CN108559014B - Organic polymer, hole transport material comprising same, solar cell, and light-emitting electronic device - Google Patents
Organic polymer, hole transport material comprising same, solar cell, and light-emitting electronic device Download PDFInfo
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Abstract
The invention provides an organic polymer, a hole transport material containing the organic polymer, a solar cell and a light-emitting electronic device, wherein the organic polymer has a structure shown in a formula (I), wherein Ar is selected from any one of a thiophene group, a bithiophene group, a trithiophene group, a benzene ring group, a naphthalene group or a phenanthrene group; m is 0 or 1; n is 10 to 1000; r1Is selected from-CH2CH3、‑NHCH3、‑OCH3or-SCH3Any one of them. The organic polymer provided by the invention has stronger hole extraction capability, has the highest occupied orbital (HOMO) of about-5.2 eV, is higher than the current most commonly used hole transport material Spiro-OMeTAD by more than 0.1eV, and can be applied to solar cells or light-emitting electronic devices.
Description
Technical Field
The invention belongs to the field of semiconductor materials, and relates to an organic polymer, a hole transport material containing the organic polymer, a solar cell and a light-emitting electronic device.
Background
In recent years, perovskite solar cells are developed rapidly, efficiency is improved very rapidly, and the efficiency of commercial solar cells is driven up in a few years. The hole transport material plays an important role in charge extraction and interface modification, and the selection of the hole transport material has great influence on the performance of the device.
Nowadays, 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino]-9,9' -spirobifluorene (Spiro-OMeTAD) has become the most applied and studiedIs a hole transport material of a wide range of perovskite solar cells. However, due to the complex synthetic route and the difficulty of purification, Spiro-OMeTAD is expensive, which severely limits its large-scale application and commercialization of perovskite solar cells. CN104844464A discloses a dendritic compound taking 9,9' -spirobifluorene as a core and methoxy-substituted diarylamine as a branch and application thereof in a perovskite solar cell; CN106748832A discloses a spiro [3,3 ]]The two patents disclosed by the novel hole transport material with heptane-2, 6-spirobifluorene as a core and methoxy-substituted diphenylamine as a modifying group have high photoelectric conversion efficiency, but are complex to synthesize and extremely low in yield. A large number of novel small molecule and polymer hole transport materials, including carbazole and thiophene based small molecules, polytriphenylamine and the like, are synthesized to act in perovskite solar cell devices. However, most hole transport materials (including Spiro-OMeTAD) have difficulty in forming planar molecular conformations, and thus have difficulty in forming strong intermolecular forces, which make the mobility thereof low and are not favorable for charge extraction. In order to increase the mobility, a method of doping a P-type dopant such as lithium salt is widely used. CN105405974 discloses a P-type doped perovskite photoelectric functional material, which is prepared from perovskite-based photoelectric functional material ABX3The perovskite-based photoelectric functional material is prepared by doping a P-type dopant as a matrix and an organic or inorganic dopant, has high hole mobility, but as an easily water-absorbing material, the addition of the lithium salt not only increases the process difficulty of device manufacturing, but also reduces the overall stability of the device. In order to improve the mobility of organic semiconductor materials, a common method at present is to design donor-acceptor type conjugated polymers or small molecules to improve the intermolecular interaction force. However, the current donor-acceptor type materials still need to use expensive raw materials and complicated synthesis steps. Moreover, donor-acceptor type materials have a relatively rigid molecular conformation, which reduces their solubility and thus their film-forming quality.
Therefore, designing a doping-free hole transport material with high mobility, simple synthesis and low price still remains a great challenge in the research of perovskite solar cells.
Disclosure of Invention
The invention aims to provide an organic polymer, a hole transport material containing the organic polymer, a solar cell and a light-emitting electronic device.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides an organic polymer having a structure represented by formula (I):
wherein Ar is selected from any one of thiophene group, bithiophene group, benzene ring group, naphthalene group or phenanthrene group; m is 0 or 1; n is 10 to 1000; r1Is selected from-CH2CH3、-NHCH3、-OCH3or-SCH3Any one of them.
In the present invention, the value of m represents the number of carbon atoms, and the value of m is 0 or 1.
According to the invention, a styrene polymer chain is taken as a main chain, Ar groups and triphenylamine derivative groups on two sides of the Ar groups are introduced into a side chain, so that a non-conjugated side chain type polymer is obtained; because the polymerization unit of the styrene polymer chain is smaller, the space distance between small molecules of the obtained organic polymer is shorter, the interaction force between small molecule monomers is stronger, and the charge mobility of the whole material can be improved.
In a second aspect, the present invention provides a method of synthesizing an organic polymer as described in the first aspect, the method comprising the steps of:
(1) condensing the compound A and the compound B to obtain a compound C;
wherein the compound a has the structure of formula (II):
the compound B has the structure of formula (III):
the compound C has the structure of formula (IV):
wherein, Y1And Y2Are each independently selected from halogen or hydroxy, Y1And Y2Is not halogen at the same time; r1Ar and m have the same ranges as in claim 1.
(2) And (2) carrying out addition polymerization on the compound C obtained in the step (1) under the action of an initiator to obtain the organic polymer.
The organic polymer provided by the invention is simple to synthesize and purify and easy to prepare.
Preferably, the molar ratio of compound A to compound B in step (1) is 1 (1.3-1.5), such as 1:1.3, 1:1.4, 1:1.5, etc.
Preferably, the solvent for the condensation of step (1) is N, N-dimethylformamide.
Preferably, the catalyst for the condensation of step (1) is NaH.
Preferably, the condensation reaction temperature in step (1) is 55-65 deg.C, such as 55 deg.C, 57 deg.C, 60 deg.C, 62 deg.C, 65 deg.C, etc.
Preferably, the reaction time of the condensation of step (1) is 24-36h, such as 24h, 28h, 30h, 32h, 34h, 36 h.
In the present invention, the initiator in step (2) is AIBN.
Preferably, the mass ratio of the initiator to the compound C in the step (2) is 1: 100.
Preferably, the polyaddition reaction of step (2) is carried out in the presence of a protective gas, preferably nitrogen.
Preferably, the reaction temperature of the addition polymerization reaction of the step (2) is 80 to 90 ℃, for example, 80 ℃, 82 ℃, 85 ℃, 87 ℃, 90 ℃ and the like.
Preferably, the reaction time of the addition polymerization reaction of step (2) is 1 to 3 days, such as 1 day, 1.5 days, 2 days, 2.5 days, 3 days, etc.
Preferably, the solvent for the addition polymerization of step (2) is any one or a combination of at least two of tetrahydrofuran, dichloromethane, chloroform and toluene.
In the invention, the preparation method of the compound A comprises the following steps: condensing compound D with compound E to provide compound a, having the formula:
preferably, the molar ratio of compound D to compound E during the preparation of compound A is 1 (2-2.3), such as 1:2, 1:2.1, 1:2.2, 1:2.3, etc.
Preferably, in the preparation of compound a, the reaction catalyst for the condensation is tetrakis (triphenylphosphine) palladium.
Preferably, in the preparation of compound a, the reaction solvent of the condensation is tetrahydrofuran.
Preferably, in the preparation of compound a, the condensation is carried out in the presence of a protective gas, preferably nitrogen.
Preferably, in the preparation of compound a, the reaction time of the condensation is 15-25h, such as 15h, 17h, 20h, 22h, 24h, 25 h.
The organic polymer provided by the invention can be prepared by the following method:
in a third aspect, the present invention provides a hole transport material comprising an organic polymer as described in the first aspect.
The term "comprising" as used herein means that it may include other components in addition to the recited components, for example, it may be doped with other elements or semiconductor materials. In addition, the term "comprising" as used herein may be replaced by "being" or "consisting of … …" as closed.
Preferably, the hole transport material is an organic polymer as described in the first aspect.
In a fourth aspect, the present invention provides a hole transport layer, and a method for preparing the hole transport layer, comprising the steps of: coating the dispersion of the organic polymer according to the first aspect on a substrate, and then curing to obtain the hole transport layer.
Preferably, the substrate comprises any one of a perovskite material, a conductive glass, a metal oxide semiconductor material, or a conductive polymer thin film.
The organic polymer provided by the invention has higher hole transport capability, and the hole mobility reaches 1.6 × 10- 4cm-2V-1S-1Close to the mobility of lithium salt doped Spiro-OMeTAD.
In a fifth aspect, the present invention provides a solar cell comprising the hole transport layer of the fourth aspect, or a hole transport layer of a solar cell comprising the hole transport material of the third aspect.
Preferably, the solar cell comprises a perovskite solar cell, preferably a lead iodide methylamine type perovskite solar cell.
To be provided with
For example, FIG. 1 is a graph of the energy levels of an organic polymer A1 and methylamine lead perovskite, wherein the HOMO level (-5.18eV) of the organic polymer A1 is higher than the HOMO level (-5.4eV) of methylamine lead perovskite to facilitate the transfer of charges from the methylamine lead perovskite layer to the hole transport layer, and the higher LUMO level (-2.35eV) of A1 is effective in preventing electrons from passing through the hole transport layer.
The organic polymer provided by the invention has stronger hole extraction capability, the highest occupied orbital HOMO is about-5.2 eV, the highest occupied orbital HOMO is higher than that of the current most commonly used hole transport material Spiro-OMeTAD by more than 0.1eV, and the organic polymer is more matched with the energy level of perovskite, in particular to lead iodide methylamine type perovskite; the perovskite solar cell device prepared by using the organic polymer as a hole transport material has higher efficiency.
In a sixth aspect, the present invention provides a light-emitting electronic device comprising the hole transport layer of the fourth aspect, or a hole transport layer of the light-emitting electronic device comprising the hole transport material of the third aspect.
Preferably, the light-emitting electronic device comprises a perovskite light-emitting diode.
The organic polymer provided by the invention has higher hole transmission capability, and can be applied to the preparation of organic electronic devices, in particular organic electronic devices with light-electricity conversion characteristics, such as perovskite solar cells or perovskite light-emitting diodes.
Compared with the prior art, the invention has the following beneficial effects:
(1) the organic polymer provided by the invention obtains a non-conjugated side chain type polymer through a styrene polymer chain, and the distance between small molecules of the polymer chain is shortened through the polymer chain, so that the interaction force between small molecule monomers is enhanced, and the charge mobility of the whole material is improved;
(2) the organic polymer provided by the invention has stronger hole extraction capability, the highest occupied orbital (HOMO) is about-5.2 eV, and the highest occupied orbital (HOMO) is higher than that of the current most commonly used hole transport material Spiro-OMeTAD by more than 0.1 eV;
(3) the organic polymer provided by the invention has higher hole transport capability, and the hole mobility reaches 1.6 × 10-4cm-2V-1S-1Mobility close to that of lithium salt doped Spiro-OMeTAD;
(4) the organic polymer provided by the invention is used as a hole transport material and is more matched with the energy level of perovskite, and the prepared perovskite solar cell device, especially a lead iodide methylamine type perovskite solar cell device, has higher efficiency, and the photoelectric conversion efficiency can reach 17.2%;
(5) the organic polymer provided by the invention can also be applied to the preparation of light-emitting electronic devices, such as perovskite light-emitting diodes;
(6) the organic polymer provided by the invention is easy to prepare, simple in synthesis and purification process and low in cost.
Drawings
Fig. 1 is an energy level diagram of an organic polymer a1 and methylamine lead perovskite.
FIG. 2 is a UV-visible absorption spectrum of an organic polymer A1 of preparation example 1 of the present invention.
FIG. 3 is a fluorescence spectrum of organic polymer A1 of preparation example 1 of the present invention.
FIG. 4 is a cyclic voltammogram of organic polymer A1 of preparation example 1 of the present invention.
Fig. 5 is a schematic structural diagram of a perovskite solar cell provided in example 1 of the present invention.
Fig. 6 is a current-voltage test pattern of the perovskite solar cell provided in example 1 of the present invention.
Fig. 7 is a schematic structural diagram of a perovskite light emitting diode provided in embodiment 2 of the present invention.
Fig. 8 is a schematic structural diagram of a solar cell provided in embodiment 3 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In preparation examples 1 to 5, the monomer structure before the addition of the double bonds of the organic polymer and the organic polymer is characterized, and the characterization of the organic polymer shows that the characteristic peak of the carbon-carbon double bonds of the monomer after polymerization disappears, which proves that the monomer is polymerized, but the nuclear magnetic spectrum of the organic polymer shows several peaks and can not accurately characterize the structure of the organic polymer, so we focus on characterizing the monomer structure of the organic polymer.
Preparation example 1
As an illustrative example, the present preparation example provides a specific preparation method of the organic polymer a1, wherein a1 has the following structure, and the polymerization degree n of a1 is 31:
the reaction scheme for the preparation of a1 is as follows:
the preparation method comprises the following steps:
(1) compound D (0.38g,1.4mmol), compound E (1.1g,3.1mmol), tetrakis (triphenylphosphine) palladium (0.08g,0.07mmol), and an aqueous potassium carbonate solution (2.0 mol. L)-13.5mL) and tetrahydrofuran (20mL) were added to a 50mL round-bottom flask, stirred under nitrogen for about 20 hours, washed with water after the reaction was completed, separated, and the organic phases were combined. The organic phase was dried over anhydrous sodium sulfate, the organic solution was removed by rotary evaporation, and the crude product was purified by silica gel chromatography (dichloromethane: methanol ═ 20:1) to give compound a (0.85g) in 85% yield.
(2) Dissolving a compound A (0.5g and 0.7mmol) in anhydrous dimethylformamide (10mL), adding sodium hydride (0.28g and 7mmol) under vigorous stirring, stirring at room temperature for 1 hour, then dropwise adding p-chloromethyl styrene, stirring at 60 ℃ for 6 hours, washing with water after the reaction is finished, separating liquid, and combining organic phases; the organic phase was dried over anhydrous sodium sulfate, the organic solution was removed by rotary evaporation, and the crude product was purified by silica gel chromatography to give compound C (0.46g) in 80% yield.
(3) Compound C (0.5g,0.6mmol), azobisisobutyronitrile (5mg) were dissolved in 1 ml of tetrahydrofuran and stirred at 85 ℃ for 3 days. The crude product was washed with methanol to give A1(0.45 g).
Characterization data for compound a are as follows:
1H NMR(400MHz,DMSO-d6)，7.44(d,J＝8.4Hz,2H),7.32(d,J＝7.4Hz,3H),7.13-6.99(m,8H),6.95-6.92(m,8H),6.82-6.70(m,4H),5.19(t,J＝5.3Hz,1H),4.42(d,J＝5.3Hz,2H),3.75(s,12H).
13C NMR(100MHz,DMSO)156.4,148.4,140.7,140.3,139.2,137.3,129.6,127.5,126.3,119.8,119.2,115.5,57.8,55.7.
MS(HRESI):m/z calcd for C45H40N2O5S:721.2731；found:721.2712.
characterization data for compound C are as follows:
1H NMR(400MHz,DMSO-d6)7.46-7.40(m,4H),7.32-7.25(m,4H),7.08-7.04(m,8H),6.97-6.92(m,8H),6.78-6.73(m,4H),6.70-6.66(m,1H),5.79(d,J＝17.7Hz,1H),5.24(d,J＝11.0Hz,1H),4.52(s,2H),4.43(s,2H),3.75(s,12H).
13C NMR(100MHz,DMSO)156.4,148.4,141.0,140.2,139.6,138.3,136.8,134.8,129.5,128.5,127.6,127.3,126.5,125.6,124.8,119.7,118.9,115.5,114.6,71.6,65.9,55.7.
MS(HRESI):m/z calcd for C54H48N2O5S:836.32784；found:836.32697.
ultraviolet-visible light absorption spectrum and fluorescence spectrum tests are carried out on the tetrahydrofuran solution A1 obtained in the preparation example; the ultraviolet-visible absorption spectrum test result is shown in FIG. 2, and the fluorescence spectrum test result is shown in FIG. 3. The absorption peak at 384nm in FIG. 2 is the maximum absorption peak of A1, and the initial absorption wavelength is 438 nm; the emission peak at 477nm in FIG. 3 is the fluorescence emission peak of A1.
Preparation examples 2 to 3
The only difference from preparation example 1 was that the polymerization degree n of the organic polymer a2 was 12 (preparation example 2) and the polymerization degree n of the organic polymer A3 was 96 (preparation example 3).
Preparation example 4
The only difference from preparation example 1 is that the organic polymer A4 of this preparation example has the following structure, wherein R1is-CH2CH3：
The monomer structure of organic polymer a4 was characterized as follows:
1H NMR(400MHz,DMSO-d6)7.46-7.40(m,4H),7.32-7.25(m,4H),7.08-7.04(m,8H),6.97-6.92(m,8H),6.78-6.73(m,4H),6.70-6.66(m,1H),5.79(d,J＝17.7Hz,1H),5.24(d,J＝11.0Hz,1H),4.52(s,2H),4.43(s,2H),2.80(q,J＝7.9Hz,8H),1.18(t,J＝8.0Hz,12H).
preparation example 5
The only difference from preparation 1 is that the organic polymer a5 of this preparation has the following structure, where Ar is a bithiophene group:
the monomer structure of organic polymer a5 was characterized as follows:
1H NMR(400MHz,DMSO-d6)7.55-7.45(m,4H),7.32-7.25(m,4H),7.10-7.06(m,8H),6.97-6.92(m,8H),6.78-6.73(m,4H),6.70-6.66(m,1H),5.79(d,J＝17.7Hz,1H),5.24(d,J＝11.0Hz,1H),4.52(s,2H),4.43(s,2H),3.75(s,12H).
preparation example 6
The only difference from preparation example 1 is that the organic polymer A6 of this preparation example has the following structure, where Ar is a bithiophene group, R1is-CH2CH3：
The monomer structure of organic polymer a6 was characterized as follows:
1H NMR(400MHz,DMSO-d6)7.55-7.45(m,4H),7.32-7.25(m,4H),7.10-7.06(m,8H),6.97-6.92(m,8H),6.78-6.73(m,4H),6.70-6.66(m,1H),5.79(d,J＝17.7Hz,1H),5.24(d,J＝11.0Hz,1H),4.52(s,2H),4.43(s,2H),2.80(q,J＝7.9Hz,8H),1.18(t,J＝8.0Hz,12H).
preparation example 7
The only difference from preparation example 1 is that the organic polymer A7 of this preparation example has the following structure, wherein Ar is a benzene ring group, R1is-NHCH3：
The structure of organic polymer a7 was characterized as follows:
1H NMR(400MHz,DMSO-d6)8.09(s,1H),7.99(d,J＝7.5Hz,1H),7.55-7.40(m,4H),7.37-7.25(m,4H),7.22(J＝7.5Hz,1H),7.10-7.06(m,8H),6.97-6.92(m,8H),6.78-6.73(m,4H),6.70-6.66(m,1H),6.5(s,4H),5.79(d,J＝11.2Hz,1H),5.24(d,J＝11.0Hz,1H),4.52(s,2H),4.43(s,2H),3.75(s,12H).
comparative preparation example 1
The only difference from preparation example 1 is that the organic polymer A8 of this preparation example had a polymerization degree n value of 2.
Comparative preparation example 2
The only difference from preparation example 1 is that the organic polymer A9 of this preparation example had a polymerization degree n value of 1100.
Performance testing
The electrochemical performance of the organic polymer A1 provided in the preparation example was subjected to a performance test.
The test method of the cyclic voltammetry comprises the following steps:
the organic polymer was dissolved in anhydrous dichloromethane (concentration: 5 mg/ml) and biased (-1.8V) to obtain cyclic voltammograms. After the test was completed, a small amount of ferrocene was added to the anhydrous dichloromethane solution of A1, and the cyclic voltammogram of ferrocene was tested. Thereby obtaining the redox potential of the polymer semiconductor material relative to ferrocene.
The highest molecular occupied orbital level (HOMO) and the lowest molecular empty orbital Level (LUMO) of a polymeric semiconductor material can be calculated by the following equations:
EHOMO＝-(Eox onset+5.10)
ELUMO＝-(EHOMO+Eg)
Eg(eV)＝1240/λonset
wherein E isox onset(eV) is the initial oxidation potential, λonset(nm) is the initial absorption wavelength.
Fig. 4 shows cyclic voltammograms obtained from the test of the organic polymer a1, which were calculated from the cyclic voltammograms of fig. 4: e of organic Polymer A1HOMOIs-5.18 eV, ELUMOIs-2.35 eV.
Electrochemical performance simulations (Gaussian 09 software, calculation method CAM-B3LYP) were performed on the organic polymers A1-A9 provided in preparation examples 1-7 and comparative preparation examples 1-2, and the simulation results are shown in Table 1:
TABLE 1
As is clear from the data in the table, the energy level structure (HOMO and LUMO energy levels) of a1 simulated was the same as the actually measured energy level structure of a1, and therefore the simulation results were reliable.
As shown in the test in Table 1, the HOMO energy level of the organic polymer provided by the invention is-5.23 to-5.13 eV, and the LOMO energy level is-2.37 to-2.32 eV, so that the organic polymer can be used as a hole transport material of a solar cell or a light-emitting electronic device.
The invention only takes the organic polymer A1 as an example to prepare the solar cell and the light-emitting diode with the following structures, and does not represent that only the organic polymer A1 can be used; compared with A1, the molecular structure of A2-A7 is similar to that of A1, and has similar energy level structures (HOMO and LUMO energy levels), so that the effect similar to that of A1 can be achieved by replacing the organic polymer A1 with the organic polymer A2-A7; in addition, the A1-A7 have long flexible polymer chains, and the polymer chains have good solubility in common solvents, so that the solution method is favorable for preparing solar cell devices.
Taking A4 as an example, the terminal group R is compared with A11is-CH2CH3The electron cloud density is relatively-OCH3Low, so that the HOMO energy level is higher, and the separation of charges is facilitated; taking A7 as an example, R1is-NHCH3The electron cloud density is relatively-OCH3And the HOMO level is high, so that the HOMO level is low, and although the charge separation efficiency is influenced at this time, the lower HOMO level is beneficial to improving the open-circuit voltage of the device, so that the conversion efficiency of the device is improved.
For the adjustment of the core group Ar, the bithiophene group and the bithiophene group have smoother molecular structures compared with thiophene, and the smoother molecular structures are beneficial to orderly accumulation of molecules, increase the intermolecular acting force and improve the mobility; compared with thiophene, the benzene ring has lower electron cloud density, so that the HOMO energy level of the polymer taking the benzene ring as the core is higher, and the improvement of open-circuit voltage is facilitated; compared with a benzene ring, the naphthalene group or the phenanthrene group has a flatter molecular structure, the flatter molecular structure is beneficial to orderly accumulation of molecules, the intermolecular acting force is increased, and the mobility is improved.
Thus, it is surmised that a2-a7 is equally suitable as hole transport material for use in perovskite solar cells and other solar cells as well as light emitting diodes.
Example 1
Fig. 5 shows a schematic structural diagram of a perovskite solar cell constructed by using the organic polymer provided by the preparation example of the invention, and the perovskite solar cell comprises the following structures from bottom to top:
a substrate 101(100nm), an ITO electrode 102(15nm), a titanium dioxide dense layer 103 (c-TiO)210nm), titanium dioxide mesoporous layer 104 (m-TiO)230nm), a perovskite light absorption layer 105(500nm), a hole transport layer 106(50nm) and a magnesium silver electrode 107(100nm), wherein the material of the hole transport layer 106 is selected from the organic polymer A1 provided by the preparation example.
Performance testing
The perovskite solar cell provided in example 1 was tested for its current-voltage spectrum by the following test method:
a Taiwan light Yan technology solar spot simulator, model Enlite SS-F7-3A, is adopted, and a light source is a 300-watt xenon lamp to simulate sunlight. The light intensity is calibrated by a standard silicon cell detector, and the spectrum of a test light source is close to the spectrum of standard sunlight (1.5G,100mW cm)-2) Applying a bias voltage of-0.2V to 1.2V to the device under simulated sunlight by using a Keithley2400 digital source table, and testing corresponding current to obtain a corresponding current-voltage curve, wherein the photoelectric conversion efficiency is equal to an open-circuit voltage × short-circuit current density × filling factor.
Fig. 6 shows a current-voltage test pattern of the perovskite solar cell provided in example 1.
The test results are shown in table 2:
TABLE 2
Test results show that the organic polymer A1 provided by the invention has higher photoelectric conversion efficiency which can reach 17.2% when being applied to perovskite organic solar cells.
Example 2
Fig. 7 shows a schematic structural diagram of a perovskite light emitting diode constructed by using the organic polymer provided by the preparation example of the invention, and the structure comprises the following structures from bottom to top:
substrate 201(100nm), ITO electrode 202(15nm), titanium dioxide dense layer 203 (c-TiO)210nm), a perovskite luminescent layer 204(30nm), a hole transport layer 205(10nm) and a magnesium silver electrode 206(15nm), wherein the material of the hole transport layer is selected from the organic polymer A1 provided by the preparation example.
The light emitting mechanism of the light emitting diode is as follows: electrons and holes are respectively injected into the electroluminescent diode device from the cathode and the anode, the electrons and the holes are compounded into excitons in the light emitting layer, the excitons return to the ground state in the form of radiation transition and emit light, when the hole transport layer has a proper HOMO energy level, the holes are favorably injected into the hole transport layer of the electroluminescent diode device from the anode, the HOMO energy level of the organic polymer provided by the invention is-5.23-5.13 eV, and the hole injection into the hole transport layer from the anode is very favorable, so that the organic polymer provided by the invention can be applied to the perovskite light emitting diode as a hole transport material.
Example 3
Fig. 8 shows a schematic structural diagram of an organic solar cell constructed by using the organic polymer provided in the preparation example of the present invention, and includes the following structures from bottom to top:
substrate 301(100nm), ITO electrode 302(15nm), hole transport layer 303(20nm), light absorbing layer 304(P3HT:PC61BM,100nm), an electron transport layer 305(LiF or ZnO,1nm), a metal electrode 306(100 nm). Wherein, the material of the hole transport layer is selected from organic polymer A1 provided by preparation example, P3HT is poly (3-hexylthiophene), PC61BM is a fullerene derivative.
Performance testing
The solar cell provided in this embodiment was subjected to a performance test:
a Taiwan light Yan technology solar spot simulator, model Enlite SS-F7-3A, is adopted, and a light source is a 300-watt xenon lamp to simulate sunlight. The light intensity is calibrated by a standard silicon cell detector, and the spectrum of a test light source is close to the spectrum of standard sunlight (1.5G,100mW cm)-2). And applying a bias voltage of-0.2 to 1.2V to the device under simulated sunlight by using a Keithley2400 digital source meter, testing corresponding current to obtain a corresponding current-voltage curve, and processing the curve to obtain related data.
The test results are shown in table 4:
TABLE 4
According to the test result, when P3HT: PC is used61When BM is used as a light absorbing layer, the photoelectric conversion efficiency is 3.5%, and it is understood from example 3 that the organic polymer provided by the present invention as a hole transport material can be applied not only to perovskite solar cells but also to other solar cells as a hole transport material.
Examples 4 to 5
The only difference from example 1 is that in this example, the material of the hole transport layer 106 is selected from the organic polymers A8 (example 4) and a9 (example 5) provided in the preparation examples.
We found that the solubility of the organic polymer a9 is poor, it is difficult to form a hole transport layer with a certain thickness during the coating process, it is impossible to achieve full coverage of the lower layer, and leakage occurs during the test process.
The perovskite solar cell provided in example 4 was tested and the test results are shown in table 4:
TABLE 4
From examples 4 to 5, it is understood that when the polymerization degree of the organic polymer is small, the photoelectric conversion efficiency is poor, presumably because: the interaction force between the small molecular monomers is not high, and the charge mobility of the whole material is low; when the polymerization degree of the organic polymer is larger, the solubility of the polymer is obviously reduced, the preparation of a device by a solution method is not facilitated, and a material with too high polymerization degree is difficult to form a hole transport layer with a certain thickness, so that the lower layer is completely covered, and the electric leakage phenomenon is easy to generate. From examples 1 to 5, it is understood that the organic polymer provided by the present invention can be preferably used as a hole transport material when the polymerization degree is 10 to 1000.
The applicant states that the present invention is illustrated by the above examples of the organic polymer, the hole transport material comprising the same, the solar cell and the light emitting electronic device of the present invention, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by relying on the above examples. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (28)
1. An organic polymer having a structure according to formula (I):
wherein Ar is selected from any one of thiophene group, bithiophene group, benzene ring group, naphthalene group or phenanthrene group; m is 0 or 1; n is 10 to 1000; r1Is selected from-CH2CH3、-NHCH3、-OCH3or-SCH3Any one of them.
2. The method for synthesizing an organic polymer according to claim 1, wherein the method comprises the steps of:
(1) condensing the compound A and the compound B to obtain a compound C;
wherein the compound a has the structure of formula (II):
the compound B has the structure of formula (III):
the compound C has the structure of formula (IV):
wherein, Y1And Y2Are each independently selected from halogen or hydroxy, and Y1And Y2Is not halogen at the same time; r1Ar, m have the same ranges as in claim 1;
(2) and (2) carrying out addition polymerization on the compound C obtained in the step (1) under the action of an initiator to obtain the organic polymer.
3. The synthesis method according to claim 2, wherein the molar ratio of the compound A to the compound B in the step (1) is 1 (1.3-1.5).
4. The method of claim 2, wherein the solvent for the condensation in step (1) is N, N-dimethylformamide.
5. The synthesis method according to claim 2, wherein the catalyst for the condensation in step (1) is NaH.
6. The method of claim 2, wherein the condensation of step (1) is carried out at a temperature of 55-65 ℃.
7. The synthesis method according to claim 2, wherein the reaction time of the condensation in the step (1) is 24-36 h.
8. The method of claim 2, wherein the initiator of step (2) is AIBN.
9. The synthesis method according to claim 2, wherein the mass ratio of the initiator to the compound C in the step (2) is 1: 100.
10. The synthesis process according to claim 2, wherein the polyaddition reaction of step (2) is carried out in the presence of a protective gas, said protective gas being nitrogen.
11. The synthesis method according to claim 2, wherein the reaction temperature of the addition polymerization reaction of the step (2) is 80 to 90 ℃.
12. The synthesis method according to claim 2, wherein the reaction time of the addition polymerization reaction of the step (2) is 1 to 3 days.
13. The synthesis method according to claim 2, wherein the solvent for the addition polymerization in step (2) is any one or a combination of at least two of tetrahydrofuran, dichloromethane, chloroform and toluene.
14. The synthesis method according to claim 2, wherein the compound A is prepared by the following steps: condensing compound D with compound E to provide compound a, having the formula:
wherein, Ar and Y1、R1Having the same range as in claim 2.
15. The synthesis method of claim 14, wherein the molar ratio of the compound D to the compound E in the preparation of the compound A is 1 (2-2.3).
16. The synthesis method according to claim 14, wherein in the preparation of the compound A, the condensation reaction catalyst is tetrakis (triphenylphosphine) palladium.
17. The synthesis method according to claim 14, wherein in the preparation of the compound a, the reaction solvent for the condensation is tetrahydrofuran.
18. The synthesis method according to claim 14, characterized in that, during the preparation of compound a, the condensation is carried out in the presence of a protective gas, which is nitrogen.
19. The synthesis method according to claim 14, wherein the reaction time of the condensation in the preparation of the compound a is 15-25 h.
20. A hole transport material comprising the organic polymer of claim 1.
21. The hole transport material of claim 20, wherein the hole transport material is the organic polymer of claim 1.
22. A hole transport layer, characterized in that it is prepared by a process comprising the steps of: the hole transport layer is obtained by applying the dispersion of the organic polymer according to claim 1 to a substrate and then curing.
23. The hole transport layer of claim 22, wherein the substrate comprises any one of a perovskite material, a conductive glass, a metal oxide semiconductor material, or a conductive polymer thin film.
24. A solar cell, characterized in that the solar cell comprises a hole transport layer according to claim 22 or 23, or the hole transport layer of the solar cell comprises a hole transport material according to claim 20 or 21.
25. The solar cell of claim 24, wherein the solar cell comprises a perovskite solar cell.
26. The solar cell of claim 25, wherein the solar cell is a lead iodide methylamine type perovskite solar cell.
27. A light-emitting electronic device characterized in that the light-emitting electronic device comprises the hole transport layer of claim 22 or 23, or the hole transport layer of the light-emitting electronic device comprises the hole transport material of claim 20 or 21.
28. The light-emitting electronic device according to claim 27 wherein the light-emitting electronic device comprises a perovskite light-emitting diode.
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