CN113173930B - Benzodithiophenedione-based non-doped hole transport material and synthesis method and application thereof - Google Patents
Benzodithiophenedione-based non-doped hole transport material and synthesis method and application thereof Download PDFInfo
- Publication number
- CN113173930B CN113173930B CN202110461386.6A CN202110461386A CN113173930B CN 113173930 B CN113173930 B CN 113173930B CN 202110461386 A CN202110461386 A CN 202110461386A CN 113173930 B CN113173930 B CN 113173930B
- Authority
- CN
- China
- Prior art keywords
- hole transport
- transport material
- benzodithiophene
- diketone
- solar cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- 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 discloses a benzodithiophene diketone-based non-doped hole transport material, a synthesis method thereof and application thereof in a perovskite solar cell. The invention takes benzodithiophene diketone with a rigid conjugated plane as a parent nucleus, and the plane conjugated structure and the electron-withdrawing capability of carbonyl can improve molecular accumulation and effectively improve the hole transport performance of the material. The synthetic method is simple, the synthetic cost is low, and the synthesized material has high hole transmission capacity and proper energy level; when the material is applied to a perovskite solar cell as a hole transport layer, high open-circuit voltage of more than 1.12V and photoelectric conversion efficiency of more than 19 percent can be obtained without doping, and the material has wide application prospect.
Description
Technical Field
The invention relates to the technical field of hole transport materials, in particular to a benzodithiophene diketone-based undoped hole transport material and a synthesis method and application thereof.
Background
The development and progress of the human society cannot be supported by energy, and the direct conversion of clean and sustainable solar energy into electric energy through a solar cell is a hot spot which is always concerned by academia and industry. The silicon-based solar cell has higher photoelectric conversion efficiency as the mainstream of the current market, but the characteristics of high energy consumption, high pollution and high cost in the production process also limit the large-scale application of the silicon-based solar cell.
Perovskite solar cells have attracted much attention in recent years due to their characteristics of high efficiency, low cost, large-scale printing and the like. Since 2009 was reported for the first time, the solar conversion efficiency of the solar cell rapidly increases from the initial 3.8% to 25.5% at present, and the efficiency progress in short and short decades exceeds the accumulation of other solar cells for decades, so that the solar cell is selected as one of ten technological breakthroughs in the year by the journal of Science in the united states in 2013, and has great industrialization potential.
In general, perovskite solar cells are sandwich-like structures consisting of an electron transport layer/perovskite/hole transport layer, wherein the hole transport layer has a critical influence on the efficiency and stability of the cell. Currently, 2,2,7, 7-tetrakis [ N, N-bis (4-methoxyphenyl) amino]9, 9-spirobifluorene (spiro-OMeTAD) is the most widely used hole transport material, but the spiro-OMeTAD has low hole mobility (10-5 cm) by itself2 V-1s-1) P-type dopants such as FK209, Li-TFSI, etc. must be used to improve conductivity, but the use of these dopants tends to result in a reduction in device lifetime, which severely hinders the progress of perovskite solar cell industrialization. Therefore, the development of the undoped hole transport material becomes a research hotspot and a key factor of industrialization in the field of perovskite solar cells.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a hole transport material which has high hole mobility and good conductivity, does not need to be doped by lithium salt, cobalt salt, tert-butylpyridine and the like, does not damage the service life and stability of a battery, and can reduce the production cost of the battery.
In order to achieve the purpose, the invention designs a benzodithiophene diketone-based non-doped hole transport material, which takes benzodithiophene diketone as a parent nucleus and thiophene-substituted methoxyl triphenylamine as a side arm, and has the following structural formula:
another object of the present invention is to provide a method for synthesizing the hole transport material, which specifically comprises the following steps:
under the protection of nitrogen, 4-methoxy-N- (4-methoxyphenyl) -N- (4- (5- (tributyltin group) thiophene-2-yl) phenyl) aniline TPA-T-Sn and 2, 6-dibromobenzo [1,2-b:4,5-b' ] dithiophene-4, 8-diketone BDT-Br are coupled under the catalysis of tetrakis (triphenylphosphine) palladium to obtain a target product BDT-T;
further, the reaction solvent is toluene.
Further, the reaction temperature was 110. + -. 10 ℃.
Furthermore, the molar ratio of the benzodithiophene dione bromo-derivative BDT-TBr, TPA-T-Sn and tetrakis (triphenylphosphine) palladium is 1:2: 0.05-1: 3: 0.2.
A third object of the present invention is to apply benzodithiophene dione based undoped hole transport materials to perovskite solar cells.
Further, in the perovskite solar cell structure, a non-doped hole transport material based on benzodithiophene diketone is coated on the surface of the perovskite thin film in a spin coating mode to serve as a hole transport layer.
Furthermore, the perovskite solar cell has a structure of glass/ITO/SnO in sequence from bottom to top2perovskite/HTM/Au, said HTM being a non-doped hole transport material based on benzodithiophenediones.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to a benzodithiophene diketone-based non-doped hole transport material, which takes benzodithiophene diketone as a parent nucleus and thiophene-substituted methoxyl triphenylamine as a side arm; the benzodithiophene diketone with a rigid conjugated plane is used as a parent nucleus, and the plane conjugated structure and the electron-withdrawing capability of carbonyl can improve molecular accumulation and effectively improve the hole transport performance of the material. The invention adopts simplified synthesis steps and synthesizes the non-doped hole transport material based on benzodithiophene diketone with low cost. The benzodithiophene condensed ring and carbonyl structure endow the material with high hole mobility, so that when the synthesized material is used as a hole transport layer of the perovskite solar cell, the high open-circuit voltage of more than 1.12V and the photoelectric conversion efficiency of more than 19 percent can be obtained without doping lithium salt, cobalt salt, tert-butylpyridine and the like, the service life and the stability of the perovskite solar cell are greatly improved, and the industrialization of the perovskite solar cell is hopefully facilitated.
Drawings
FIG. 1 is a cyclic voltammogram of a BDT-T material prepared by the present invention;
FIG. 2 is a J-V curve of BDT-T prepared by the invention as an undoped hole transport material for perovskite solar cells;
FIG. 3 is a schematic structural diagram of a perovskite solar cell prepared by the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments.
Example 1:
synthesis of BDT-T:
the compound TPA-T-Sn was prepared and synthesized according to documents k.do, h.choi, k.lim, h.jo, j.w.cho, m.k.nazeerudin, j.ko, chem.commun.2014,50,10971; the compound BDT-Br was prepared according to the literature C. -Y.Kuo, W.Nie, H.Tsai, H. -J.Yen, A.D.Mohite, G.Gupta, A.M.Dattelbaum, D.J.William, K.C.cha, Y.Yang, L.Wang, H. -L.Wang, Macromolecules 2014,47,1008.
TPA-T-Sn (1.97g, 2.91mmol) and BDT-Br (0.50g, 1.32mmol) and tetrakis (triphenylphosphine) palladium (0.15g, 0.13mmol) were added sequentially to a 100mL two-necked flask under nitrogen blanket. To the reaction system, 40mL of dry toluene was added and nitrogen was bubbled for 20 min. The reaction solution was heated to 120 ℃ and refluxed for 48 h. After the reaction solution was cooled to room temperature, the solvent was removed by a rotary evaporator to obtain a crude product. The crude product was separated by chromatography column eluting with petroleum ether/dichloromethane (1:1, v/v) to give BDT-T as a tan solid in 78% yield.
The nuclear magnetic hydrogen spectrum of the BDT-T prepared by the method is characterized in that:1H NMR(400MHz,CDCl3δ 7.88(s,2H),7.37(s,4H),7.31(s,4H),7.12(s,8H),6.97(s,12H),3.81(s, 12H). As shown in FIG. 1, the HOMO level of BDT-T was measured to be-5.18 eV using electrochemical cyclic voltammetry.
Example 2:
the non-doped hole transport material BDT-T prepared in example 1 was used as a hole transport layer to prepare a perovskite solar cell, as shown in fig. 3, which has the following structure: glass/ITO/SnO2perovskite/HTM/Au. And (3) ultrasonically cleaning the ITO conductive glass for 30min by using an alkaline glass cleaning agent, deionized water, acetone and isopropanol in sequence. After nitrogen blow-drying, the ITO glass is cleaned for 15min by adopting plasma. SnO is treated by adopting a spin coating instrument2Spin-coating on ITO, and carrying out thermal annealing treatment at 150 ℃ for 30 min. Next, 1.5M MA was added0.7FA0.3PbI3Perovskite solution spin coating to SnO2And carrying out thermal annealing treatment on the surface for 5min at 100 ℃. After cooling, BDT-T obtained in example 1 was spin-coated on the surface of the perovskite thin film as a hole transport layer, and the concentration of chlorobenzene solution was 15mg mL-1. Finally, a layer of Au with the thickness of 50nm is evaporated in vacuum to be used as an electrode, so that the preparation of the perovskite solar cell device is completed, and the effective area of the device is 4mm2. Using a xenon lamp solar simulator, testing the light source intensity of AM 1.5G, 100mW cm-2And testing the open-circuit voltage, the short-circuit current and the filling factor of the prepared battery device.
Perovskite solar cell devices were prepared and characterized according to the procedure described above, based on the BDT-T prepared in example 1. The current-voltage (J-V) characteristic curve of the device performance is shown in FIG. 2, whereinLine voltage Voc1.123V, short-circuit current density JscIs 23.23mA/cm2The fill factor FF was 0.758, and the photoelectric conversion efficiency was 19.77%.
Therefore, when the BDT-T hole transport material is applied to the perovskite solar cell, the high open-circuit voltage of more than 1.12V and the photoelectric conversion efficiency of more than 19 percent can be obtained without doping, and the BDT-T hole transport material has wide application prospect.
Although the present invention has been described with reference to the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications, equivalents and alternatives falling within the spirit and scope of the invention.
Claims (8)
1. A benzodithiophenedione-based undoped hole transport material, characterized in that: has the following structural formula:
2. a method of synthesizing the undoped hole transport material of claim 1, wherein: the method comprises the following steps:
under the protection of nitrogen, 4-methoxy-N- (4-methoxyphenyl) -N- (4- (5- (tributyltin group) thiophene-2-yl) phenyl) aniline TPA-T-Sn and 2, 6-dibromobenzo [1,2-b:4,5-b' ] dithiophene-4, 8-diketone BDT-Br are coupled under the catalysis of tetrakis (triphenylphosphine) palladium to obtain a target product BDT-T;
3. the method of synthesizing an undoped hole transport material according to claim 2, wherein: the reaction solvent was toluene.
4. The method of synthesizing an undoped hole transport material according to claim 2, wherein: the reaction temperature was 110. + -. 10 ℃.
5. The method of synthesizing an undoped hole transport material according to claim 2, wherein: the molar ratio of the benzodithiophene dione bromo-derivative BDT-Br, TPA-T-Sn and tetrakis (triphenylphosphine) palladium is 1:2: 0.05-1: 3: 0.2.
6. Use of an undoped hole transport material according to claim 1, wherein: the non-doped hole transport material based on benzodithiophene diketone is applied to the perovskite solar cell.
7. Use of the undoped hole transport material of claim 6, wherein: in the perovskite solar cell structure, a non-doped hole transport material based on benzodithiophene diketone is coated on the surface of a perovskite thin film in a spinning mode to serve as a hole transport layer.
8. Use of the undoped hole transport material of claim 7, wherein: the perovskite solar cell is sequentially formed by glass/ITO/SnO 2/perovskite/HTM/Au from bottom to top, and the HTM is an undoped hole transport material based on benzodithiophene diketone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2021102547681 | 2021-03-09 | ||
| CN202110254768 | 2021-03-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113173930A CN113173930A (en) | 2021-07-27 |
| CN113173930B true CN113173930B (en) | 2022-04-19 |
Family
ID=76926640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110461386.6A Active CN113173930B (en) | 2021-03-09 | 2021-04-27 | Benzodithiophenedione-based non-doped hole transport material and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113173930B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276325B (en) * | 2021-12-10 | 2023-05-26 | 常州大学 | Organic molecular material containing diphenyl [ b, d ] benzothiophene-5, 5' -dioxide and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103262279A (en) * | 2010-11-22 | 2013-08-21 | 加利福尼亚大学董事会 | Organic small molecule semiconducting chromophores for use in organic electronic devices |
| CN105753883A (en) * | 2016-03-31 | 2016-07-13 | 中南大学 | Triphenylamine-benzothiophene organic small-molecule hole transporting material and application thereof |
| CN105968124A (en) * | 2016-05-12 | 2016-09-28 | 华东师范大学 | 2,6-bis(triphenylamine)-4,8-bis(alkoxy)benzo[1,2-b:4,5-b']bithiophene and preparation for same |
| CN106397355A (en) * | 2016-09-05 | 2017-02-15 | 华南理工大学 | Self-doped conjugated phenolamine hole-transporting material and its preparation method and use |
| JP2018129510A (en) * | 2017-02-06 | 2018-08-16 | 日本化薬株式会社 | Organic photoelectric conversion material for image pickup device and organic photoelectric conversion device and organic imaging device using the same |
| CN109053635A (en) * | 2018-08-01 | 2018-12-21 | 华南理工大学 | A kind of application of Organic micromolecular semiconductor material as organic ferromagnetic material |
| CN111909169A (en) * | 2020-08-10 | 2020-11-10 | 泰州市海创新能源研究院有限公司 | Hole transport material with benzodithiophene diketone as core, synthesis method and application in perovskite solar cell |
-
2021
- 2021-04-27 CN CN202110461386.6A patent/CN113173930B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103262279A (en) * | 2010-11-22 | 2013-08-21 | 加利福尼亚大学董事会 | Organic small molecule semiconducting chromophores for use in organic electronic devices |
| US20140167002A1 (en) * | 2010-11-22 | 2014-06-19 | The Regents Of The University Of California | Organic small molecule semiconducting chromophores for use in organic electronic devices |
| CN105753883A (en) * | 2016-03-31 | 2016-07-13 | 中南大学 | Triphenylamine-benzothiophene organic small-molecule hole transporting material and application thereof |
| CN105968124A (en) * | 2016-05-12 | 2016-09-28 | 华东师范大学 | 2,6-bis(triphenylamine)-4,8-bis(alkoxy)benzo[1,2-b:4,5-b']bithiophene and preparation for same |
| CN106397355A (en) * | 2016-09-05 | 2017-02-15 | 华南理工大学 | Self-doped conjugated phenolamine hole-transporting material and its preparation method and use |
| JP2018129510A (en) * | 2017-02-06 | 2018-08-16 | 日本化薬株式会社 | Organic photoelectric conversion material for image pickup device and organic photoelectric conversion device and organic imaging device using the same |
| CN109053635A (en) * | 2018-08-01 | 2018-12-21 | 华南理工大学 | A kind of application of Organic micromolecular semiconductor material as organic ferromagnetic material |
| CN111909169A (en) * | 2020-08-10 | 2020-11-10 | 泰州市海创新能源研究院有限公司 | Hole transport material with benzodithiophene diketone as core, synthesis method and application in perovskite solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113173930A (en) | 2021-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kang et al. | A printable organic cathode interlayer enables over 13% efficiency for 1-cm2 organic solar cells | |
| JP3204770U (en) | Organic solar cell | |
| Guo et al. | Effect of energy alignment, electron mobility, and film morphology of perylene diimide based polymers as electron transport layer on the performance of perovskite solar cells | |
| Kooistra et al. | Increasing the open circuit voltage of bulk-heterojunction solar cells by raising the LUMO level of the acceptor | |
| Schulze et al. | Efficient vacuum‐deposited organic solar cells based on a new low‐bandgap oligothiophene and fullerene C60 | |
| Wynands et al. | Correlation between morphology and performance of low bandgap oligothiophene: C60 mixed heterojunctions in organic solar cells | |
| CN113173923B (en) | Self-assembled monomolecular layer type non-doped hole transport material and synthetic method and application thereof | |
| TW201210935A (en) | Cross-linkable fullerene derivatives and inverted solar cells thereof | |
| Liu et al. | A rational design and synthesis of cross-conjugated small molecule acceptors approaching high-performance fullerene-free polymer solar cells | |
| Ni et al. | A new oligobenzodithiophene end-capped with 3-ethyl-rhodanine groups for organic solar cells with high open-circuit voltage | |
| Hu et al. | Enhanced performance of inverted perovskite solar cells using solution-processed carboxylic potassium salt as cathode buffer layer | |
| Zhou et al. | High open-circuit voltage solution-processed organic solar cells based on a star-shaped small molecule end-capped with a new rhodanine derivative | |
| CN113173930B (en) | Benzodithiophenedione-based non-doped hole transport material and synthesis method and application thereof | |
| CN113410391B (en) | Organic solar cell with blending layer and preparation method | |
| CN112661940B (en) | Thiophene thiadiazole-based n-type water/alcohol-soluble conjugated polyelectrolyte, and preparation and application thereof | |
| CN111689867B (en) | Hole transport layer material and preparation method thereof, perovskite solar cell and preparation method thereof | |
| Liu et al. | ADA-type small molecular acceptor with one hexyl-substituted thiophene as π bridge for fullerene-free organic solar cells | |
| Abdullah et al. | Highly stable bulk heterojunction organic solar cells based on asymmetric benzoselenadiazole‐oriented organic chromophores | |
| CN109851571B (en) | Conjugated organic small molecule interface modification material, preparation method and organic solar cell formed by conjugated organic small molecule interface modification material | |
| CN113173936B (en) | Non-doped hole transport material based on condensed ring electron-withdrawing parent nucleus and synthesis method and application thereof | |
| CN112646130B (en) | N-type water/alcohol-soluble conjugated polyelectrolyte based on double free radical benzobisthiadiazole, and preparation and application thereof | |
| CN108912125B (en) | Non-fullerene acceptor material based on tetraarylpyrrole nucleus and application thereof | |
| Gao et al. | A‐π‐D‐π‐A type Small Molecules Using Ethynylene Linkages for Organic Solar Cells with High Open‐circuit Voltages | |
| Gong et al. | Large open-circuit voltage polymer solar cells by poly (3-hexylthiophene) with multi-adducts fullerenes | |
| Wu et al. | Polar side-chain tuning of perylene diimide and fluorene-based cathode interfacial material for high-performance inverted perovskite solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |