CN110698654A - Hyperbranched conjugated polyelectrolyte based on trimeric indole, preparation method and application thereof - Google Patents
Hyperbranched conjugated polyelectrolyte based on trimeric indole, preparation method and application thereof Download PDFInfo
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- CN110698654A CN110698654A CN201810749599.7A CN201810749599A CN110698654A CN 110698654 A CN110698654 A CN 110698654A CN 201810749599 A CN201810749599 A CN 201810749599A CN 110698654 A CN110698654 A CN 110698654A
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- Prior art keywords
- conjugated polyelectrolyte
- hyperbranched conjugated
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- indole
- compound
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- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229920000867 polyelectrolyte Polymers 0.000 title claims abstract description 62
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 title claims abstract description 49
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000005525 hole transport Effects 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000013086 organic photovoltaic Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 9
- -1 small molecule compound Chemical class 0.000 claims description 7
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 6
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical group O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 5
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 claims description 4
- SDXUIOOHCIQXRP-UHFFFAOYSA-N 1,2,4,5-tetrafluorobenzene Chemical compound FC1=CC(F)=C(F)C=C1F SDXUIOOHCIQXRP-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 238000006619 Stille reaction Methods 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 3
- 238000006254 arylation reaction Methods 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 238000007336 electrophilic substitution reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000005693 optoelectronics Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 21
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000005829 trimerization reaction Methods 0.000 abstract description 7
- 238000010129 solution processing Methods 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 239000011368 organic material Substances 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QZSXXAOHMOQXAZ-UHFFFAOYSA-N 2',7'-bis(diphenylphosphoryl)-9,9'-spirobi[fluorene] Chemical compound C=1C=CC=CC=1P(C=1C=C2C3(C4=CC=CC=C4C4=CC=CC=C43)C3=CC(=CC=C3C2=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 QZSXXAOHMOQXAZ-UHFFFAOYSA-N 0.000 description 2
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 1
- FFZHICFAHSDFKZ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-thiophen-2-yl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CS1 FFZHICFAHSDFKZ-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- QNLOWBMKUIXCOW-UHFFFAOYSA-N indol-2-one Chemical compound C1=CC=CC2=NC(=O)C=C21 QNLOWBMKUIXCOW-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 description 1
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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Abstract
The invention belongs to the field of organic semiconductor photoelectric materials, and particularly relates to a hyperbranched conjugated polyelectrolyte based on trimeric indole, and a preparation method and application thereof. The hole transport material solves the technical problems that in the prior art, a hole transport material based on the trimerization indole and the derivatives thereof has poor film forming property, a device is difficult to be prepared by solution processing by an orthogonal solvent method, and the efficiency of the prepared device is low. The pH value of the hyperbranched conjugated polyelectrolyte material based on the trimeric indole is neutral, and corresponding electrodes and organic materials cannot be corroded; the organic photoelectric device hole transport layer can be prepared by solution processing by an orthogonal solvent method; the light-transmitting material has the advantages of good light transmittance in a visible light region, good thermal stability and the like. The hyperbranched conjugated polyelectrolyte based on the trimeric indole prepared by the invention is used as a hole transport layer to prepare an organic photovoltaic device or an organic electroluminescent device, and has higher efficiency.
Description
Technical Field
The invention belongs to the field of organic semiconductor photoelectric materials, and particularly relates to a hyperbranched conjugated polyelectrolyte based on trimeric indole, and a preparation method and application thereof.
Background
Organic semiconductor material having a matrixThe light, cheap and flexible solution can be processed to prepare large-area devices, and the like, thereby obtaining wide attention and having huge application prospect. In recent decades, Organic Light Emitting Diodes (OLEDs) and organic solar cells (OPVs) have gained significant development as two important applications of organic semiconductor photovoltaic materials. In both types of devices, the interfacial layer plays an important role in improving device performance. The interface layer includes a hole transport layer and an electron transport layer, which facilitate ohmic contact between the respective electrodes and the light emitting layer (in an OLED device) or the active layer (in an OPV device), and can selectively transport holes or electrons. Among them, the hole transport material has been attracting attention. In the OLED device, the hole transport layer can improve the transport efficiency of holes in the device, block electrons in the light emitting layer, reduce the energy barrier of the holes in the injection process, increase the hole injection efficiency, realize the maximum recombination of carriers, improve the brightness of the device and prolong the service life of the device. In the OPV device, the hole transport layer can block electrons in the active layer, and simultaneously, the energy barrier during hole collection is reduced, the hole collection efficiency is increased, and the photoelectric conversion efficiency of the device is improved. Currently, the most commonly used hole transport material is poly (3, 4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT: PSS) in water, which has the advantages of appropriate work function, high conductivity, and weak absorption in the visible light region. However, PEDOT: PSS is an acidic material, and can corrode an electrode and a light-emitting layer or an active layer, thereby causing instability of a device. In OPV, some inorganic materials such as MoO3Etc. may also be used in the hole transport layer, but these materials generally have disadvantages of inflexibility, low conductivity, complicated preparation process, etc. Therefore, a new organic hole transport material capable of replacing PEDOT (Poly ethylene glycol ether ketone) PSS is developed, and the service life and the stability of the device are favorably improved.
Tribenzazole is an electron-rich planar C3A symmetric fused ring molecule. Due to the characteristics of high HOMO energy level and high hole mobility, the trimeric indole and the derivatives thereof are favorable for being used as hole transport materials in OLED or OPV devices. At present, hole transport materials based on trimerization indole and derivatives thereof are rarely reported, and the reported molecules are all water-insolubleThe small molecules have poor film-forming property, and are difficult to process and prepare devices by using an orthogonal solvent method, and the prepared devices have low efficiency. Compared with small molecules, the conjugated polyelectrolyte generally has better hole transport performance, and is beneficial to improving the performance of devices. Meanwhile, the conjugated polyelectrolyte has good film forming property, and a device can be prepared by solution processing by an orthogonal solvent method. However, due to the difficulty of synthesis, trimeric indole-based conjugated polyelectrolytes have not been reported. Therefore, the development of the conjugated polyelectrolyte based on the trimeric indole as a hole transport material has important significance for realizing solution processing of OLED and OPV devices by an orthogonal solvent method and improving the efficiency of the devices.
Disclosure of Invention
The invention provides a hyperbranched conjugated polyelectrolyte based on trimerization indole, a preparation method and application thereof, aiming at solving the technical problems that a hole transport material based on the trimerization indole and derivatives thereof has poor film forming property, is difficult to process and prepare a device by an orthogonal solvent method and has low efficiency of the prepared device in the prior art.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a hyperbranched conjugated polyelectrolyte based on trimeric indole, which has a structural formula as follows:
wherein,
represents a continuation of the conjugated backbone of the polymer;
in the formula (I), the structure of R is shown as formulas (II), (III) and (IV):
the structure of D is any one of the following structures:
wherein R is1Is C1To C8Alkyl group of (1).
In the technical scheme, R is-C4H8SO3Na and D have the structure
In the technical scheme, R is-C4H8SO3Na and D have the structure
In the technical scheme, R is-C4H8SO3Na and D have the structure
The invention also provides a preparation method of the trimeric indole-based hyperbranched conjugated polyelectrolyte, which comprises the following steps:
step 1, carrying out electrophilic substitution reaction on a compound of formula (V) in the presence of NaH to form a small molecule compound of formula (VI);
the structure of M is any one of the following structures:
the structure of R is shown in formulas (II), (III) and (IV):
step 2-1, carrying out Suzuki coupling reaction on a compound shown in a formula (VI) and a compound D in the presence of a catalyst to form hyperbranched conjugated polyelectrolyte shown in a formula (I);
or step 2-2, performing Stille coupling reaction on the compound of the formula (VI) and the compound D in the presence of a catalyst to form the hyperbranched conjugated polyelectrolyte of the formula (I);
or step 2-3, carrying out direct arylation coupling reaction on the compound shown in the formula (VI) and the compound D in the presence of a catalyst to form the hyperbranched conjugated polyelectrolyte shown in the formula (I);
in the formula (I), D has any one of the following structures:
wherein R is1Is C1To C8Alkyl group of (1).
In the technical scheme, M is 1, 4-butanesultone, and the compound D is 1, 4-benzene diboronic acid, thiophene-2, 5-diboronic acid dipinacol ester, 2, 5-bis (trimethyltin) thiophene or 1,2,4, 5-tetrafluorobenzene.
The invention also provides application of the hyperbranched conjugated polyelectrolyte based on the trimeric indole, and the hyperbranched conjugated polyelectrolyte based on the trimeric indole is used as a hole transport layer for preparing an organic photoelectric device.
The invention also provides an organic photovoltaic device taking the trimeric indole-based hyperbranched conjugated polyelectrolyte as a hole transport layer.
The invention also provides an organic electroluminescent device using the trimeric indole-based hyperbranched conjugated polyelectrolyte as a hole transport layer.
Compared with the prior art, the invention has the following advantages:
(1) the trimeric indole-based hyperbranched conjugated polyelectrolyte material provided by the invention has neutral pH value and does not corrode corresponding electrodes and organic materials.
(2) The hyperbranched conjugated polyelectrolyte material based on the trimeric indole can be used for preparing a hole transport layer of an organic photoelectric device by solution processing with an orthogonal solvent method.
(3) The hyperbranched conjugated polyelectrolyte material based on the trimeric indole provided by the invention has the advantages of good light transmittance in a visible light region, good thermal stability and the like.
(4) The hyperbranched conjugated polyelectrolyte TAT-H-P based on the trimeric indole prepared by the invention is used as a hole transport layer to prepare an organic photovoltaic device, and the structure of the device is as follows: ITO/TAT-H-P/PTB7 PC71BM/Ca (20nm)/Al (100nm), and the measured short-circuit current Jsc of the device is 13.81mA/cm2The open circuit voltage Voc is 0.75V, the fill factor FF is 66.13%, and the energy conversion efficiency PCE is 6.85%.
(5) The hyperbranched conjugated polyelectrolyte TAT-T-P based on the trimeric indole prepared by the invention is used as a hole transport layer to prepare an organic electroluminescent device, and the structure of the device is as follows: ITO/TAT-T-P/G2P2/TmPyPB (50nm)/LiF (1nm)/Al (100nm), the properties of the resulting EL device were as follows: the start-up voltage is 2.5V, the maximum luminous efficiency is 46.0cd/A, the maximum power efficiency is 52.6lm/W, and the maximum brightness is 48277cd/m2。
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a current density-voltage curve of a solar cell using the hyperbranched conjugated polyelectrolyte TAT-H-P prepared in example 1 as a hole transport layer.
FIG. 2 is a luminance-voltage curve of an organic light emitting diode using the hyperbranched conjugated polyelectrolyte TAT-T-P prepared in example 2 as a hole transport layer.
FIG. 3 is a current efficiency-luminance curve of an organic light emitting diode using the hyperbranched conjugated polyelectrolyte TAT-T-P prepared in example 2 as a hole transport layer.
FIG. 4 is an emission spectrum of an organic light emitting diode using the hyperbranched conjugated polyelectrolyte TAT-T-P prepared in example 2 as a hole transport layer.
FIG. 5 is a thermogravimetric analysis curve of the hyperbranched conjugated polyelectrolyte TAT-H-P prepared in example 1.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The invention provides a hyperbranched conjugated polyelectrolyte based on trimeric indole, which has a structural formula as follows:
in the formula (I), the structure of R is shown as formulas (II), (III) and (IV):
the structure of D is any one of the following structures:
wherein R is1Is C1To C8Alkyl group of (1).
Preferably, R in the hyperbranched conjugated polyelectrolyte based on trimeric indole is-C4H8SO3Na and D have the structure
Preferably, R in the hyperbranched conjugated polyelectrolyte based on trimeric indole is-C4H8SO3Na and D have the structure
Preferably, R in the hyperbranched conjugated polyelectrolyte based on trimeric indole is-C4H8SO3Na and D have the structure
The invention also provides a preparation method of the trimeric indole-based hyperbranched conjugated polyelectrolyte, which comprises the following steps:
step 1, carrying out electrophilic substitution reaction on a compound of formula (V) in the presence of NaH to form a small molecule compound of formula (VI);
m is the following structure:
the structure of R is shown in formulas (II), (III) and (IV):
step 2-1, carrying out Suzuki coupling reaction on the compound shown in the formula (VI) in the presence of a catalyst to form hyperbranched conjugated polyelectrolyte shown in the formula (I);
or step 2-2, performing Stille coupling reaction on the compound of the formula (VI) in the presence of a catalyst to form the hyperbranched conjugated polyelectrolyte of the formula (I);
or step 2-3, carrying out direct arylation coupling reaction on the compound shown in the formula (VI) in the presence of a catalyst to form the hyperbranched conjugated polyelectrolyte shown in the formula (I);
in the formula (I), D has any one of the following structures:
wherein R is1Is C1To C8Alkyl group of (1).
Preferably, M is 1, 4-butanesultone, and the compound D is 1, 4-benzene diboronic acid, thiophene-2, 5-diboronic acid dipinacol ester, 2, 5-bis (trimethyltin) thiophene or 1,2,4, 5-tetrafluorobenzene.
The invention also provides application of the hyperbranched conjugated polyelectrolyte based on the trimeric indole, and the hyperbranched conjugated polyelectrolyte based on the trimeric indole is used as a hole transport layer for preparing an organic photoelectric device.
The invention also provides an organic photovoltaic device taking the trimeric indole-based hyperbranched conjugated polyelectrolyte as a hole transport layer.
The invention also provides an organic electroluminescent device using the trimeric indole-based hyperbranched conjugated polyelectrolyte as a hole transport layer.
The first embodiment is as follows:
a trimerization indole-based hyperbranched conjugated polyelectrolyte with a structure of TAT-H-P is prepared by the following synthetic route:
(1) synthesis of an intermediate of chemical structure a: under the protection of argon, 2-indolone (3g,22.5mmol) and phosphorus oxychloride (10mL) are added into a 100mL two-neck bottle, and the mixture is heated to 100 ℃ for reaction for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, added to ice water and stirred, and added with an aqueous sodium hydroxide solution to neutralize the acidity of the system to a neutral pH. Filtration, dissolution of the residue in acetone, drying over anhydrous sodium sulfate, filtration followed by spin-drying, column chromatography with petroleum ether/ethyl acetate (5:1) as eluent, and recrystallization from acetone gave 0.75g of yellowish crystals in 29.0% yield. 1H NMR (400MHz, DMSO) δ 11.87(s,3H),8.68(d, J ═ 7.5Hz,3H),7.73(d, J ═ 7.8Hz,3H),7.36(dt, J ═ 22.3,7.2Hz,6H).
(2) Synthesis of an intermediate of chemical structure b: a250 mL single-neck flask was charged with trimeric indole (0.75g,2.17mmol) as compound a and 100mL acetone, and stirred at 0 ℃. NBS (1.20g,6.73mmol) is dissolved in 10ml DMF, added dropwise to the acetone solution of the trimeric indole, stirred at 0 ℃ for 0.5h, and heated to 25 ℃ for reaction for 12 h. After the reaction was completed, the mixture was extracted with water/dichloromethane, dried over anhydrous sodium sulfate, filtered, dried by spin-drying, and subjected to column chromatography, eluting with petroleum ether/ethyl acetate (5:1), and recrystallized from acetone to obtain 0.79g of a white powder with a yield of 63.1%.1H NMR(400MHz,DMSO)δ12.14(s,3H),8.59(d,J＝8.2Hz,3H),7.83(s,3H),7.52(d,J＝7.7Hz,3H).
(3) Synthesis of an intermediate of chemical structure c: under the protection of argon, compound b (0.79g,1.37mmol), sodium hydride (131.5mg,5.48mmol) and 100mL of tetrahydrofuran were added to a 250mL two-necked flask, and the mixture was stirred at 0 ℃ for 1 hour. A solution of 1, 4-butanesultone (746mg,5.48mmol) in tetrahydrofuran was added and the mixture was heated to 88 ℃ for 12 h. After the reaction was complete, it was cooled to room temperature, precipitated in acetone, filtered and recrystallized from water/methanol to yield 1.23g of a pale yellow powder in 85.3% yield.1H NMR(400MHz,DMSO)δ8.18(d,J＝8.8Hz,3H),8.13(d,J＝1.7Hz,3H),7.50(dd,J＝8.6,1.6Hz,3H),4.86(m,6H),2.40(m,6H),1.91(m,6H),1.62(m,6H).
(4) Synthesis of TAT-H-P: under the protection of argon, a 50mL two-necked flask is charged with compound c (300mg,0.28mmol), 1, 4-benzenediboronic acid (69.6mg,0.42mmol), tetrakis (triphenylphosphine) palladium (9.9mg,0.0085mmol), sodium carbonate (226.5mg,2.14mmol), 12mL of DMDMF and 3mL of water, and reacted at 90 ℃ for 12 h. And (3) performing a phenylboronic acid end capping reaction for 12 hours, and performing a bromobenzene end capping reaction for 12 hours. After the reaction, the mixture was cooled to room temperature, precipitated with acetone, filtered, and dialyzed against an aqueous phase (molecular weight cut-off of dialysis bag is 3500). 202.1mg of a dark and bright powder was obtained in a yield of 76.2%.
As can be seen from the thermogravimetric analysis curve of FIG. 5, the thermal decomposition temperature of the obtained conjugated polyelectrolyte with the structure of TAT-H-P is 320 ℃, and the thermal stability is good.
Example two:
a trimerization indole-based hyperbranched conjugated polyelectrolyte with a structure of TAT-T-P is prepared by the following synthetic route:
wherein, the synthesis of the intermediates a, b and c is the same as that of the first embodiment.
Synthesis of TAT-T-P: under the protection of argon, a 50mL two-necked flask is charged with the compound c (300mg,0.28mmol), thiophene-2, 5-diboronic acid dipinacol ester (72.1mg,0.42mmol), tetrakis (triphenylphosphine) palladium (9.9mg,0.0085mmol), sodium carbonate (226.5mg,2.14mmol), 12mL of DMMF and 3mL of water, and reacted at 90 ℃ for 12 h. The thiophene-2-boronic acid pinacol ester is subjected to end capping reaction for 12 hours, and the 2-bromothiophene is subjected to end capping reaction for 12 hours. After the reaction, the mixture was cooled to room temperature, precipitated with acetone, filtered, and dialyzed against an aqueous phase (molecular weight cut-off of dialysis bag is 3500). 249.1mg of a dark and bright powder was obtained, yield 93.0%.
Example three:
a trimerization indole-based hyperbranched conjugated polyelectrolyte with a structure of TAT-T-P is prepared by the following synthetic route:
wherein, the synthesis of the intermediates a, b and c is the same as that of the first embodiment.
Synthesis of TAT-T-P: under the protection of argon, a 50mL two-necked bottle is added with the compound c (300mg,0.28mmol), 2, 5-bis (trimethyltin) thiophene (72.1mg,0.42mmol), tetrakis (triphenylphosphine) palladium (9.9mg,0.0085mmol) and 15mLDMF, and reacted for 12h at 90 ℃. 2-tributylstannyl thiophene end capping reaction is carried out for 12h, and 2-bromothiophene end capping reaction is carried out for 12 h. After the reaction, the mixture was cooled to room temperature, precipitated with acetone, filtered, and dialyzed against an aqueous phase (molecular weight cut-off of dialysis bag is 3500). 147.2mg of a dark and bright powder were obtained, yield 55.0%.
Example four:
a hyperbranched conjugated polyelectrolyte based on trimeric indole with a structure of TAT-4FH-P is synthesized by the following steps:
wherein, the synthesis of the intermediates a, b and c is the same as that of the first embodiment.
Synthesis of TAT-4 FH-P: under the protection of argon, a 50mL two-necked bottle is added with the compound c (300mg,0.28mmol), 1,2,4, 5-tetrafluorobenzene (63.03mg,0.42mmol), palladium acetate (6.40mg,0.028mmol), sodium carbonate (90.59mg,0.85mmol), 6mLDMF and 6mLDMSO, and reacted for 24h at 100 ℃. And (3) carrying out end capping reaction on pentafluorobenzene for 12h, and carrying out end capping reaction on bromobenzene for 12 h. After the reaction was complete, the reaction mixture was cooled to room temperature, acetone was precipitated, filtered and dialyzed against the aqueous phase (cut-off molecular weight of dialysis bag 3500) to give 190.7mg of a light black powder in a yield of 64.5%.
The compound D used in the above examples was replaced with the corresponding compound having the following structure, except that M used in the above examples was 1, 4-butanesultone and 1, 3-propanesultone or 3-methyl-1, 3-propanesultone:
preparing the hyperbranched conjugated polyelectrolyte based on the trimeric indole with the corresponding structure.
Preparation and performance test of the organic photovoltaic device:
for the given example, an organic photovoltaic device was prepared using TAT-H-P as the hole transport layer, the structure of the device being: ITO/TAT-H-P/PTB7 PC71BM/Ca (20nm)/Al (100 nm). The assembly process of the device is as follows
Sequentially and respectively ultrasonically cleaning Indium Tin Oxide (ITO) glass for 10 minutes by using a cleaning agent, deionized water, acetone and isopropanolAnd then dried at 120 ℃ for 1 hour. After UV/ozone treatment for 25min, a layer of TAT-H-P of example I was spin-coated as a hole transport layer and dried at 120 ℃ for 30 min. Polymer donor material PTB7 and fullerene acceptor PC71BM (weight ratio 1:1.5) was dissolved in CB/DIO (volume ratio 0.97:0.03) to prepare a 10mg PTB7 solution, and was spin-coated on the hole transport layer of TAT-H-P to form an active layer of the device. Then transferred to a vacuum chamber at 2X 10-4And under the Pa vacuum degree, evaporating Ca with the thickness of 20nm on the active layer, and then evaporating Al with the thickness of 100nm as a cathode of the photovoltaic device. The effective area of the device is 8mm2。
An XES-40S2-CE solar simulator with an AM 1.5G filter was used as a simulated solar light source at 100mWcm–2Carrying out photovoltaic performance test on the device under the light intensity; the current density-voltage curve (J-V) of the device was tested using Keithley 2400.
The I-V curve of a solar cell prepared by taking a hyperbranched conjugated polyelectrolyte based on TAT-H-P as a hole transport layer is shown in figure 1, and the measured short-circuit current Jsc of the device is 13.81mA/cm2The open circuit voltage Voc is 0.75V, the fill factor FF is 66.13%, and the energy conversion efficiency PCE is 6.85%.
Preparation and performance test of the organic electroluminescent device:
for the given example, an organic electroluminescent device was prepared using TAT-T-P as the hole transport layer, the structure of the device being: ITO/TAT-T-P/G2P2(40nm)/SPPO13(50nm)/LiF (1nm)/Al (150 nm). The assembly process of the device is as follows:
indium Tin Oxide (ITO) glass was ultrasonically cleaned with a cleaner, deionized water, acetone, and isopropyl alcohol, respectively, for 10 minutes, and then dried at 120 ℃ for 1 hour. After UV/ozone treatment for 25min, a layer of TAT-T-P of example II was spin-coated as a hole transport layer and dried at 120 ℃ for 30 min. G2P2 was dissolved in chlorobenzene to prepare a 10mg/mL solution, which was spin-coated on TAT-T-P to serve as a light-emitting layer. Under vacuum condition 4X 10-4Pa, 50nm thick SPPO13 was evaporated on the light-emitting layer as an electron transport layer, followed by sequentially evaporating LiF with a thickness of 1nm and Al electrode with a thickness of 150 nm.
Hyperbranched co-polymer based on TAT-T-PThe luminance-voltage curve, the current efficiency-luminance curve and the emission spectrum of the organic light emitting diode prepared by using the hole transport layer as the polyelectrolyte are shown in fig. 2, fig. 3 and fig. 4 respectively. As can be seen from the figure: the properties of the resulting EL device were as follows: the start-up voltage is 2.5V, the maximum luminous efficiency is 46.0cd/A, the maximum power efficiency is 52.6lm/W, and the maximum brightness is 48277cd/m2。
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. A hyperbranched conjugated polyelectrolyte based on trimeric indole is characterized in that the structural formula is as follows:
in the formula (I), the structure of R is shown as formulas (II), (III) and (IV):
the structure of D is any one of the following structures:
wherein R is1Is C1To C8Alkyl group of (1).
2. According to claim 1The hyperbranched conjugated polyelectrolyte based on the trimeric indole is characterized in that R is-C4H8SO3Na and D have the structure
3. The trimeric indole-based hyperbranched conjugated polyelectrolyte according to claim 1, wherein R is-C4H8SO3Na and D have the structure
4. The trimeric indole-based hyperbranched conjugated polyelectrolyte according to claim 1, wherein R is-C4H8SO3Na and D have the structure
5. The preparation method of the trimeric indole-based hyperbranched conjugated polyelectrolyte according to claim 1, which is characterized by comprising the following steps:
step 1, carrying out electrophilic substitution reaction on a compound of formula (V) in the presence of NaH to form a small molecule compound of formula (VI);
the structure of M is any one of the following structures:
the structure of R is shown in formulas (II), (III) and (IV):
step 2-1, carrying out Suzuki coupling reaction on a compound shown in a formula (VI) and a compound D in the presence of a catalyst to form hyperbranched conjugated polyelectrolyte shown in a formula (I);
or step 2-2, performing Stille coupling reaction on the compound of the formula (VI) and the compound D in the presence of a catalyst to form the hyperbranched conjugated polyelectrolyte of the formula (I);
or step 2-3, carrying out direct arylation coupling reaction on the compound shown in the formula (VI) and the compound D in the presence of a catalyst to form the hyperbranched conjugated polyelectrolyte shown in the formula (I);
in the formula (I), D has any one of the following structures:
wherein R is1Is C1To C8Alkyl group of (1).
6. The method for preparing the trimeric indole-based hyperbranched conjugated polyelectrolyte according to claim 5, wherein M is 1, 4-butanesultone, and the D compound is 1, 4-benzenediboronic acid, thiophene-2, 5-diboronic acid dipinacol ester, 2, 5-bis (trimethyltin) thiophene or 1,2,4, 5-tetrafluorobenzene.
7. Use of the trimeric indole-based hyperbranched conjugated polyelectrolyte according to claim 1 as a hole transport layer for the production of organic opto-electronic devices.
8. An organic photovoltaic device comprising the trimeric indole-based hyperbranched conjugated polyelectrolyte of claim 1 as a hole transport layer.
9. An organic electroluminescent device comprising the trimeric indole-based hyperbranched conjugated polyelectrolyte of claim 1 as a hole transport layer.
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