CN114656367B - Organic micromolecular functional material with anthraquinone as core, and synthesis method and application thereof - Google Patents
Organic micromolecular functional material with anthraquinone as core, and synthesis method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 41
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 14
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 238000009830 intercalation Methods 0.000 claims abstract description 26
- 230000002687 intercalation Effects 0.000 claims abstract description 26
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000005525 hole transport Effects 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 43
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- 238000000034 method Methods 0.000 claims description 11
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
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- 239000002184 metal Substances 0.000 claims description 6
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- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 5
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- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 4
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- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 2
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
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- 229910000160 potassium phosphate Inorganic materials 0.000 description 4
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 description 2
- 239000012391 XPhos Pd G2 Substances 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- RSLSVURFMXHEEU-UHFFFAOYSA-M chloropalladium(1+);dicyclohexyl-[3-[2,4,6-tri(propan-2-yl)phenyl]phenyl]phosphane;2-phenylaniline Chemical compound [Pd+]Cl.NC1=CC=CC=C1C1=CC=CC=[C-]1.CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC(P(C2CCCCC2)C2CCCCC2)=C1 RSLSVURFMXHEEU-UHFFFAOYSA-M 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
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- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
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- ADSOSINJPNKUJK-UHFFFAOYSA-N 2-butylpyridine Chemical group CCCCC1=CC=CC=N1 ADSOSINJPNKUJK-UHFFFAOYSA-N 0.000 description 1
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VUWBMXNMKRWSEI-UHFFFAOYSA-N C1(CCCCC1)P(C1=C(C=CC=C1)C1=C(C=C(C=C1C(C)C)C(C)C)C(C)C)C1CCCCC1.[Cl] Chemical group C1(CCCCC1)P(C1=C(C=CC=C1)C1=C(C=C(C=C1C(C)C)C(C)C)C(C)C)C1CCCCC1.[Cl] VUWBMXNMKRWSEI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UJQAHAANAPEYLR-UHFFFAOYSA-N [2-chloro-6-[2,4,6-tri(propan-2-yl)phenyl]phenyl]-dicyclohexylphosphane Chemical group CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC(Cl)=C1P(C1CCCCC1)C1CCCCC1 UJQAHAANAPEYLR-UHFFFAOYSA-N 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention belongs to the field of organic semiconductor functional materials, and relates to an organic micromolecular functional material taking anthraquinone as a core, a synthesis method thereof and a lead-free Cs 2 AgBiBr 6 Use in a double perovskite solar cell. The organic micromolecular functional material with symmetrical structure is constructed by taking anthraquinone as a core structure and 4, 4-dimethoxy triphenylamine as a peripheral group and is used as lead-free Cs 2 AgBiBr 6 Interfacial functional intercalation of double perovskite/Spiro-OMeTAD hole transport layer applied to lead-free Cs 2 AgBiBr 6 In a double perovskite solar cell: on one hand, the introduction of the functional material with anthraquinone as a core structure is beneficial to reasonably optimizing the energy level arrangement in the battery, improving the charge transmission efficiency, avoiding excessive energy loss and further improving the photoelectric conversion efficiency of the battery; on the other hand, the functional material has stronger hydrophobicity, and effectively prevents harmful doping agent and water vapor in the hole transport layer from facing Cs 2 AgBiBr 6 The permeation of the double perovskite layer inhibits the degradation of perovskite and improves the stability of the battery.
Description
Technical Field
The invention belongs to the field of organic semiconductor functional materials, and relates to an organic micromolecular functional material taking anthraquinone as a core and a synthesis method thereofAnd in lead-free Cs 2 AgBiBr 6 Use in a double perovskite solar cell.
Background
Perovskite solar cells (Perovskite solar cells, PSCs) are considered to be one of the most promising future photovoltaic devices. Since the first report in 2009, the Photoelectric Conversion Efficiency (PCE) of PSCs has rapidly increased to 25.7% over a period of decades (A.Kojima, K.Teshima, Y.Shirai, T.Miyasaka, J.Am.Chem.Soc.2009,131,6050; H.Min, D.Y.Lee, J.Kim, G.Kim, K.S.Lee, J.Kim, M.J.Paik, Y.K.Kim, K.S.Kim, M.G.Kim, T.J.Shin, S.Il seak, nature 2021,598,444). However, as a core component of the conventional perovskite solar cell, the organic-inorganic hybrid perovskite material contains Pb element with stronger toxicity, and once the cell leaks during use or recovery, the environment is polluted, which severely limits the commercial application of the lead-based perovskite solar cell. To cope with this problem, a number of groups have succeeded in producing a non-lead-based perovskite solar cell using other elements such as Sn, ge, bi, sb instead of Pb element, and have made good progress (W.Ke, M.G.Kanatzidis, nat.Commun.2019,10,965;Q.Fan,G.V.Biesold-McGee, J.Ma, Q.Xu, S.Pan, J.Peng, Z.Lin, angew.Chem.Int.Ed.2020,59,1030;Z.Xiao,Z.Song,Y.Yan,Adv.Mater.2019,31,1803792). Wherein, cs based on Bi and Ag elements 2 AgBiBr 6 Double perovskite solar cells were first reported by Greul et al in 2017 and initially obtained 2.5% photoelectric conversion efficiency, such as Cs 2 AgBiBr 6 Double perovskite batteries exhibit higher stability in air and are considered to be one of the powerful candidates for non-lead based perovskite batteries (E.Greul, M.L.Petrus, A.Binek, P.Docampo, T.Bein, J.Mater.Chem.A 2017,5,19972;X.Q.Yang,Y.H.Chen,P.Y.Liu,H.M.Xiang,W.Wang,R.Ran,W.Zhou,Z.P.Shao,Adv.Funct.Mater.2020,30,2001557;T.Luo,Y.L.Zhang,X.M.Chang,J.J.Fang,T.Q.Niu,J.Lu,Y.Y.Fan,Z.C.Ding,K.Zhao,S.Z.Liu,J.Energy Chem.2021,53,372.). In recent years, various subject groups have been devoted to improving Cs by means of precursor liquid component regulation, solvent and additive engineering and the like 2 AgBiBr 6 Double perovskite film quality, and then promote Cs 2 AgBiBr 6 Photoelectric properties of double perovskite solar cells (E.Greul, M.L.Petrus, A.Binek, P.Docampo, T.Bein, J.Mater.Chem.A 2017,5,19972;C.Wu,Q.Zhang,Y.Liu,W.Luo,X.Guo,Z.Huang,H.Ting,W.Sun,X.Zhong,S.Wei,S.Wang,Z.Chen,L.Xiao,Adv.Sci.2018,5,1700759;F.Igbari,R.Wang,Z.K.Wang,X.J.Ma,Q.Wang,K.L.Wang,Y.Zhang,L.S.Liao,Y.Yang,Nano Lett.2019,19,2066.). At present, cs 2 AgBiBr 6 The highest photoelectric conversion efficiency of the double perovskite solar cell was only 3.11%, which is still very different from the theoretical limiting efficiency of 8% (Wang, b.; li, n.; yang, l.; dall' Agnese, c.; jena, a.k.; sasaki, s.i.; miyasaka, t.; tamiaki, h.; wang, x.f.j.am. Chem. Soc.2021,143, 2207.).
Except for preparing high-quality Cs 2 AgBiBr 6 Outside the double perovskite film, cs is reasonably regulated and controlled 2 AgBiBr 6 The arrangement of the energy levels inside a double perovskite solar cell is another critical means to improve the cell efficiency. At Cs 2 AgBiBr 6 In a double perovskite solar cell, 2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group]9,9' -spirobifluorene (Spiro-OMeTAD) is a common classical hole transport material, however, its molecular energy level is equal to Cs 2 AgBiBr 6 The conduction band and the valence band of the device are not matched, so that the hole extraction and transmission performance is lower, and larger internal energy loss is generated, so that the device efficiency is lower; meanwhile, additives such as Tertiary Butyl Pyridine (TBP) with high volatility, lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) with high hydrophilicity and the like are required to be introduced when the Spiro-OMeTAD is used, so that the stability of a battery device is adversely affected. Thus, there is a need for lead-free Cs 2 AgBiBr 6 The interface between the double perovskite/Spiro-OMeTAD hole transport layers is subjected to process optimization, and the design and development can reasonably optimize the internal energy level arrangement of the device, effectively isolate functional intercalation of perovskite and water and oxygen contact, improve the photoelectric conversion efficiency of the device and greatly enhance the stability of the device.
Disclosure of Invention
Aiming at the defects of classical hole transport materials, the invention aims to develop a class of organic with deep energy level, strong hydrophobicity, high hole mobility and conductivitySmall molecular functional material and application thereof and lead-free Cs 2 AgBiBr 6 In a double perovskite solar cell. The organic small molecular functional material takes anthraquinone as a core structure and 4, 4-dimethoxy triphenylamine as a peripheral group, so that the organic small molecular functional material with a symmetrical structure is constructed. The material has the advantages of simple synthesis, low cost, good chemical stability and the like, and is used as lead-free Cs 2 AgBiBr 6 Interfacial functional intercalation of double perovskite/Spiro-OMeTAD hole transport layer applied to lead-free Cs 2 AgBiBr 6 In a double perovskite solar cell: on one hand, the introduction of the functional material with anthraquinone as a core structure is beneficial to reasonably optimizing the energy level arrangement in the battery, improving the charge transmission efficiency, avoiding excessive energy loss and further improving the photoelectric conversion efficiency of the battery; on the other hand, the functional material has stronger hydrophobicity, and effectively prevents harmful doping agent and water vapor in the hole transport layer from facing Cs 2 AgBiBr 6 The permeation of the double perovskite layer inhibits the degradation of perovskite and improves the stability of the battery.
The invention adopts the technical scheme that:
an organic small molecule functional material with anthraquinone as a core structure, wherein anthraquinone as a core structure and 4, 4-dimethoxy triphenylamine as a peripheral group are used for constructing an organic small molecule functional material with a symmetrical structure, the chemical name of the functional material is 2, 6-bis (4-methoxy phenyl) amino) phenyl) anthracene-9, 10-dione, which is called AD-MP for short, and the chemical structure is as follows:
the synthesis method of the organic micromolecular functional material AD-MP comprises the following steps: the compound 1 and 4-borate-4 ',4' -dimethoxy triphenylamine undergo carbon-carbon coupling reaction to obtain a final product AD-MP, and the steps are as follows:
adding a compound 1, 4-borate-4 ',4' -dimethoxy triphenylamine, a potassium phosphate aqueous solution, chlorine (2-dicyclohexylphosphino-2 ',4',6 '-triisopropyl-1, 1' -biphenyl) [2- (2 '-amino-1, 1' -biphenyl) ] palladium (II) (Xphos Pd G2) and tetrahydrofuran into a reaction container, stirring uniformly under the protection of nitrogen to obtain a reaction solution, heating to 40-60 ℃ for reaction for 16-24 hours, cooling the reaction solution to room temperature after the reaction is finished, and extracting and separating the reaction solution by using a dichloromethane solution for several times. The organic layer is collected, the solvent is removed under reduced pressure, the obtained solid is separated and purified, and vacuum drying is carried out, thus obtaining the brown solid organic micromolecular functional material AD-MP, and the specific synthesis flow is as follows:
the compound 1: 4-borate-4 ',4' -dimethoxytriphenylamine: chloro (2-dicyclohexylphosphino-2 ',4',6 '-triisopropyl-1, 1' -biphenyl) [2- (2 '-amino-1, 1' -biphenyl) ] palladium (II): the molar ratio of the potassium phosphate is 1:2.2:0.03:0.7-1; in the reaction solution, the concentration of the compound 1 is 0.34-0.5mol/L;
leadless Cs 2 AgBiBr 6 The double perovskite solar cell device comprises a transparent conductive substrate, an electron transport layer and lead-free Cs 2 AgBiBr 6 A double perovskite active layer, an AD-MP functional intercalation layer, a Spiro-OMeTAD hole transport layer and a metal electrode. The method comprises the following specific steps:
(1) Cutting a transparent conductive substrate into a fixed size, adopting laser to etch a specific surface area, sequentially adopting deionized water, acetone and absolute ethyl alcohol to ultrasonically clean the etched conductive substrate for 30min, and drying for later use;
(2) Preparing an electron transport layer on the transparent conductive substrate obtained in the step (1) by using a spray pyrolysis method and/or a spin coating method;
(3) The substrate with the electron transport layer was subjected to ozone treatment for 20min and then transferred to a glove box, and lead-free Cs was removed by spin coating 2 AgBiBr 6 Spin-coating the double perovskite precursor solution on the top of the electron transport layer to form lead-free Cs 2 AgBiBr 6 A double perovskite active layer;
(4) In a glove box, spin-coating a chlorobenzene solution of an organic micromolecular functional material AD-MP prepared in advance on lead-free Cs by using a spin-coating method 2 AgBiBr 6 Forming AD-MP functional intercalation on the top of the double perovskite active layer;
(5) In a glove box, spin-coating a chlorobenzene solution of the pre-prepared Spiro-OMeTDA hole transport layer on the top of the AD-MP functional intercalation by using a spin-coating method to form the Spiro-OMeTDA hole transport layer;
(6) A metal electrode was deposited on top of the spira-ome tda hole transport layer using vacuum evaporation.
In the step (1), the transparent conductive substrate is any one of FTO conductive glass, ITO conductive glass or transparent flexible conductive substrate;
in the step (2), the electron transport layer is one of metal oxides such as titanium dioxide and tin dioxide;
in the step (3), the lead-free Cs 2 AgBiBr 6 The preparation method of the double perovskite precursor solution comprises the following steps: dissolving cesium bromide, silver bromide and bismuth tribromide in N, N-dimethylformamide solution, heating and stirring for 2h at 100 ℃, cooling the solution to room temperature, and sealing and preserving;
in the step (4), the concentration of the AD-MP in the chlorobenzene solution of the organic micromolecular functional material AD-MP prepared in advance is 10-30mg/mL;
in the step (5), the pre-prepared Spiro-OMeTDA hole transport layer chlorobenzene solution comprises Spiro-OMeTAD, additives LiTFSI, TBP and FK209;
in the step (6), the metal electrode is one of gold, silver or copper.
The invention has the following advantages:
(1) The organic micromolecular functional material AD-MP provided by the invention has the advantages of simple reaction steps and low cost, and can be synthesized by one-step reaction.
(2) The organic micromolecular functional material AD-MP provided by the invention is used as leadless Cs 2 AgBiBr 6 The interface functional intercalation of the double perovskite/Spiro-OMeTDA hole transport layer is applied to the perovskite solar cell, so that the energy level arrangement inside the device is successfully optimized, the charge transport efficiency is increased, the internal energy loss is reduced, and the efficiency of the perovskite solar cell is further improvedThe rate.
(2) The organic micromolecular functional material AD-MP provided by the invention has stronger hydrophobicity, effectively prevents the permeation of harmful doping agents and water vapor to perovskite, inhibits the degradation rate of the perovskite, and improves the stability of the battery.
Drawings
FIG. 1 shows the chemical structural formulas of the organic small molecule functional material AD-MP synthesized by the examples 1 and 2.
FIG. 2 shows the AD-MP functional intercalation-based Cs prepared in examples 1 and 2 of the present invention 2 AgBiBr 6 Energy level layout of a double perovskite solar cell.
FIG. 3 shows the AD-MP functional intercalation-based Cs prepared in comparative examples and examples 1 and 2 of the present invention 2 AgBiBr 6 J-V graph of double perovskite solar cell.
FIG. 4 shows the AD-MP functional intercalation-based Cs prepared in comparative examples and examples 1 and 2 of the present invention 2 AgBiBr 6 IPCE profile of a double perovskite solar cell.
FIG. 5 shows the AD-MP functional intercalation-based Cs prepared in comparative examples and examples 1 and 2 of the present invention 2 AgBiBr 6 Stability test chart for double perovskite solar cell.
Detailed Description
The invention will be further described with reference to specific examples for a better understanding of the invention by those skilled in the art, but the scope of the invention is not limited to the following examples, which are set forth in the claims.
Example 1:
synthesis of organic micromolecular functional material AD-MP with anthraquinone as core and lead-free Cs thereof 2 AgBiBr 6 Application in double perovskite solar cells:
into a dry reaction vessel was charged compound 1 (1.5 g,4.12 mmol), 4-boronic acidEster-4 ',4' -Dimethoxytriphenylamine (3.9 g,9.06 mmol), chloro (2-dicyclohexylphosphino-2 ',4',6 '-triisopropyl-1, 1' -biphenyl) [2- (2 '-amino-1, 1' -biphenyl)]Palladium (II) (0.1 g,0.12 mmol), aqueous potassium phosphate (0.5M, 8 mL) and tetrahydrofuran (4 mL) were stirred uniformly under nitrogen protection, and heated to 40℃for 16h, after the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was separated three times by extraction with methylene chloride solution (150 mL), the organic layer was collected, the solvent was removed under reduced pressure, the collected was separated and extracted with a silica gel column chromatography, petroleum ether/methylene chloride (1.5:1 vol/vol) was used as an eluent, and vacuum-dried to obtain a brown solid organic small molecule functional material AD-MP (0.378 g, yield: 62.3%). 1 H NMR(400MHz,CDCl 3 )8.52(d,J＝2Hz,2H),8.35(d,J＝8Hz,2H),8.19(d,J＝8.4Hz 2H),7.60(d,J＝8.4Hz,4H),7.16-7.13(m,J＝9.2Hz,8H)7.03(d,J＝8.8Hz 4H)6.91-6.89(m,J＝8.8Hz8H)3.84(s,12H)。
The synthesized organic micromolecular functional material AD-MP is used as functional intercalation to be applied to Cs 2 AgBiBr 6 The preparation method and the process of the double perovskite solar cell are as follows:
the perovskite solar cell has the structure of FTO/c-TiO 2 /m-TiO 2 /Cs 2 AgBiBr 6 AD-MP/Spiro-OMeTAD/Au, the preparation process is as follows:
(1) Cutting a transparent conductive substrate FTO into a size of 1.5cm x 1.5cm, adopting laser etching to treat a specific surface area, sequentially adopting deionized water, acetone and absolute ethyl alcohol to ultrasonically clean the etched conductive substrate for 30min, and drying the FTO substrate for later use;
(2) And (3) uniformly spraying a mixed solution of 0.2M titanium tetraisopropoxide and 2M acetylacetone and isopropanol on the FTO substrate obtained in the step (1) by using a spray pyrolysis method. Annealing at 500 deg.c for 2 hr, cooling to room temperature to form FTO/c-TiO 2 A substrate; 390mg/mL nano TiO 2 Spin-coating ethanol solution of (C) TiO on c-TiO 2 The top part is annealed at a rotation speed of 5000rpm/s for 30s at 100 ℃ for 10min and 500 ℃ for 60min, and cooled to room temperature to obtain FTO/c-TiO 2 /m-TiO 2 The substrate is moved to a glove box filled with nitrogen for standby after being treated by ozone for 20min;
(3) Cesium bromide, silver bromide and bismuth bromide in the stoichiometric ratio of 2:1:1 are dissolved in 1mL of dimethyl sulfoxide solvent in a glove box, heated and stirred at 100 ℃ for 2h, and then naturally cooled to room temperature. Spin-coating cooling liquid on the top of electron transport layer at 1000rpm/s and 4000rpm/s for 10s and 40s respectively, annealing at 250deg.C for 10min, and naturally cooling to room temperature to obtain FTO/c-TiO 2 /m-TiO 2 /Cs 2 AgBiBr 6 A substrate.
(4) In a glove box, 15mg of organic small molecule functional material AD-MP was dissolved in 1mL of chlorobenzene solution by spin coating, and spin-coated to lead-free Cs 2 AgBiBr 6 The top of the double perovskite film has the rotating speed of 4000rpm/s and the rotating time of 30s, and the FTO/c-TiO is obtained 2 /m-TiO 2 /Cs 2 AgBiBr 6 AD-MP substrate.
(5) In a glove box, 80mg of Spiro-OMeTAD, 17.5. Mu.L of LiTFSI in acetonitrile (520 mg/mL), 125. Mu.L of TBP in chlorobenzene (270 mg/mL) and 9. Mu.L of LFK209 in acetonitrile (300 mg/mL) were dissolved in 845. Mu.L of chlorobenzene, and then spin-coated on top of AD-MP film at 4000rpm/s for 30s to obtain FTO/c-TiO 2 /m-TiO 2 /Cs 2 AgBiBr 6 AD-MP/Spiro-OMeTAD substrate.
(6) Deposition of Au onto FTO/c-TiO by vacuum evaporation 2 /m-TiO 2 /Cs 2 AgBiBr 6 A coverage area of 20mm for Au on top of the/AD-MP/Spiro-OMeTAD substrate 2 The thickness was 100nm.
Example 2
Synthesis of organic micromolecular functional material AD-MP with anthraquinone as core and lead-free Cs thereof 2 AgBiBr 6 Application in double perovskite solar cells:
in a dry reaction vessel were charged compound 1 (1.5 g,4.12 mmol), 4-borate-4 ',4' -dimethoxytriphenylamine (3)9g,9.06 mmol), chloro (2-dicyclohexylphosphino-2 ',4',6 '-triisopropyl-1, 1' -biphenyl) [2- (2 '-amino-1, 1' -biphenyl)]Palladium (II) (0.1 g,0.12 mmol), aqueous potassium phosphate (0.5M, 6 mL) and tetrahydrofuran (3 mL) were stirred uniformly under nitrogen protection, and heated to 50℃for 20h, after the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was separated three times by extraction with methylene chloride solution (140 mL), the organic layer was collected, the solvent was removed under reduced pressure, the collected was separated and extracted with a silica gel column chromatography, petroleum ether/methylene chloride (1.5:1 vol/vol) was used as an eluent, and vacuum-dried to obtain a brown solid organic small molecule functional material AD-MP (0.396 g, yield: 65.3%). 1 H NMR(400MHz,CDCl 3 )8.52(d,J＝2Hz,2H),8.35(d,J＝8Hz,2H),8.19(d,J＝8.4Hz 2H),7.60(d,J＝8.4Hz,4H),7.16-7.13(m,J＝9.2Hz,8H)7.03(d,J＝8.8Hz 4H)6.91-6.89(m,J＝8.8Hz8H)3.84(s,12H).
The synthesized organic micromolecular functional material AD-MP is used as functional intercalation to be applied to Cs 2 AgBiBr 6 The preparation method and the process of the double perovskite solar cell are as follows:
the perovskite solar cell has a device structure of FTO/c-TiO 2 /m-TiO 2 /Cs 2 AgBiBr 6 AD-MP/Spiro-OMeTAD/Au, the preparation process is as follows:
(1) Cutting a transparent conductive substrate FTO into a size of 1.5cm x 1.5cm, adopting laser etching to treat a specific surface area, sequentially adopting deionized water, acetone and absolute ethyl alcohol to ultrasonically clean the etched conductive substrate for 30min, and drying the FTO substrate for later use;
(2) And (3) uniformly spraying a mixed solution of 0.2M titanium tetraisopropoxide and 2M acetylacetone and isopropanol on the FTO substrate obtained in the step (1) by using a spray pyrolysis method. Annealing at 500 deg.c for 2 hr, cooling to room temperature to form FTO/c-TiO 2 A substrate; 390mg/mL nano TiO 2 Spin-coating ethanol solution of (C) TiO on c-TiO 2 The top part is annealed at a rotation speed of 5000rpm/s for 30s at 100 ℃ for 10min and 500 ℃ for 60min, and cooled to room temperature to obtain FTO/c-TiO 2 /m-TiO 2 The substrate is moved to a glove box filled with nitrogen for standby after being treated by ozone for 20min;
(3) At the position ofCesium bromide, silver bromide and bismuth bromide in the stoichiometric ratio of 2:1:1 are dissolved in 1mL dimethyl sulfoxide solvent in a glove box, heated and stirred at 100 ℃ for 2h, and then naturally cooled to room temperature. Spin-coating cooling liquid on the top of electron transport layer at 1000rpm/s and 4000rpm/s for 10s and 40s respectively, annealing at 250deg.C for 10min, and naturally cooling to room temperature to obtain FTO/c-TiO 2 /m-TiO 2 /Cs 2 AgBiBr 6 A substrate.
(4) In a glove box, 20mg of organic small molecule functional material AD-MP was dissolved in 1mL of chlorobenzene solution by spin coating, and spin-coated to lead-free Cs 2 AgBiBr 6 The top of the double perovskite film has the rotating speed of 4000rpm/s and the rotating time of 30s, and the FTO/c-TiO is obtained 2 /m-TiO 2 /Cs 2 AgBiBr 6 AD-MP substrate.
(5) In a glove box, 80mg of Spiro-OMeTAD, 17.5. Mu.L of LiTFSI in acetonitrile (520 mg/mL), 125. Mu.L of TBP in chlorobenzene (270 mg/mL) and 9. Mu.L of LFK209 in acetonitrile (300 mg/mL) were dissolved in 845. Mu.L of chlorobenzene, and then spin-coated on top of AD-MP film at 4000rpm/s for 30s to obtain FTO/c-TiO 2 /m-TiO 2 /Cs 2 AgBiBr 6 AD-MP/Spiro-OMeTAD substrate.
(6) Deposition of Au onto FTO/c-TiO by vacuum evaporation 2 /m-TiO 2 /Cs 2 AgBiBr 6 A coverage area of 20mm for Au on top of the/AD-MP/Spiro-OMeTAD substrate 2 The thickness was 100nm.
Comparative example:
traditional Cs 2 AgBiBr 6 Preparation method and process of double perovskite solar cell (without AD-MP functional intercalation):
the perovskite solar cell has a device structure of FTO/c-TiO 2 /m-TiO 2 /Cs 2 AgBiBr 6 The preparation process of the composition is as follows:
(1) Cutting a transparent conductive substrate FTO into a size of 1.5cm x 1.5cm, adopting laser etching to treat a specific surface area, sequentially adopting deionized water, acetone and absolute ethyl alcohol to ultrasonically clean the etched conductive substrate for 30min, and drying the FTO substrate for later use;
(2) And (3) uniformly spraying a mixed solution of 0.2M titanium tetraisopropoxide and 2M acetylacetone and isopropanol on the FTO substrate obtained in the step (1) by using a spray pyrolysis method. Annealing at 500 deg.c for 2 hr, cooling to room temperature to form FTO/c-TiO 2 A substrate; 390mg/mL nano TiO 2 Spin-coating ethanol solution of (C) TiO on c-TiO 2 The top part is annealed at a rotation speed of 5000rpm/s for 30s at 100 ℃ for 10min and 500 ℃ for 60min, and cooled to room temperature to obtain FTO/c-TiO 2 /m-TiO 2 The substrate is moved to a glove box filled with nitrogen for standby after being treated by ozone for 20min;
(3) Cesium bromide, silver bromide and bismuth bromide in the stoichiometric ratio of 2:1:1 are dissolved in 1mL of dimethyl sulfoxide solvent in a glove box, heated and stirred at 100 ℃ for 2h, and then naturally cooled to room temperature. Spin-coating cooling liquid on the top of electron transport layer at 1000rpm/s and 4000rpm/s for 10s and 40s respectively, annealing at 250deg.C for 10min, and naturally cooling to room temperature to obtain FTO/c-TiO 2 /m-TiO 2 /Cs 2 AgBiBr 6 A substrate.
(5) In a glove box, 80mg of Spiro-OMeTAD, 17.5. Mu.L of LiTFSI in acetonitrile (520 mg/mL), 125. Mu.L of TBP in chlorobenzene (270 mg/mL) and 9. Mu.L of LFK209 in acetonitrile (300 mg/mL) were dissolved in 845. Mu.L of chlorobenzene, which was then spin-coated onto Cs 2 AgBiBr 6 The top of the film, the rotating speed is 4000rpm/s, and the rotating time is 30s to obtain FTO/c-TiO 2 /m-TiO 2 /Cs 2 AgBiBr 6 A Spiro-OMeTAD substrate.
(6) Deposition of Au onto FTO/c-TiO by vacuum evaporation 2 /m-TiO 2 /Cs 2 AgBiBr 6 A coverage area of 20mm for Au on top of the/AD-MP/Spiro-OMeTAD substrate 2 The thickness was 100nm.
FIG. 1 shows the chemical structural formulas of the organic small molecule functional material AD-MP synthesized by the examples 1 and 2.
FIG. 2 shows the AD-MP functional intercalation-based Cs prepared in examples 1 and 2 of the present invention 2 AgBiBr 6 Double calcium titaniumEnergy level layout of the mine solar cell. From the figure, the introduction of the organic micromolecular functional material AD-MP leads to the device Cs 2 AgBiBr 6 The perovskite/AD-MP functional intercalation/Spiro-OMeTAD hole transport layer presents step-shaped distribution among three functional layers, so that the energy level arrangement is optimized, and the charge extraction efficiency is increased.
FIG. 3 shows the AD-MP functional intercalation-based Cs prepared in comparative examples and examples 1 and 2 of the present invention 2 AgBiBr 6 J-V graph of double perovskite solar cell. As can be seen from the figures, the AD-MP functional intercalation-based Cs prepared in examples 1 and 2 2 AgBiBr 6 Double perovskite solar cells obtained 1.2% and 0.8% PCE, respectively, and comparative cells obtained only 0.4% PCE.
FIG. 4 shows the AD-MP functional intercalation-based Cs prepared in comparative examples and examples 1 and 2 of the present invention 2 AgBiBr 6 IPCE profile of a double perovskite solar cell. As can be seen from the figures, the AD-MP functional intercalation-based Cs prepared in examples 1 and 2 2 AgBiBr 6 The double perovskite solar cell obtained 2.29 and 1.36mA/cm respectively 2 Is only 0.8mA/cm for the comparative example cell 2 Is provided. Meanwhile, by reasonably regulating and controlling the solution concentration of the AD-MP, the IPCE value of the battery prepared in the embodiment 1 is remarkably improved, and further the photoelectric conversion efficiency of the battery is improved.
FIG. 5 shows the AD-MP functional intercalation-based Cs prepared in comparative examples and examples 1 and 2 of the present invention 2 AgBiBr 6 Stability test chart for double perovskite solar cell. As can be seen from the figures, the AD-MP functional intercalation-based Cs prepared in examples 1 and 2 2 AgBiBr 6 The double perovskite solar cell still keeps 83.1% and 79.5% of the original efficiency to continue working after 1440h aging; whereas the solar cell efficiency of the comparative example has decayed rapidly to 4.7% of the original efficiency.
Claims (7)
1. Preparation of leadless Cs by taking anthraquinone as core organic micromolecular functional material as intercalation material 2 AgBiBr 6 Use of a double perovskite solar cell device characterized in thatThe chemical name of the organic micromolecular functional material taking anthraquinone as a core is 2, 6-bis (4-methoxyphenyl) amino) phenyl) anthracene-9, 10-dione, which is called AD-MP for short, and the chemical structure is as follows:
2. the use according to claim 1, wherein the lead-free Cs 2 AgBiBr 6 The double perovskite solar cell device comprises a transparent conductive substrate, an electron transport layer and lead-free Cs 2 AgBiBr 6 A double perovskite active layer, an AD-MP functional intercalation layer, a Spiro-OMeTAD hole transport layer and a metal electrode.
3. The use according to claim 2, wherein the lead-free Cs 2 AgBiBr 6 The preparation method of the double perovskite solar cell device comprises the following steps:
(1) Cutting a transparent conductive substrate into a fixed size, adopting laser to etch a specific surface area, sequentially adopting deionized water, acetone and absolute ethyl alcohol to ultrasonically clean the etched conductive substrate, and drying for later use;
(2) Preparing an electron transport layer on the transparent conductive substrate obtained in the step (1) by using a spray pyrolysis method and/or a spin coating method;
(3) The substrate with the electron transport layer is moved to a glove box after being treated by ozone, and lead-free Cs is treated by a spin coating method 2 AgBiBr 6 Spin-coating the double perovskite precursor solution on the top of the electron transport layer to form lead-free Cs 2 AgBiBr 6 A double perovskite active layer;
(4) In a glove box, spin-coating a chlorobenzene solution of an organic micromolecular functional material AD-MP prepared in advance on lead-free Cs by using a spin-coating method 2 AgBiBr 6 Forming AD-MP functional intercalation on the top of the double perovskite active layer;
(5) In a glove box, spin-coating a chlorobenzene solution of the pre-prepared Spiro-OMeTDA hole transport layer on the top of the AD-MP functional intercalation by using a spin-coating method to form the Spiro-OMeTDA hole transport layer;
(6) A metal electrode was deposited on top of the spira-ome tda hole transport layer using vacuum evaporation.
4. The use of claim 3, wherein in step (1), the transparent conductive substrate is any one of FTO conductive glass, ITO conductive glass, or transparent flexible conductive substrate; the ultrasonic cleaning time is 30min;
in the step (2), the electron transport layer is titanium dioxide or tin dioxide.
5. The method according to claim 3, wherein in step (3),
the ozone treatment time is 20min;
the lead-free Cs 2 AgBiBr 6 The preparation method of the double perovskite precursor solution comprises the following steps: cesium bromide, silver bromide and bismuth tribromide are dissolved in N, N-dimethylformamide solution, heated and stirred for 2 hours at 100 ℃, and then the solution is cooled to room temperature for sealing and preservation.
6. The use according to claim 3, wherein in step (4), the concentration of AD-MP in the chlorobenzene solution of AD-MP is 10-30mg/mL.
7. The use according to claim 3, wherein in step (5), the spira-ome tda hole transport layer chlorobenzene solution comprises spira-ome tad and additives LiTFSI, TBP and FK209;
in the step (6), the metal electrode is one of gold, silver or copper.
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