis side
Method and route are as follows:
Three aldehyde radical intermediate IIs and strong electrophilic end groups A are dissolved in chloroformic solution, catalysis alkali, under nitrogen atmosphere, 80 is added dropwise
DEG C reaction 12-24h, after be cooled to room temperature through extraction and chromatography obtain final product I.
6. a kind of preparation method of multi-arm structure organic photovoltaic material according to claim 5, which is characterized in that specific packet
Include following steps:
Step 1: bridging unit 2.8mmol, n,N-Dimethylformamide 4.5mmol and phosphorous oxychloride 2.8mmol are placed in
It dissolves in 30mL 1,2- dichloroethanes, is reacted 24 hours at 100 DEG C, washed, extraction, obtains intermediate 1 at drying after purification；
Step 2: 0.88mmol intermediate 1 being dissolved in 5mL methylene chloride, ice bath is protected from light；It is added dropwise to and is dissolved with again
The n,N-Dimethylformamide solution 1mL of 1.06mmol N- bromo-succinimide, is stirred overnight, and obtains intermediate 2 after purification；
Step 3: by three thiophene of 0.9mmol intermediate 2 and 0.3mmol benzo, 0.024mmol Pd (PPh3)4It is dissolved in 20mL chlorobenzene
In, substitute nitrogen, flow back 24 hours at 120 DEG C, it is cooling after through extraction, drying, after purification intermediate 3；
Step 4: by 0.09mmol intermediate 3,0.36mmol it is strong electrophilic end groups A, 0.1mL pyridine are dissolved in 4mL chloroform, 80
It is stirred 24 hours at DEG C, is cooled to room temperature and is extracted and obtain final product after chromatography.
7. a kind of preparation method of multi-arm structure organic photovoltaic material according to claim 5, which is characterized in that described three
The molar ratio of aldehyde radical intermediate and strong electrophilic end groups A are 1:4, and concentration of the three aldehyde radicals intermediate in chloroformic solution is
0.0225mmol/mL。
8. a kind of preparation method of multi-arm structure organic photovoltaic material according to claim 5, which is characterized in that catalysis alkali
For pyridine, the molar ratio range with strong electrophilic end groups A is (0.1-1): 1.
9. a kind of application of multi-arm structure organic photovoltaic material as described in any of the claims 1 to 8, which is characterized in that the material
Material can be used as active layer material or addO-on therapy for organic solar batteries devices such as binary, polynary or laminations.
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| CN113387965A (en) * | 2021-06-17 | 2021-09-14 | 南京邮电大学 | Organic electron acceptor material and preparation method and application thereof |
| CN113480560A (en) * | 2021-06-17 | 2021-10-08 | 南京邮电大学 | Preparation method of non-fullerene electron acceptor, product and application |
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