CN113087876A - Free radical polymer and application thereof - Google Patents
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Abstract
The invention discloses a free radical polymer, which has a structural formula I:
or, formula II:
the free radical polymer can be used as an additive or a photoelectric active component for excitons in organic/polymer optoelectronic devicesThe behaviors of splitting, charge transfer state triplet state concentration, carrier recombination and the like are regulated and controlled.
Description
Technical Field
The invention relates to the technical field of organic/polymer photoelectronic devices, in particular to a free radical polymer and application thereof.
Background
In the clean and green Solar Energy utilization technology, Polymer Solar Cells (OPVs) have a Broad development prospect due to the outstanding advantages of low cost, light weight, simple manufacturing process, capability of preparing large-area flexible devices and the like, and have become the most vigorous research directions in the fields of new Materials and new Energy sources (Li g., Zhu r.and yang y.polymer Solar Cells [ J ], nat. photon, 2012,6, 153-, jia z., men l., Zhang J., Zhang h., huangang w., Yuan J., Gao f., Wan y., Zhang z., Li y.pro-moving charging in tertiary organic cells over 17.5% [ J ], Nano Energy,2020,78,105272 (1-8); liu q., Jiang y., Jin k., Qin J., Xu J., Li w., Xiong J., Liu J., Xiao z., Sun k., Yang s., Zhang x., Ding l.18% Efficiency organic solar cells [ J ], sci.fill.2020, 65, 272-. However, the improvement of OPVs performance is currently achieved by adjusting the absorption spectrum, energy level, charge transfer and aggregation behavior of organic/polymer semiconductor materials, and device structure optimization and preparation process innovation, which are approaching to theoretical expectations, and it is necessary to find and establish a new method for improving the photovoltaic performance of organic/polymer solar cell devices to further improve the performance of optoelectronic devices.
As the most studied and promising organic/polymer optoelectronic device structure at present, the nano-range phase structure and higher charge concentration in interpenetrating network bulk heterojunction organic/polymer solar cells (BHJ-OPVs) will result in electrons and electrons in the device and higher charge concentration as in organic/polymer light emitting devicesHole efficient recombination to generate singlet-triplet charge transfer excitons1CTs,3CTs). When in use3The energy level of CTs is higher than the triplet state (T) of the conjugated electron donor polymer or the organic small molecule electron donor material in the BHJ-OPVs optical active layer1) At energy level, in BHJ-OPVs devices3CTs can be via T of electron donor materials1States, which fall back from the excited state to the ground state in a non-radiative manner, are one of the main channels of energy loss in organic/polymer solar cells (RaoA., Chow P.C.Y., Gellinas S., Schlenker C.W., Li C. -Z., Yip H. -L., Jen A.K. -Y., Ginger D.S., and Friend R.H. roll of pin in the electronic control of recombination in organic photovoltials [ J.],Nature,2013,500,435-440)。
Although in BHJ-OPVs in which the phase structure of the active layer is good,3the rate of reformation of free charges by CTs is much greater than its passage through the electron donor material T1The velocity of the energy level from the excited state to the ground state is such that the effect of this energy loss channel on device performance is greatly reduced, but is currently observed in most BHJ-OPVs3Presence of CTs, thereby suppressing or eliminating the presence of CTs in the device3CTs by T1The energy level from the excited state to the ground state is of great importance for further improving the performance of BHJ-OPVs (RaoA., Chow P.C.Y., G é linas., Schlenker C.W., Li C. -Z., YIp H. -L., JenA.K. -Y., Ginger D.S., and Friend R.H. the role of the kinetic control of the regulation in organic photovoltaics [ J.],Nature,2013,500,435-440)。
In 2012, z.valyvardeny et al found that a galaxane radical (2, 6-di-tert-butyl- (3, 5-di-tert-butyl-4-oxo-2, 5-cyclohexadiene) -P-tolyloxy radical) was introduced as an additive to poly (3-hexyl) thiophene (P3HT) and methyl (6,6) -phenylcarb-61-butanoate (PC) methyl ester61BM) is the active layer, the photoelectric conversion efficiency of the device was found to be 18% higher (3.4% to 4.0%) than the device not doped with the radical additive. They speculate that the reason for the introduction of the Galvanh radical into the organic/polymer optoelectronic device, which leads to the improvement of the corresponding device performance, is due to the single electron energy (SOMO) of the Galvanh radical and the P3HT/PC61The charge transfer state energy levels in the optoelectronic device of BM are relatively similar, so that a stronger coupling effect exists between the charge transfer state energy levels and a polaron bound by coulomb force generated by photoinduction in the optical active layer, and spin resonance exchange occurs between the polaron generated by photoinduction and a free radical, so that the singlet polaron pair is converted into a triplet polaron pair with a longer service life, and the efficiency of dissociating the photogenerated polaron pair into free charges (charge carriers) in the device is further improved, and the short-circuit current and energy conversion efficiency of the device are improved (Zhang y, base t.p., gateway b.r., Yang x., Mascaro d.j., Liu f.and vaenrdy Z.V. [ J].Spin-enhanced Organic Bulk Heterojunction Photovoltaic Solar Cells.Nat.Commun.2012,3,1043.)。
In 2015, Z.Valy Vardeny et al introduced the free radical as poly [ (4, 8-bis ((2-ethylhexyl) oxy) -benzo [1,2-b:4,5-b']Dithien-2, 6-diyl) (3-fluoro-2- ((2-ethylhexyl) carbonyl) thiophene [3,4-b]Bithiophene](PBT7) with PC61The BM is an active layer of the optoelectronic device, so that the energy conversion efficiency of the optoelectronic device is improved by 36% (5.2% to 6.8%) compared with the device which is not doped with the free radical additive. They speculated that the Karmen free radical is introduced into PBT7/PC based on previous work61The reason for the improved performance of the optoelectronic devices of BM is due to PBT7/PC61In the BM photoelectronic device, the energy level of a charge transfer state is lower than the triplet energy level of PBT7, and the single electron energy level of a Galvanan free radical and PBT7/PC61The charge transfer state energy levels in the photoelectronic devices of the BM are close, and resonance can occur. The addition of the Karmen radical additive of spin1/2 promotes the singlet state of charge transfer state (R) ((R))1CTs) and triplet charge transfer states ((C)3CTs) to inhibit charge transfer states through the electron donor material T1The state is returned to the ground state, which results in an increase in the efficiency of charge transfer state dissociation into free charges or a decrease in carrier recombination, resulting in an increase in the energy conversion efficiency of the device (base T., Huynh U., Zheng T., Xu T., Yu L and Vardeny Z.V.optical, Electrical, and Magnetic studios of Organic Solar Cells Based on Low band code Copolymer with Spin1/2 radial Additives [ J].Adv.Funct.Mater.,2015,25,1895-1902)。
Unfortunately, however, the Karmen radical of spin1/2, as an additive, can only be used for P3 HT/PC-based61BM and PBT7/PC61Optoelectronic devices of BM, not even for PBT7/PC71Optoelectronic devices of BM (Basel T., Huynh U., ZHEN T., Xu T., Yu L and Vardeny Z.V.optical, electric, and Magnetic students of Organic Solar Cells Based on Low band Copolymer with Spin1/2 radial Additives [ J]Adv.funct.mater, 2015,25, 1895-1902). This method is not universal and its effectiveness remains to be confirmed (Cho j.m., Kim d.s., Bae s., Moon s. -j., Shin w.s., Kim d.h., Kim s.h., sterlich a,
S.,Dyakonov V.,Lee J.-K.Light-induced Electron Spin Resonance Study of Galvinoxyl-doped P3HT/PCBM Bulk Heterojunctions[J].Organic Electronics2015,27,119–125)。
recently, the applicant has made the following work to introduce different types of radical groups into active layers of organic polymer solar cell devices of different systems, and has reached the following conclusion:
the introduction of free conjugated radical polymers (fig. 1(1)) containing 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO) as pendant groups, and free radical non-conjugated polymers (PTEO, fig. 14) into BHJ-OPVs optically active layers in combination with the use of solvent additives such as chloronaphthalene, 1, 8-diiodooctane, etc., allows the current major BHJ-OPVs material systems such as: p3HT/PC71BM,PTB7/PC61BM,PTB7/PC71BM,PTB7-Th/PC71BM,PBDB-T/PC71Short-circuit current of the optoelectronic device with the optical active layers of BM, PBDB-T/ITIC, PBDB-T/IT4F, J61/ITIC, PM6/iT-4F and PM6/Y6 is improved, and energy conversion efficiency of the optoelectronic device doped with the free radical polymer is improved by 1% -3% (relatively improved by 7% -30%) compared with that of the optoelectronic device not doped with the free radical polymer. Wherein the TEMPO doped device has the structure of ITO/PEDOT: PSS/PM6: Y6(W: W; 1:1.2)/PDINO/Al, the performance of the solar cell is reduced to 15.15% from 15.7-15.9%, and the energy conversion efficiency of the PTEO doped device is 15.7The percent-15.95 percent is improved to 17.3 percent to 17.5 percent.
2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (fig. 1(3)) and alpha, beta-bis-diphenylene-beta-phenylallyl radical (fig. 1(5)) are introduced into an optoelectronic device of which PM6/Y6 is an optically active layer, the energy conversion efficiency of the device will be reduced; the energy conversion efficiency of the optoelectronic device with the optically active layer of PM6/Y6 is slightly improved by introducing Galvanda free radicals (figure 1(4)) and N-tertiary butyl-3-trifluoromethylphenyl-nitroxide free radicals (figure 1 (6)).
Through testing absorption, grazing incidence angle X-ray diffraction, surface morphology and optical stability of the PM 6/Y6-based photosensitive active layer of the doped and undoped free radical polymer GDTA, the fact that the absorption, aggregation behavior and surface morphology of the PM 6/Y6-based photosensitive active layer are not obviously influenced by the addition of a small amount of free radical polymer additive is found.
Through the test of the charge transfer performance of the PM 6/Y6-based photosensitive active layer before and after the addition of the free radical polymer additive by the space charge (induced) limited current method, the charge transfer performance of the PM 6/Y6-based photosensitive active layer after the doping of a small amount of free radical polymer is not obviously changed.
Based on a photovoltaic device with an optically active layer of GDTA and PTEO doped PM6/Y6, the magneto-optical current of the photovoltaic device doped with the free radical polymer is inhibited relative to the photovoltaic device with an optically active layer of undoped PM6/Y6, and the triplet state charge transfer state (the following description shows that in the device)3CT) polarons are suppressed.
Compared with a free radical small molecule compound, the free radical conjugated polymer or the free radical non-conjugated polymer is proved to be a novel method for improving the energy conversion efficiency of the organic/polymer photoelectronic device, which has wide universality and can be combined with solvent additives to optimize the phase structure of an active layer of the photoelectronic device, the energy levels of an electron donor material and an electron acceptor material, the spectral response range, the charge transmission performance, the compatibility of the electron donor material and the electron acceptor material and the like.
The Galavan free radical micromolecules are used as additives and introduced into a photoelectronic device with PM6/Y6 as an optical active layer, the efficiency of the device is improved by 16.2% from 15.7% -15.9%, and the change of the performance of the device is within an error range by adding the Galavan free radical micromolecules.
The conjugated polymer PG-1 (figure 15) with the pendant group of the Karmen free radical is taken as an additive and is introduced into an optoelectronic device with the PM6/Y6 as an optical active layer, and the efficiency of the device is improved by 17.2 percent from 15.7 to 15.9 percent. The use of PG-1 as an additive in combination with solvent additives such as chloronaphthalene, 1, 8-diiodooctane and the like allows the use of material systems such as: p3HT/PC71BM,PTB7/PC61BM,PTB7/PC71BM,PTB7-Th/PC71BM,PBDB-T/PC71The energy conversion efficiency of the optoelectronic device with the optical active layers of BM, PBDB-T/ITIC, PBDB-T/IT4F, J61/ITIC, PM6/iT-4F and PM6/Y6 is improved by 1-2.3%.
Conjugated polymer PG-2 with pendant group N-tert-butyl-3-trifluoromethylphenyl-nitroxide radical (fig. 15), as an additive, can increase the energy conversion efficiency of PM6/Y6 based optoelectronic devices from 15.7% -15.9% to 17.1%.
The random polymer PG-3 (figure 16) of 3- (4-oxyl-2, 2,6, 6-tetramethylpiperidin-1-oxyl) propane and 3-carbazolylpropane can be used as an additive to improve the energy conversion efficiency of the photoelectronic device based on PM6/Y6 from 15.7-15.9% to 17.4%.
Disclosure of Invention
In view of the above, the present invention provides a radical polymer and its application as an additive, a photoelectric active component or an interface modification material in an organic/polymer optoelectronic device.
In order to achieve the purpose, the invention adopts the following technical scheme:
a free radical polymer characterized by the structural formula i:
or, formula II:
in the formula I, m and n are natural numbers of 5-100;
in the formula II, x and y are both natural numbers of 0-5, m is a natural number of 1-3, n is a natural number of 1-5, B1And B2Are any one of oxygen, nitrogen, sulfur and phosphorus;
in the formula I and the formula II, Fr is any one of formula Fr-1 to formula Fr-8:
in the formulas Fr-1 to Fr-8, the dotted line is the linking position of Fr and a straight chain or branched chain halogenated alkyl, alkenyl, alkyl, aralkyl, heteroalkyl, alkoxy, alkylthio or ester group with the carbon number of 1-30.
The free radical polymer has the following beneficial effects:
the alternating, random, block, graft and star-shaped, tree-shaped conjugated or unconjugated high molecular polymer of the free radical polymer is used as an additive or a modifier and a photoelectric active component to inhibit the generation of a triplet state charge transfer state in an organic/polymer photoelectronic device;
the free radical polymer is used as an additive or modifier and a photoelectric active component and is used for organic/polymer semiconductor photoelectronic devices;
the free radical polymer is used as an additive or a photoelectric active component to regulate and control an excited state, charge transfer and carrier behavior in an organic/polymer light-emitting optoelectronic device.
Further, in the above formulae I and II, Ar1And Ar2Are independently any one of formulas I-1 to I-48:
in the formulas I-1 to I-48, the dotted line is Ar1And or Ar2The attachment site of (a);
in the formulae I-1 to I-44, R1、R2And R3Independently selected from any one of hydrogen, halogen, straight chain or branched chain halogenated alkyl with 1-30 carbon atoms, alkenyl, alkyl, aralkyl, heteroalkyl, alkoxy, alkylthio, cyano, nitro and ester group;
in the formulae I-45 and I-46, R1、R2And R3Independently selected from any one of hydrogen, halogen, straight chain or branched chain alkyl with 1-30 carbon atoms, alkenyl, alkoxy and alkylthio, or any one of aromatic heterocyclic group and aromatic ring group substituted by hydrogen, halogen, straight chain or branched chain alkyl with 1-30 carbon atoms, alkenyl, alkoxy or alkylthio.
The invention also claims the application of the free radical polymer in preparing organic/polymer optical devices.
Further, due to the effect of the radical polymer on triplet charge transfer state, triplet excitons in the organic/polymeric photoelectronic device, the above organic/polymeric photoelectronic device comprises: organic/polymer light emitting devices, organic/polymer photovoltaic devices, organic/polymer photodetectors, organic/polymer thin film transistors, organic/polymer memory devices, and organic/polymer logic devices.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
tests carried out by the applicant have demonstrated that: compared with free radical small molecular compounds such as 2,2,6, 6-tetramethylpiperidine-nitrogen-oxide (TEMPO), Galvanne free radical, alpha, gamma-bis-diphenylene-beta-phenylallyl (BDPA), N-tertiary butyl-2-trifluoromethyl phenyl-nitroxide free radical and the like, the organic/polymer photovoltaic device performance of the doped free radical conjugated polymer (I) or the free radical unconjugated polymer (II) is improved more obviously.
The invention provides the free radical polymer as an additiveThe combination of agents or modifiers, with solvent additives such as chloronaphthalene, 1, 8-diiodooctane, and the like, allows current major organic/polymeric photovoltaic material systems such as: p3HT/PC71BM,PTB7/PC61BM,PTB7/PC71BM,PTB7-Th/PC71BM,PBDB-T/PC71The energy conversion efficiency of the photoelectronic device taking the blend films of BM, PBDB-T/ITIC, PBDB-T/IT4F, J61/ITIC, PM 6/ITT-4F, PM6/Y6 and the like as photosensitive active layers is improved by 1-3%. The method is universal and can be used for improving the energy conversion efficiency of the organic/polymer optoelectronic device.
The photovoltaic device with the optically active layer of PM6/Y6 doped with GDTA and PETO respectively has the magneto-optical current suppressed compared with the photovoltaic device with the optically active layer of undoped PM6/Y6 doped with free radical polymer, which shows that the magneto-optical current of the photovoltaic device doped with free radical polymer is suppressed3CT polarons are inhibited, and are important factors for improving the photovoltaic performance of the device.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
In fig. 1, (1) to (6) are chemical structural formulas of a radical polymer GDTA, a conjugated polymer GDZZ, a radical polymer TEMPO, a galaxy radical GFR, an α, γ -bis-diphenylene- β -phenylallyl radical BPFR and an N-tert-butyl-3-trifluoromethylphenyl-nitroxy radical FBFR, respectively;
FIG. 2 is a scheme of synthesis of GDTA;
FIG. 3 is an electron paramagnetic resonance spectrum of GDTA;
FIG. 4 is a UV-VISIBLE absorption spectrum of GDTA;
FIG. 5 is a thermogravimetric plot of GDTA;
FIG. 6 is a cyclic voltammogram of a GDTA solid film;
FIG. 7 is a permeation chromatogram of a free radical conjugated polymer GDTA;
FIG. 8 is the UV-visible absorption spectra of PM6/Y6 blended films with doped and undoped GDTA additives;
FIG. 9 is the UV-VIS absorption spectra of a PM6/Y6 film doped and undoped with GDTA additive under UV irradiation at different times;
FIG. 10 is a J/V curve for organic/polymer photovoltaic devices of PM6/Y6 thin films doped and undoped with GDTA additive;
FIG. 11 is a J/V curve for TEMPO, GFR, BPFR, FBFR doped PM6/Y6 blended films for organic/polymer photovoltaic devices;
FIG. 12 is a space charge limited current-voltage (SCLC) curve for PM6/Y6 thin films doped and undoped with GDTA additive;
FIG. 13 is a magneto-optical current curve for organic/polymer photovoltaic devices of PM6/Y6 thin films doped and undoped with GDTA additive;
FIG. 14 is a chemical structural formula of a non-conjugated radical polymer PETO;
FIG. 15 shows the chemical structures of the radical conjugated polymers PG-1, PG-2 and PM6-NO 5;
FIG. 16 shows the chemical structure of a radical unconjugated random polymer PG-3 based on 3- (4-oxy-2, 2,6, 6-tetramethylpiperidin-1-oxy) propane and 3-carbazolylpropane.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following embodiments, some drawings use english vocabulary for more accurate expression, and the chinese meaning of the related english terms is as follows:
| English | chinese character |
| Voltage | Voltage of |
| ShortCircuitCurrentDensity | Short circuit current density (J)SC) |
| Wavelength | Wavelength of light |
| CurrentDensity | Current density |
| FillFactor | Fill Factor (FF) |
| nm | Nanometer |
| PCE | Photoelectric conversion efficiency |
| Open-circuitVoltage | Open circuit voltage (V)OC) |
| EQE | External quantum efficiency |
In the following examples, the chemical structures of the organic/polymeric photovoltaic materials used are abbreviated as follows:
in the following examples, optoelectronic device structures were tested: except based on P3HT/PC71The device with BM as photosensitive active layer has ITO/ZnO/active layer/MoO structure3Other photovoltaic material systems than Ag are for example: PTB7/PC61BM、PTB7/PC71BM、PTB7-Th/PC71BM、PBDB-T/PC71The structures of the optoelectronic devices taking blend films such as BM, PBDB-T/ITIC, PBDB-T/IT4F, J61/ITIC, PM6/IT-4F, PM6/Y6 and the like as photosensitive active layers are as follows: ITO/PEDOT PSS/active layers/PDINO/Ag; the area of the device is 0.05-0.1cm2。
In the following embodiment, a test system for testing a J-V characteristic curve of an optoelectronic device is an optoelectronic device parameter test system based on a sunlight simulation light source system, a digital source meter, a sample holder and a data processing system; the method specifically comprises the following steps: the quasi-radiation intensity of the standard cell is 100mW cm-2The AM1.5G standard solar simulator (XES-70S1, San-Ei Electric company, japan) simulates standard sunlight to irradiate a device to be tested, then a Keithley 2400 type source meter is connected between a cathode and an anode of the device, current corresponding to different voltages is applied to the device to be tested accurately, data is collected through test software, and open-circuit voltage (V) is obtainedOC) Short-circuit current (J)SC) Fill Factor (FF), PCE, etc.
Example 1
The conjugated free radical polymer GDTA shown in the chemical structural formula (1) of figure 1 and the conjugated polymer GDZZ shown in the chemical structural formula (2) of figure 1 are synthesized according to the synthetic route shown in figure 2 by the following steps.
Preparation of free radical conjugated polymer GDTA: 2, 6-bis (trimethylstannyl) -4, 8-bis (4, 5-dioctylthiophen-2-yl) benzo [1, 2-b; 4,5-b' ] dithiophene ] (129.5mg, 0.32 mmol), 2, 5-dibromo-1, 4-benzenedicarboxylic acid (4-oxo-2, 2,6, 6-tetramethylpiperidinyloxy) ester (200.0mg, 0.32 mmol) were dissolved in a mixed solution of 6 ml of toluene and 0.7 ml of N, N-dimethylformamide, followed by argon bubbling for 10 minutes, tris (dibenzylideneacetone) dipalladium (0) (2.0mg) and tris (2-methylphenyl) phosphine (4.0mg) were added, and heated under argon atmosphere for 72 hours. Before the polymerization reaction was completed, 2-tributylstannylthiophene (25.0mg) and 2-bromothiophene (30mg) were added in this order to react for 8 hours to effect end-capping reaction. The resulting reaction solution was cooled to room temperature, poured into 300 ml of methanol, and the resulting solid was filtered and then purified by silica gel chromatography (toluene as an eluent), the toluene solution of the polymer was concentrated, and then chromatographically pure methanol was dropped thereto, and the resulting solid was dried under vacuum to obtain the objective polymer GDTA in a yield of 74.3%.
Preparation of conjugated polymer GDZZ: the same procedure as for the preparation and purification of GDTA was followed, except that ethyl 2, 5-dibromo-1, 4-benzenedicarboxylate (4-oxo-2, 2,6, 6-tetramethylpiperidinyloxy free) was replaced with ethyl 2, 5-dibromo-1, 4-benzenedicarboxylate. The yield was 86.6%.
FIG. 3 shows the electron paramagnetic resonance spectrum of a toluene solution (2mg/mL) of the radical-conjugated polymer GDTA. Typical paramagnetic resonance peaks for the N-O radical (g ═ 2.006) appear, and from this figure, TEMPO radicals are present in GDTA.
FIG. 4 shows the UV-VIS absorption spectrum of GDTA as a radical-conjugated polymer. As can be seen from this figure, GDTA absorbs between 300nm and 510 nm.
FIG. 5 is a thermogravimetric plot of GDTA showing a GDTA thermal decomposition temperature of about 268.3 deg.C. From this figure, it is clear that the polymer GDTA has good thermal stability.
FIG. 6 shows GDTA as a solid film in 0.1M tetrabutylammonium hexafluorophosphate acetonitrile solution, Ag/Ag+A reference electrode, a platinum carbon electrode as a working electrode, a platinum wire as a counter electrode, and a scanning speed of 50 mV/min. It was found that the radical polymer GDTA had a first oxidation onset potential of about +0.36V and a second oxidation onset potential of about + 0.79V; the first reduction potential and the second reduction potential are about-0.26V and-1.75 eV. Fc/Fc taking into account the conditions for determining the cyclic voltammogram of GDTA+Has an oxidation potential of about +0.1V according to the empirical formula (E)HOMO＝-(4.70+Eox)eV；ELUMO＝(4.70+Ered) eV) and a first oxidation initiation potential corresponding to GDZZ, a conjugated polymer having the same conjugated backbone as GDTA, of +0.74 eV; the first oxidation initiation potential and the reduction potential of the TEMPO radical are at +0.26V and-0.73V, respectively. As can be seen from this figure, the GDTA has a single electron occupied level of about-5.06 eV for the radical, a highest occupied orbital (HOMO) level of about-5.49 eV for the conjugated main chain, and a lowest unoccupied orbital (LUMO) level of about-2.95 eV for the conjugated main chain.
FIG. 7 is a permeation chromatogram of a free radical conjugated polymer GDTA with tetrahydrofuran as a mobile phase and polystyrene as a standard. As can be seen from the graph, the GDTA has a number average molecular weight of about 23400g/mol and a dispersion coefficient (M)W/Mn＝2.67)。
FIG. 8 is the UV-visible absorption spectra of PM6/Y6 blended films with doped and undoped GDTA additives. From this figure, it can be seen that the addition of the radical conjugated polymer GDTA does not significantly affect the uv-vis absorption of the PM6/Y6 based photoactive layer.
FIG. 9 shows UV (360nm, 400W/m) at various times for PM6/Y6 films doped and undoped with GDTA additive2) Uv-vis absorption spectrum under light irradiation. From the figure, it can be seen that the doped radical conjugated polymer GDTA does not have a significant effect on the light stability of the PM6/Y6 blend film under ultraviolet light.
FIG. 10 is a J/V curve for organic/polymer photovoltaic devices of PM6/Y6 thin films doped and undoped with GDTA additive. From the figure, the addition of 2% GDTA improves the energy conversion efficiency of the corresponding organic/polymer photovoltaic device from 15.7-15.9% to 16.8-17.0%.
FIG. 11 is a J/V curve for an organic/polymeric photovoltaic device doped with a PM6/Y6 thin blend film of a small molecule free radical compound TEMPO, a Galvanh Free Radical (GFR), an α, γ -bis-diphenylene- β -phenylallyl free radical (BPFR), and an N-tert-butyl-3-trifluoromethylphenyl-nitroxide radical (FBFR). As can be seen from fig. 10 and 11, the addition of small molecule radicals has limited improvement of the energy conversion efficiency of the photovoltaic device with PM6/Y6 as the optically active material (TEMPO, α, γ -bis-diphenylene- β -phenylallyl radical addition causes the device performance to be reduced; kallman radical, N-t-butyl-3-trifluoromethylphenyl-nitroxide radical addition causes the device efficiency to be slightly improved).
FIG. 12 shows the structure of the device of the doped and undoped GDTA additive PM6/Y6 thin film as ITO/PEDOT/PSS/Blend films/MoO3Space charge limited Current-Voltage (SCLC) curves of/Ag, ITO/PEDOT ITO/ZnO/Blend films/PFN/Ag. From this figure in conjunction with table 2, it can be seen that although the addition of GDTA may slightly improve the electron and hole mobilities of the PM6/Y6 blended film, the measurement error considering the film thickness measured using the step meter is about ± 10 nm; the effect of film thickness measurement error is much greater than the difference between the PM6/Y6 film carrier (electron and hole) mobilities of doped and undoped GDTA additives; therefore, it can be seen that the addition of GDTA can change the electron and hole mobility of the PM6/Y6 blend film negligibly.
FIG. 13 is a magneto-optical current curve for organic/polymer photovoltaic devices of PM6/Y6 thin films doped and undoped with GDTA additive. From the figure, it can be seen that the addition of 2% GDTA significantly reduces the magneto-optical current corresponding to the organic/polymer photovoltaic device, which indicates that the addition of a small amount of GDTA suppresses the triplet charge transfer state (or triplet charge transfer state exciton) in the corresponding photovoltaic device.
Fig. 14 is the chemical structure of a non-conjugated radical polymer PETO.
FIG. 15 shows the chemical structures of the radical conjugated polymers PG-1, PG-2 and PM6-NO 5.
FIG. 16 shows the chemical structure of a radical unconjugated random polymer PG-3 based on 3- (4-oxo-2, 2,6, 6-tetramethylpiperidin-1-oxo) propane and 3-carbazolylpropane.
Example 2
Preparation and photoelectric performance test of a PM6/Y6 device added with GDTA:
firstly, ITO cleaning: cleaning the surface of the substrate with a surfactant, then ultrasonically cleaning the substrate, sequentially and respectively cleaning twice with a cleaning solution, once with ultrapure water, twice with acetone, once with ultrapure water and twice with isopropanol in sequence, ultrasonically cleaning for 10-20min each time, and storing the substrate in isopropanol after cleaning to prevent the substrate from being polluted by dust before use; secondly, the ITO substrate is processed by ozone plasma,the time is 10 min; thirdly, instantly spin-coating PEDOT doped with glycerol with different concentrations on the ITO glass treated by the plasma, wherein the rotation speed is 3000-4000r/s and 40s, then annealing for 30min at the temperature of 100-150 ℃, subsequently transferring into a glove box, and preparing a 110nm blended film by using PM6 and Y6 as solutes, chloroform as a solvent and 0.5% chloronaphthalene as a solvent additive, or adding 2% GDTA (mass percentage of GDTA to PM 6) into the solution; then annealing the film at 110 ℃ for 10 min; finally, the prepared blended film is spin-coated to prepare PDINO as a cathode buffer layer (5-10 nm); then utilizing a vacuum coating machine to ensure that the vacuum degree is more than 5 multiplied by 10-4Under the condition of (1), using 0.057cm2The mask plate is evaporated to prepare an Al (100nm) electrode, and the polymer solar cell with the forward structure is obtained.
Filling the prepared photovoltaic device with N2Using the AM1.5G intensity of the solar simulator in the glove box (100 mW/cm)2) Three parameters of open-circuit voltage, short-circuit current and filling factor of the prepared polymer solar cell device are tested, and the test results are shown in table 1.
TABLE 1 parameters of PM6/Y6 organic/polymer photovoltaic devices doped and undoped GDTA
As can be seen from table 1, the PCE of the photovoltaic device doped with the radical polymer GDTA was increased by about 7.55% compared to the photovoltaic device not doped with the radical polymer GDTA in the PM6/Y6 blend film.
Example 3
Active layer P3HT/PC71The battery performance of 2 percent GDTA added into BM, and the structure of the device is ITO/ZnO/P3HT: PC71BM/MoO3P3HT/PC with/Ag, doped and undoped GDTA additives71BM device preparation and testing procedures as described in example 2, based on P3HT/PC71The photovoltaic devices of the BM did not use solvent additives and the device test results are shown in table 2.
TABLE 2P 3HT/PC for doped and undoped GDTA71Performance parameters of BM optoelectronic devices
As can be seen from Table 2, the comparison is not in P3HT/PC71The GDTA-doped photovoltaic device in the BM blend film has the PCE improved by about 8 percent.
Example 4
Active layer PTB7/PC61The battery performance of 2% GDTA added into BM, and the device structure is ITO/PEDOT: PSS/PTB7: PC61BM/PDINO/Al, PTB7/PC with doped and undoped GDTA additives61BM device preparation and testing procedures were as described in example 2, with the solvent additive CN being replaced with 1, 8-diiodooctane and the device test results are shown in table 3.
TABLE 3 GDTA doped and undoped PTB7/PC61Performance parameters of BM optoelectronic devices
As can be seen from Table 3, in contrast to the comparison not in PTB7/PC61The GDTA-doped photovoltaic device in the BM blend film has the PCE improved by about 7.75 percent.
Example 5
Active layer PTB7/PC71The battery performance of 2% GDTA added into BM, and the device structure is ITO/PEDOT: PSS/PTB7: PC71BM/PDINO/Al, PTB7/PC with doped and undoped GDTA additives71BM device preparation and testing procedures were as described in example 2, and device testing results are shown in table 4.
TABLE 4 GDTA doped and undoped PTB7/PC71Performance parameters of BM optoelectronic devices
As can be seen from Table 4, in contrast to PBT7/PC71In BM blend filmsThe PCE of the photovoltaic device doped with the GDTA is improved by about 7.71 percent.
Example 6
Active layer PTB7-Th/PC71The battery performance of 2 percent GDTA added into BM, and the device structure is ITO/PEDOT: PSS/PTB7-Th: PC71BM/PDINO/Al, PTB7-Th/PC with doped and undoped GDTA71BM device preparation and testing procedures were as described in example 2, and device testing results are shown in table 5.
TABLE 5 GDTA doped and undoped PTB7-Th/PC71Performance parameters of BM optoelectronic devices
As can be seen from Table 5, in comparison with the results not shown in PTB7-Th/PC71The GDTA-doped photovoltaic device in the BM blend film has the PCE improved by about 13 percent.
Example 7
Active layer J61: cell performance with 2% GDTA added to the ITIC, device structure ITO/PEDOT: PSS/J61: ITIC/PDINO/Al, preparation and testing procedure of J61/ITIC device with doped and undoped GDTA as described in example 2, and test results are shown in Table 6.
TABLE 6 Performance parameters of GDTA doped and undoped J61/ITIC optoelectronic devices
As can be seen from table 6, the PCE of the GDTA doped photovoltaic device was increased by about 9% compared to the photovoltaic device not doped with GDTA in the J61/ITIC blend film.
Example 8
Active layer PBDB-T/PC71The battery performance of 2 percent GDTA added into BM, and the device structure is ITO/PEDOT: PSS/PBDB-T: PC71BM/PDINO/Al, GDTA doped and undoped PBDB-T/PC71BM device preparation and testing procedures were as described in example 2, and the test results are shown in table 7.
TABLE 7 doping andGDTA undoped PBDB-T/PC71Performance parameters of BM optoelectronic devices
As can be seen from Table 7, compared with PBDB-T/PC without GDTA doping in the active layer71The BM blend film is a photovoltaic device with an optical active layer, and the PCE of the photovoltaic device doped with GDTA is improved by about 8.8%.
Example 9
The cell performance of the active layer PBDB-T/ITIC with 2% GDTA added, the device structure is ITO/PEDOT: PSS/PBDB-T: ITIC/PDINO/Al, the PBDB-T/ITIC device preparation and test process of the doped and undoped GDTA are as described in example 2, and the test results are shown in Table 8.
TABLE 8 Performance parameters of GDTA doped and undoped PBDB-T/ITIC optoelectronic devices
As can be seen from table 8, the PCE of the GDTA doped photovoltaic device was increased by about 9.21% compared to the photovoltaic device not doped with GDTA in the PBDB-T/ITIC blend film.
Example 10
The cell performance of the active layer PBDB-T/IT4F with 2% GDTA added, the device structure is ITO/PEDOT: PSS/PBDB-T: IT4F/PDINO/Al, the PBDB-T/IT4F device preparation and test process of the doped and undoped GDTA are as described in example 2, and the test results are shown in Table 9.
TABLE 9 Performance parameters of GDTA doped and undoped PBDB-T/IT4F optoelectronic devices
As can be seen from table 9, PCEs of the GDTA doped photovoltaic devices was increased by about 14% compared to the photovoltaic devices not doped with GDTA in the PBDB-T/IT4F blend film.
Example 11
The battery performance of the active layer PM6/IT4F with 2% GDTA added is that the device structure is ITO/PEDOT: PSS/PM6: IT4F/PDINO/Al, and the PM6/IT4F device with doped GDTA and undoped GDTA is prepared and tested by the steps as described in example 2, and the test results are shown in Table 10.
TABLE 10 Performance parameters of GDTA doped and undoped PM6/IT4F optoelectronic devices
As can be seen from table 10, the PCE of the GDTA doped photovoltaic device is increased by about 8.86% compared to the photovoltaic device not doped with GDTA in the PM6/IT4F blend film.
Example 12
The cell performance of the active layer PM6/Y6 with 1% PTEO added thereto was determined, and devices having ITO/PEDOT: PSS/PM6: Y6/PDINO/Al, and PM6/Y6 doped and undoped with PTEO were prepared and tested as described in example 2, and the results are shown in Table 11.
TABLE 11 Performance parameters of PTEO doped and undoped PM6/Y6 optoelectronic devices
As can be seen from table 11, PCEs of PTEO doped photovoltaic devices was increased by about 11.4% compared to photovoltaic devices not doped with PTEO in the PM6/Y6 blended thin film.
Example 13
Cell performance of 2% PG-1 added to PM6/Y6 of active layer, device structure ITO/PEDOT: PSS/PM6: Y6/PDINO/Al, PM6/Y6 doped and undoped GP-1, device preparation and testing were as described in example 2, and device results are shown in Table 12.
TABLE 12 Performance parameters of GP-1 doped and undoped PM6/Y6 optoelectronic devices
As can be seen from Table 12, the PCE of the PG-1 doped photovoltaic device was increased by about 8.7% compared to the photovoltaic device not doped with PG-1 in the PM6/Y6 blended film.
Example 14
Cell performance of 2% PG-2 added to PM6/Y6 of active layer, devices with ITO/PEDOT: PSS/PM6: Y6/PDINO/Al, PM6/Y6 doped and undoped PG-2 were prepared and tested as described in example 2, and the device results are shown in Table 13.
TABLE 13 Performance parameters of PM6/Y6 optoelectronic devices doped and undoped PG-2
As can be seen from Table 13, the PCE of the PG-2 doped photovoltaic device was increased by about 8.87% compared to the photovoltaic device not doped with PG-2 in the PM6/Y6 blended film.
Example 15
Cell performance of active layer PM6/Y6 with 8% PM6-NO5 added, device structures of ITO/PEDOT: PSS/PM6: Y6/PDINO/Al, and PM6/Y6 doped and undoped PM6-NO5 were prepared and tested as described in example 2, and device results are shown in Table 14.
TABLE 14 Performance parameters of PM6/Y6 optoelectronic devices doped and undoped PM6-NO5
Table 14 can see that the PCE of the PM6-NO5 doped photovoltaic device is increased by about 7% compared to the photovoltaic device not doped with PM6-NO5 in the PM6/Y6 blended film.
Example 16
Cell performance of active layer PM6/Y6 with 1% PG3 added, device structures ITO/PEDOT: PSS/PM6: Y6/PDINO/Al, and doped and undoped PG-3 PM6/Y6 were prepared and tested as described in example 2, and device results are shown in Table 15.
TABLE 15 Performance parameters of PM6/Y6 optoelectronic devices doped and undoped PG-3
As can be seen from Table 15, the energy conversion efficiency (PCEs) of the photovoltaic devices doped with the radical polymer GP-3 was increased by about 10% compared to the photovoltaic devices not doped with the radical polymer GP-3 in the PM6/Y6 blend film.
Example 17
The cell performance of the active layer PM6/Y6 with small molecule radical compound added, the device structure is ITO/PEDOT: PSS/PM6: Y6/PDINO/Al, the PM6/Y6 blend film device with small molecule radical compound TEMPO, GFR, BPFR, FBFR added is prepared and tested as described in example 2, and the device results are shown in Table 16.
TABLE 16 Performance parameters of PM6/Y6 optoelectronic devices doped and undoped TEMPO, GFR, BPFR, FBFR
Claims (4)
1. A free radical polymer having the formula i:
or, formula II:
in the formula I, m and n are natural numbers of 5-100;
in the formula II, x and y are both natural numbers of 0-5, m is a natural number of 1-3, n is a natural number of 1-5, B1And B2Are any one of oxygen, nitrogen, sulfur and phosphorus;
in the formula I and the formula II, Fr is any one of formula Fr-1 to formula Fr-8:
in the formulas Fr-1 to Fr-8, the dotted line is the linking position of Fr and a straight chain or branched chain halogenated alkyl, alkenyl, alkyl, aralkyl, heteroalkyl, alkoxy, alkylthio or ester group with the carbon number of 1-30.
2. A free radical polymer as claimed in claim 1 wherein in formulae I and II, Ar1And Ar2Are independently any one of formulas I-1 to I-48:
in the formulas I-1 to I-48, the dotted line is Ar1And or Ar2The attachment site of (a);
in the formulae I-1 to I-44, R1、R2And R3Independently selected from any one of hydrogen, halogen, straight chain or branched chain halogenated alkyl with 1-30 carbon atoms, alkenyl, alkyl, aralkyl, heteroalkyl, alkoxy, alkylthio, cyano, nitro and ester group;
in the formulae I-45 and I-46, R1、R2And R3Independently selected from any one of hydrogen, halogen, straight chain or branched chain alkyl with 1-30 carbon atoms, alkenyl, alkoxy and alkylthio, or any one of aromatic heterocyclic group and aromatic ring group substituted by hydrogen, halogen, straight chain or branched chain alkyl with 1-30 carbon atoms, alkenyl, alkoxy or alkylthio.
3. Use of a radical polymer as claimed in claim 1 or 2 for the production of organic/polymeric optoelectronic devices.
4. Use according to claim 3, wherein the organic/polymeric optoelectronic device comprises: organic/polymer light emitting devices, organic/polymer photovoltaic devices, organic/polymer photodetectors, organic/polymer thin film transistors, organic/polymer memory devices, and organic/polymer logic devices.
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