CN109651435B - Bipolar organic photoelectric functional material and preparation method thereof - Google Patents
Bipolar organic photoelectric functional material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 150000002642 lithium compounds Chemical class 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 4
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- -1 and after cooling Chemical compound 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 229950000688 phenothiazine Drugs 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- MZQCTQHUJODVPG-UHFFFAOYSA-N tert-butylphosphane dihydrochloride Chemical compound Cl.Cl.CC(C)(C)P MZQCTQHUJODVPG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- NMJASRUOIRRDSX-UHFFFAOYSA-N tert-butyl(dichloro)phosphane Chemical compound CC(C)(C)P(Cl)Cl NMJASRUOIRRDSX-UHFFFAOYSA-N 0.000 claims description 2
- 238000013086 organic photovoltaic Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 12
- 239000012043 crude product Substances 0.000 description 9
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
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- ATTVYRDSOVWELU-UHFFFAOYSA-N 1-diphenylphosphoryl-2-(2-diphenylphosphorylphenoxy)benzene Chemical compound C=1C=CC=CC=1P(C=1C(=CC=CC=1)OC=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ATTVYRDSOVWELU-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
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- SPPLEVHTUMPNLQ-UHFFFAOYSA-N 10-[4-(4-carbazol-9-ylphenyl)sulfonylphenyl]-9,9-dimethylacridine Chemical compound C1=2C=CC=CC=2N(C2=C1C=CC=C2)C1=CC=C(S(=O)(=O)C2=CC=C(N3C4=CC=CC=C4C(C4=C3C=CC=C4)(C)C)C=C2)C=C1 SPPLEVHTUMPNLQ-UHFFFAOYSA-N 0.000 description 1
- VCSYPBKEYNDNQU-UHFFFAOYSA-N Cl.Cl.CCCCP Chemical compound Cl.Cl.CCCCP VCSYPBKEYNDNQU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
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Abstract
The invention discloses a bipolar organic photoelectric functional material, which is obtained by connecting an N-P ═ X resonance structure with a donor unit, and has a structure shown in a general formula (I):
the band gap of the invention reaches 3.85eV, the triplet state energy level reaches 2.97eV, and the invention also has higher photoelectric property, stability, film forming property, solubility and the like. The electroluminescent device prepared by the invention has higher external quantum efficiency which reaches 18.3 percent.
Description
Technical Field
The invention relates to an organic photoelectric material and a preparation method thereof, in particular to a bipolar organic photoelectric functional material and a preparation method thereof.
Background
Organic light-emitting diodes (OLEDs) have excellent characteristics such as low driving voltage, high light-emitting efficiency, wide viewing angle, and wide operating temperature range, and thus have important application prospects in the fields of illumination and flat panel display. In order to balance the carrier injection rate of a light emitting device and improve the light emitting efficiency, an electron transport layer made of an electron transport material and a hole transport layer made of a hole transport material are generally introduced into the light emitting device, but the introduction of the transport layers often increases the manufacturing cost of the light emitting device, and the development of a bipolar transport material having both hole conduction and electron conduction properties has become a research hotspot in order to simplify the structure of the light emitting device. At present, most of the constructed bipolar transmission materials are based on a Donor (Donor) -Acceptor (Acceptor) structure, and a Donor unit for hole transmission and an Acceptor unit for charge transmission are simultaneously introduced into the same molecule, so that bipolar transmission of holes and electrons is realized. However, in such a Donor-Acceptor structure, a pi-conjugation effect generally exists between a Donor unit and an Acceptor unit, which reduces the triplet energy level of the material and a narrower band gap.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a bipolar organic photoelectric functional material, which has a blue light material with a wider band gap and a triplet state energy level.
The invention also aims to provide a preparation method of the bipolar organic photoelectric functional material.
The technical scheme is as follows: the invention provides a bipolar organic photoelectric functional material, which is obtained by connecting a donor unit through an N-P ═ X resonance structure, and the structure of the bipolar organic photoelectric functional material is shown as a general formula (I):
wherein P is a phosphorus atom, X is an oxygen atom, a sulfur atom, or a selenium atom, and R is any one of the following groups:
wherein N is a nitrogen atom, O is an oxygen atom, and S is a sulfur atom.
The bipolar organic photoelectric functional material can enable the original hole-transferring group to have certain electron-transferring capacity through resonance adjustment, endows the hole-transferring and electron-transferring capacity with excellent hole-transferring and electron-transferring capacity, realizes the bipolar transfer property without acceptor groups, ensures that the material has higher triplet state energy level through the non-conjugated connection mode of the resonance structure, and can well inhibit energy from being transferred back to the host material from the guest material.
Further, the structural formula of the bipolar organic photoelectric functional material is any one of the following formulas:
the preparation method of the bipolar organic photoelectric functional material comprises the following steps:
(1) under the protection of nitrogen, carbazole, phenoxazine, phenothiazine or acridine is dissolved in tetrahydrofuran, and after cooling, n-butyl lithium is added dropwise for reaction to form an organic lithium compound system;
(2) under the protection of nitrogen, adding tert-butyl phosphine dichloride into the organic lithium compound system in the step (1) to obtain a derivative containing an N-P structure;
(3) dissolving the derivative containing the N-P structure obtained in the step (2) in dichloromethane, adding a hydrogen peroxide solution for oxidation reaction, extracting, performing rotary evaporation, and passing through a column to obtain a solid, namely the bipolar organic photoelectric functional material with the N-P ═ O resonance structure; dissolving the N-P structure derivative obtained in the step (2) in dichloromethane, adding sulfur simple substance, carrying out vulcanization reaction, extracting, rotary evaporating and passing through a column to obtain a solid, namely the bipolar organic photoelectric functional material with an N-P ═ S resonance structure; and (3) dissolving the N-P structure derivative obtained in the step (2) in chloroform, adding selenium powder, carrying out a selenization reaction, and extracting, carrying out rotary evaporation and passing through a column to obtain a solid, namely the bipolar organic photoelectric functional material with an N-P ═ Se resonance structure.
Further, the molar ratio of carbazole, phenoxazine, phenothiazine or acridine to n-butyllithium in the step (1) is 1: 1-2. The molar ratio of the mono-tert-butyl phosphine dichloride to the organic lithium compound system in the step (2) is 0.5: 1. The mass concentration of the hydrogen peroxide solution in the step (3) is 30%. And (3) reacting at room temperature for 4-12 h, wherein the molar ratio of the hydrogen oxide solution to the N-P structure-containing derivative in the peroxidation reaction in the step (3) is 1-2: 1. The molar ratio of the sulfur simple substance in the vulcanization reaction in the step (3) to the derivative containing the N-P structure is 1-5: 1, and the reaction is carried out for 4-12 hours at room temperature. And (3) reacting the selenium powder and the derivative containing the N-P structure at room temperature for 4-12 hours, wherein the molar ratio of the selenium powder to the derivative containing the N-P structure in the selenizing reaction in the step (3) is 1-5: 1.
Further, the bipolar organic photoelectric functional material is applied to an organic electroluminescent device.
Has the advantages that: the invention has wider band gap (3.85eV), higher triplet state energy level (2.97eV), higher photoelectric property, stability, film forming property, solubility and the like. The electroluminescent device prepared by the invention has higher external quantum efficiency which reaches 18.3 percent.
Drawings
FIG. 1 shows ultraviolet absorption (UV) spectrum and fluorescence emission (PL) spectrum of the products of examples 1, 2 and 3 in the state of dichloromethane and thin film;
FIG. 2 is a graph showing energy levels of vapor deposition type electroluminescent devices produced in examples 1 and 2;
FIG. 3 is a graph of current density-voltage-luminance of an evaporation type electroluminescent device produced in examples 1 and 2;
FIG. 4 is a graph showing the efficiency of evaporation type electroluminescent devices of the products of examples 1 and 2;
FIG. 5 is a graph of energy levels of spin-on electroluminescent devices of the products of examples 1 and 2;
FIG. 6 is a graph of current density-voltage-luminance of a spin-on type electroluminescent device of the products of examples 1 and 2;
fig. 7 is a graph of the efficiency of spin-on electroluminescent devices of the products of examples 1 and 2.
Detailed Description
The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1: synthesis of photoelectric functional material 1(t-BuPO)
Taking two reaction bottles, adding 1.0g of carbazole, sealing, vacuumizing, blowing argon for three times, adding 20mL of anhydrous tetrahydrofuran under the protection of nitrogen, and placing in a dry ice/acetone bath at-78 ℃ for cooling for 10 min. 2.9mL of n-butyl lithium n-hexane solution is measured by a syringe, added into a reaction bottle dropwise and protected by nitrogenReacting at-78 ℃ for 1h, adding 0.62mL of monobutyl phosphine dichloride, reacting at room temperature for 8h, quenching the reaction liquid by 10mL of water, extracting by 3 × 30mL of dichloromethane solution, collecting the organic phase, drying by anhydrous sodium sulfate, concentrating to obtain a crude product, dissolving the obtained crude product by dichloromethane, dropwise adding 0.4mL of 30% hydrogen peroxide solution under 0 ℃ ice bath, reacting at room temperature for 6h, quenching the reaction liquid by 10mL of water, extracting by 3 × 30mL of dichloromethane solution, collecting the organic phase, drying by anhydrous sodium sulfate, concentrating to obtain a crude product, and separating and purifying by column chromatography to obtain 1.88g of white solid with the yield of 72%.1H NMR(DMSO-d6，400MHz)(ppm)：8.18-8.16(m，4H)，7.60-7.57(m，4H)，7.29-7.26(m，8H)，1.60(d，J＝20Hz，9H).13C NMR(CDCl3，100MHz)(ppm)：141.11，141.08，126.61，126.48，126.42122.32，119.90，114.97，39.89，38.85，26.43.HRMS(EI)：m/z calcd for C28H25N2PO[M+Na]+：459.1602；found：459.1601.Anal.calcd for C28H25N2PO：C 77.05，H 5.77，N 6.42；found：C 77.07，H5.68，N6.16。
The structure is as follows:
example 2: synthesis of photoelectric functional material 2(t-BuPS)
Adding 1.0g of carbazole into a two-mouth reaction bottle, sealing, vacuumizing, blowing argon for three times, adding 20mL of anhydrous tetrahydrofuran under the protection of nitrogen, placing the mixture into a dry ice/acetone bath at the temperature of-78 ℃ for cooling for 10min, measuring 2.9mL of n-butyl lithium n-hexane solution by using an injector, dropwise adding the n-butyl lithium n-hexane solution into the reaction bottle, reacting for 1h at the temperature of-78 ℃ under the protection of nitrogen, then adding 0.62mL of mono-tert-butyl phosphine dichloride, reacting for 8h at room temperature, quenching the reaction liquid by using 10mL of water, extracting by using 3 × 30mL of dichloromethane solution, collecting organic phases, drying by using anhydrous sodium sulfate, concentrating to obtain a crude product, dissolving the obtained crude product by using dichloromethane, adding 0.29g of sulfur, reacting for 6h at room temperature, reacting for 6h by using simple substanceThe reaction was quenched with 10mL of water, extracted with 3 × 30mL of dichloromethane solution, the organic phase was collected and dried over anhydrous sodium sulfate, concentrated to give the crude product, which was purified by column chromatography to give 1.43g of a white solid, 53% yield.1H NMR(DMSO-d6，400MHz)(ppm)：8.18(d，J＝8Hz，4H)，7.61(d，J＝8Hz，4H)，7.29-7.20(m，8H)，1.74(d，J＝20Hz，9H).13C NMR(CDCl3，100MHz)(ppm)：141.10，141.07，126.85，126.79，126.22，122.34，119.77，115.78，46.06，45.31，28.10.HRMS(EI)：m/z calcd for C28H25N2PS[M+H]+：453.1554；found：453.1548.Anal.calcd for C28H25N2PS：C 74.31，H5.57，N 6.19；found：C 74.43H 5.54，N5.94。
The structure is as follows:
example 3: synthesis of photoelectric functional material 3(t-BuPSe)
Taking two reaction bottles, adding 1.0g of carbazole, sealing, vacuumizing, blowing argon for three times, adding 20mL of anhydrous tetrahydrofuran under the protection of nitrogen, placing the mixture in a dry ice/acetone bath at-78 ℃ for cooling for 10min, measuring 2.9mL of n-butyl lithium n-hexane solution by using an injector, dropwise adding the n-butyl lithium n-hexane solution into the reaction bottles, reacting for 1h at-78 ℃ under the protection of nitrogen, then adding 0.62mL of mono-tert-butyl phosphine dichloride, reacting for 8h at room temperature, quenching the reaction liquid by using 10mL of water, extracting by using 3 × 30mL of dichloromethane solution, collecting organic phase, drying by using anhydrous sodium sulfate, concentrating to obtain a crude product, dissolving the obtained crude product by using dichloromethane, adding 0.71g of selenium powder, reacting for 6h at room temperature, quenching the reaction liquid by using 10mL of water, extracting by using 3 × 30mL of dichloromethane solution, collecting the organic phase, drying by using anhydrous sodium sulfate, concentrating to obtain the crude product, separating and purifying by column chromatography to obtain 1.43g of white solid, wherein the yield is 45%.1H NMR(DMSO-d6，400MHz)(ppm)：8.18(d，J＝8Hz，4H)，7.63-7.61(m，4H)，7.29-7.20(dt，J＝36Hz，8H)，1.78(d，J＝20Hz，9H).13C NMR(CDCl3，100MHz)(ppm)：141.10，141.07，126.85，126.79，126.22，122.34，119.77，115.78，46.06，45.31，28.10.Anal.calcd for C28H25N2PSe：C 67.33，H 5.05，N 5.61；found：C 67.26，H 5.34，N5.21。
The structure is as follows:
example 4: performance test of evaporation type organic electroluminescent device
The device of the present invention having the complex as a light-emitting layer may include: 1. a conductive glass layer (ITO); 2. hole injection layer PEDOT: PSS; 3. a hole transport layer (TAPC); 4. exciton blocking layer (mCP); 5. a light emitting layer; 6. an electron transport layer (TmPyPB); 7. an electron injection Layer (LiF); 8. and a cathode Al. The energy diagram of the evaporation type electroluminescent device is shown in fig. 2.
The manufacturing method of the evaporation type organic electroluminescent device comprises the following steps: firstly, spin-coating PEDOT on a cleaned glass substrate (ITO): PSS hole injection layer, then evaporation in turn. ITO/PEDOT: PSS (30nm)/1, 3, 5-Triazo-2, 4, 6-triphosphorine-2, 2, 4, 4, 6, 6-Tetrachlororide (TAPC) (20nm)/N, N' -dicarbazo lyol-3, 5-bezene (mCP) (8 nm)/host: 15 wt% FIrpic (22nm)/1, 3, 5-tri (m-pyridine-3-yl-phenyl) bezene (TmPyPB) (35nm)/LiF (1nm)/Al (100 nm). Wherein Host is the material 1(t-BuPO) or the material 2(t-BuPS) prepared in the above examples. The current density-voltage-luminance curve of the evaporation type electroluminescent device is shown in fig. 3. The efficiency curve of the electroluminescent device provided by the invention is shown in fig. 4. The test results are shown in table 1:
TABLE 1 results of the experiment
aThe data order is current efficiency, power efficiency, external quantum efficiency.
bData sequence is luminance of 100cd m-2Luminance of 1000cd m-2。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention and are intended to be equivalent substitutions are included in the scope of the present invention.
Example 5: performance test of spin-on type organic electroluminescent device
The device of the present invention having the complex as a light-emitting layer may include: 1. a conductive glass layer (ITO); 2. hole injection layer PEDOT: PSS; 3. a light emitting layer; 4. exciton blocking layers (DPEPO); 5. an electron transport layer (TmPyPB); 6. an electron injection layer (Liq); 7. and a cathode Al. The energy level diagram of the spin-on electroluminescent device is shown in fig. 5.
The manufacturing method of the spin coating type organic electroluminescent device comprises the following steps: firstly, spin-coating PEDOT on a cleaned glass substrate (ITO): PSS hole injection layer and luminescent layer, then in order to evaporate. ITO/PEDOT: PSS (60 nm)/host: 20 wt% of 10- (4- ((4- (9H-carbazol-9-yl) phenyl) sulfonyl) phenyl) -9, 9-dimethyl-9, 10-dihydroacridinine (CzAcSF): 15 wt% FIr6(40nm)/bis [2- (diphenylphosphino) phenyl ] ether oxide (DPEPO) (10nm)/TmPyPB (50 nm)/8-hydroxyquinonolato-lithium (Liq) (1nm)/Al (100 nm). Wherein Host is the blending of material 1(t-BuPO) or material 2(t-BuPS) and CZAcSF prepared in the above examples. The current density-voltage-luminance curve of the spin-on type electroluminescent device is shown in fig. 6. The efficiency curve of the electroluminescent device provided by the invention is shown in fig. 7. The test results are shown in table 2:
TABLE 2 test results
aThe data order is current efficiency, power efficiency, external quantum efficiency.
bData sequence is luminance of 100cd m-2Luminance of 1000cd m-2。
Claims (10)
1. A bipolar organic photoelectric functional material is characterized in that: the bipolar organic photoelectric functional material is obtained by connecting a donor unit through an N-P ═ X resonance structure, and the structure of the bipolar organic photoelectric functional material is shown as a general formula (I):
wherein P is a phosphorus atom, X is an oxygen atom, a sulfur atom, or a selenium atom, and R is any one of the following groups:
wherein N is a nitrogen atom, O is an oxygen atom, and S is a sulfur atom.
2. The bipolar organic photoelectric functional material according to claim 1, wherein: the structural formula of the bipolar organic photoelectric functional material is any one of the following structures:
3. the method for preparing a bipolar organic photoelectric functional material according to claim 1, wherein: the method comprises the following steps:
(1) under the protection of nitrogen, carbazole, phenoxazine, phenothiazine or acridine is dissolved in tetrahydrofuran, and after cooling, n-butyl lithium is added dropwise for reaction to form an organic lithium compound system;
(2) under the protection of nitrogen, adding tert-butyl phosphine dichloride into the organic lithium compound system in the step (1) to obtain a derivative containing an N-P structure;
(3) dissolving the derivative containing the N-P structure obtained in the step (2) in dichloromethane, adding a hydrogen peroxide solution for oxidation reaction, extracting, performing rotary evaporation, and passing through a column to obtain a solid, namely the bipolar organic photoelectric functional material with the N-P ═ O resonance structure; dissolving the N-P structure derivative obtained in the step (2) in dichloromethane, adding sulfur simple substance, carrying out vulcanization reaction, extracting, rotary evaporating and passing through a column to obtain a solid, namely the bipolar organic photoelectric functional material with an N-P ═ S resonance structure; and (3) dissolving the N-P structure derivative obtained in the step (2) in chloroform, adding selenium powder, carrying out a selenization reaction, and extracting, carrying out rotary evaporation and passing through a column to obtain a solid, namely the bipolar organic photoelectric functional material with an N-P ═ Se resonance structure.
4. The method for preparing a bipolar organic photoelectric functional material according to claim 3, wherein: the molar ratio of carbazole, phenoxazine, phenothiazine or acridine to n-butyllithium in the step (1) is 1: 1-2.
5. The method for preparing a bipolar organic photoelectric functional material according to claim 3, wherein: the molar ratio of the mono-tert-butyl phosphine dichloride to the organic lithium compound system in the step (2) is 0.5: 1.
6. The method for preparing a bipolar organic photoelectric functional material according to claim 3, wherein: the mass concentration of the hydrogen peroxide solution in the step (3) is 30%.
7. The method for preparing a bipolar organic photoelectric functional material according to claim 3, wherein: and (3) reacting for 4-12 h at room temperature in the oxidation reaction, wherein the molar ratio of the hydrogen peroxide solution to the derivative containing the N-P structure is 1-2: 1.
8. The method for preparing a bipolar organic photoelectric functional material according to claim 3, wherein: and (3) reacting at room temperature for 4-12 h in the vulcanization reaction, wherein the molar ratio of the sulfur simple substance to the derivative containing the N-P structure is 1-5: 1.
9. The method for preparing a bipolar organic photoelectric functional material according to claim 3, wherein: and (3) reacting at room temperature for 4-12 h, wherein the molar ratio of the selenium powder to the N-P structure-containing derivative is 1-5: 1.
10. Use of the ambipolar organic photovoltaic functional material according to claim 1 in an organic electroluminescent device.
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