CN105470397A - Preparation method of organic and inorganic hybrid perovskite film possessing high moisture stability and photoelectric conversion efficiency - Google Patents

Preparation method of organic and inorganic hybrid perovskite film possessing high moisture stability and photoelectric conversion efficiency Download PDF

Info

Publication number
CN105470397A
CN105470397A CN201510822273.9A CN201510822273A CN105470397A CN 105470397 A CN105470397 A CN 105470397A CN 201510822273 A CN201510822273 A CN 201510822273A CN 105470397 A CN105470397 A CN 105470397A
Authority
CN
China
Prior art keywords
preparation
thin film
ammonium iodide
perovskite
perovskite thin
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.)
Pending
Application number
CN201510822273.9A
Other languages
Chinese (zh)
Inventor
杨化桂
杨双
侯宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China University of Science and Technology
Original Assignee
East China University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by East China University of Science and Technology filed Critical East China University of Science and Technology
Priority to CN201510822273.9A priority Critical patent/CN105470397A/en
Publication of CN105470397A publication Critical patent/CN105470397A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • 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

Landscapes

  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention relates to a preparation method of an organic and inorganic hybrid perovskite film possessing high moisture stability and photoelectric conversion efficiency. The method is characterized by processing a CH3NH3PbI3 material surface; replacing hydrophilic methylamine cations of the surface; and self-assembling ammonium ions possessing a hydrophobic structure so as to form a layer of monomolecular film so that sensitivity of a perovskite material to water is greatly reduced. The perovskite material possessing a waterproof structure has a very important meaning to perovskite material processing and preparation under an atmospheric environment.

Description

A kind of preparation method with the organic-inorganic mixed type perovskite thin film of high humidity stability and electricity conversion
Technical field
The present invention relates to a kind of preparation method with the organic-inorganic mixing perovskite thin film of high electricity conversion and moisture stability, the method has important use in the preparation of novel solar battery and manufacture field.
Background technology
Energy shortage and environmental pollution are the two large problems that the current mankind are badly in need of solving.We need energy-conservation on the one hand, reduce the consumption of the energy, and use reproducible clean energy resource as much as possible; On the other hand we must the discharge of decreasing pollution thing, eliminates environmental pollution.Sunlight is clean energy resource, how sunlight is changed into our energy easy to use and utilize sunlight to eliminate the focus that environmental pollution becomes research.Semiconductor functional material is absorbing and is utilizing the advantage having uniqueness in sunlight.Such as organic-inorganic mixed type perovskite solar cell, converts our electric energy easy to use to sunlight.
Ca-Ti ore type solar cell is usually in sandwich structure, be specially electro-conductive glass/titanium dioxide dense film/perovskite/hole transmission layer/back electrode, wherein organic-inorganic mixed type perovskite thin film is its key component, carries the important function of the generation of charge carrier, separation and transmission.At present, the Laboratory efficiencies of Ca-Ti ore type solar cell breaks through 20%, has reached commercialization threshold, but its stability (especially in wet environment) limits its key issue further developed.For these problems, D.McGehee etc. report and adopt 2D type perovskite structure, and its photoelectric conversion efficiency reaches 4.73% (Angew.Chem.Int.Ed.2014,126,11414-11417).X.Tao etc. once reported the CH with certain moisture tolerance 3nH 3pb (SCN) 2i structure, although stability promotes to some extent, its device efficiency can only reach 8% (Angew.Chem.Int.Ed.2015,127,7729-7730).The absolute efficiency of these novel perovskite materials, far below 20%, can not meet the demand of actual production.
In the application, we adopt hydrophobic type ammonium iodide aqueous isopropanol process perovskite thin film, react 5 ~ 600s, clean subsequently with pure aqueous isopropanol under normal temperature, obtain the perovskite thin film that surface has monolayer modification.It is corresponding that the film made maintains excellent photoelectricity, and its electricity conversion can more than 15%, and meanwhile, the stability of its perovskite structure significantly promotes, and can store more than 30 days under 90% relative humidities.
Summary of the invention
In view of above problem, the invention provides a kind of preparation method with the organic-inorganic mixing perovskite thin film of high electricity conversion and moisture stability.Concrete technical scheme is as follows:
There is a preparation method for the organic-inorganic mixed type perovskite thin film of high humidity stability and electricity conversion, comprise following steps:
First, with the aqueous isopropanol process perovskite thin film of 5 ~ 40mM ammonium iodide, at 15 ~ 50 DEG C, react 5 ~ 600s; Usually, every 1g perovskite needs the above-mentioned reactant liquor of employing 5 ~ 20mL;
Then, clean up with pure aqueous isopropanol, obtain the perovskite thin film that surface has monolayer modification;
Finally, after adopting standard technology assembling perovskite solar cell, testing photoelectronic transformation efficiency.
Described perovskite thin film is the CH of 400 ~ 600nm thickness 3nH 3pbI 3or NH 2cHNH 2pbI 3film.
Described ammonium iodide has hydrophobic structure, is selected from tetramethyl-ammonium iodide, tetraethyl ammonium iodide, tetrabutylammonium iodide, four pentyl ammonium iodide and cetyl trimethyl ammonium iodide.
Described perovskite thin film before treatment rear surface pattern has slight change, and its surface roughness increases, and surface produces the monomolecular film of one deck waterproof, and thickness is relevant with the molecular dimension of adopted amino molecule, is generally the thickness of a molecular layer.
Compared with existing perovskite thin film method, the present invention has the following advantages: preparation process is simple, and wet environment stability inferior is good, and photoelectric conversion efficiency is high.
Accompanying drawing explanation
Fig. 1 is the ultraviolet-visible spectrogram before and after embodiment 5 processes;
Fig. 2 is the volt-ampere characteristic figure of embodiment 5;
Fig. 3 is the water contact angle change schematic diagram before and after embodiment 5 processes; Standard is the contact angle photo of sample before process, and TEAI is the contact angle photo with sample after TEAI process;
Fig. 4 is the scanning electron microscopic picture after embodiment 5 processes;
Fig. 5 is that the perovskite material before and after processing in embodiment 5 stores the XRD collection of illustrative plates after 30 days under 90% relative humidity.
Embodiment
Below, further illustrate content of the present invention by embodiment, but protection scope of the present invention is not limited in embodiment.To the other changes and modifications that those skilled in the art makes when not deviating from the present invention's spirit and protection range, be still included within scope.
Embodiment 1
With the tetramethyl-ammonium iodide aqueous isopropanol process perovskite thin film of 40mM, react 60s under normal temperature, clean 3 times with pure aqueous isopropanol subsequently, after drying, obtain the perovskite thin film that surface has monolayer modification.After finally adopting standard technology assembling perovskite solar cell, electricity conversion reaches 12.89% (short circuit current 21.0mA/cm 2, open circuit voltage 990mV, fill factor, curve factor 0.62).
Embodiment 2
With the tetrabutylammonium iodide aqueous isopropanol process perovskite thin film of 20mM, react 300s under normal temperature, clean 3 times with pure aqueous isopropanol subsequently, after drying, obtain the perovskite thin film that surface has monolayer modification.After finally adopting standard technology assembling perovskite solar cell, electricity conversion reaches 11.94% (short circuit current 19.7mA/cm 2, open circuit voltage 950mV, fill factor, curve factor 0.64).
Embodiment 3
With the four pentyl ammonium iodide aqueous isopropanol process perovskite thin film of 25mM, react 60s under normal temperature, clean 3 times with pure aqueous isopropanol subsequently, after drying, obtain the perovskite thin film that surface has monolayer modification.After finally adopting standard technology assembling perovskite solar cell, electricity conversion reaches 7.15% (short circuit current 12.8mA/cm 2, open circuit voltage 900mV, fill factor, curve factor 0.62).
Embodiment 4
With the tetraethyl ammonium iodide aqueous isopropanol process perovskite thin film of 10mM, react 600s under normal temperature, clean 3 times with pure aqueous isopropanol subsequently, after drying, obtain the perovskite thin film that surface has monolayer modification.After finally adopting standard technology assembling perovskite solar cell, electricity conversion reaches 13.65% (short circuit current 20.0mA/cm 2, open circuit voltage 1000mV, fill factor, curve factor 0.68).
Embodiment 5
With the tetraethyl ammonium iodide aqueous isopropanol process perovskite thin film of 25mM, react 20s under normal temperature, clean 3 times with pure aqueous isopropanol subsequently, after drying, obtain the perovskite thin film that surface has monolayer modification, the water contact angle on surface obviously promotes, as shown in Figure 3.As shown in Figure 1, after process, the scanning electron microscopic picture of sample as shown in Figure 4 for uv-vis spectra before and after sample treatment.By sample storage under 90% relative humidity, find after 30 days, overall crystal phase structure change is little, and comparative sample severe decomposition.As shown in Figure 5, perovskite material before treatment has obvious decomposition, and the sample decomposition peak after process is not obvious.Finally adopt standard
After technique assembling perovskite solar cell, electricity conversion reaches 15.05% (short circuit current 20.2mA/cm 2, open circuit voltage 995mV, fill factor, curve factor 0.75), as shown in Figure 2.
The test result of embodiment 1 to 4 is similar to Example 5.

Claims (4)

1. there is a preparation method for the organic-inorganic mixed type perovskite thin film of high humidity stability and electricity conversion, comprise following steps:
First, with the aqueous isopropanol process perovskite thin film of 5 ~ 40mM ammonium iodide, at 15 ~ 50 DEG C, 5 ~ 600s is answered; Wherein, the aqueous isopropanol of the corresponding described ammonium iodide of 1g perovskite is 5 ~ 20mL;
Then, clean up with pure aqueous isopropanol, obtain the perovskite thin film that surface has monolayer modification;
Finally, after adopting standard technology assembling perovskite solar cell, testing photoelectronic transformation efficiency.
2. preparation method according to claim 1, is characterized in that, described perovskite thin film is the CH of 400 ~ 600nm thickness 3nH 3pbI 3or NH 2cHNH 2pbI 3film.
3. preparation method according to claim 1, is characterized in that, described ammonium iodide has hydrophobic structure, is selected from tetramethyl-ammonium iodide, tetraethyl ammonium iodide, tetrabutylammonium iodide, four pentyl ammonium iodide and cetyl trimethyl ammonium iodide.
4. preparation method according to claim 1, it is characterized in that, described perovskite thin film before treatment rear surface pattern has slight change, its surface roughness increases, surface produces the monomolecular film of one deck waterproof, thickness is relevant with the molecular dimension of adopted amino molecule, is the thickness of a molecular layer.
CN201510822273.9A 2015-11-24 2015-11-24 Preparation method of organic and inorganic hybrid perovskite film possessing high moisture stability and photoelectric conversion efficiency Pending CN105470397A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510822273.9A CN105470397A (en) 2015-11-24 2015-11-24 Preparation method of organic and inorganic hybrid perovskite film possessing high moisture stability and photoelectric conversion efficiency

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510822273.9A CN105470397A (en) 2015-11-24 2015-11-24 Preparation method of organic and inorganic hybrid perovskite film possessing high moisture stability and photoelectric conversion efficiency

Publications (1)

Publication Number Publication Date
CN105470397A true CN105470397A (en) 2016-04-06

Family

ID=55607908

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510822273.9A Pending CN105470397A (en) 2015-11-24 2015-11-24 Preparation method of organic and inorganic hybrid perovskite film possessing high moisture stability and photoelectric conversion efficiency

Country Status (1)

Country Link
CN (1) CN105470397A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105932164A (en) * 2016-04-27 2016-09-07 上海交通大学 Method for improving stability of perovskite film through sulphuring treatment
CN107304167A (en) * 2016-04-25 2017-10-31 松下知识产权经营株式会社 Light absorbing material and the solar cell using the light absorbing material
CN107833970A (en) * 2017-10-19 2018-03-23 华中科技大学鄂州工业技术研究院 A kind of surface modification method of perovskite thin film
CN108649119A (en) * 2018-04-08 2018-10-12 中国石油大学(华东) A kind of perovskite thin film hydrophobic modification method based on fatty amine hydriodate type organic
CN109148687A (en) * 2017-06-16 2019-01-04 韩国化学研究院 Perovskite series solar battery and its manufacturing method comprising broad-band gap
WO2019128864A1 (en) * 2017-12-30 2019-07-04 杭州纤纳光电科技有限公司 Ion stabilizer-doped perovskite film, preparation method therefor and application thereof
CN109994608A (en) * 2017-12-29 2019-07-09 比亚迪股份有限公司 A kind of perovskite battery and preparation method thereof
CN112909184A (en) * 2021-01-15 2021-06-04 邵阳学院 Low-grain-boundary perovskite crystal thin film, battery and preparation method of thin film
CN113105882A (en) * 2020-12-14 2021-07-13 中国计量大学上虞高等研究院有限公司 CsPbI for improving stability3Nanocrystalline composite material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013171518A1 (en) * 2012-05-18 2013-11-21 Isis Innovation Limited Optoelectronic device comprising porous scaffold material and perovskites
CN204029873U (en) * 2014-08-12 2014-12-17 中国乐凯集团有限公司 A kind of planar heterojunction perovskite solar cell
CN104576930A (en) * 2015-01-06 2015-04-29 宁波大学 Perovskite solar cell and manufacturing method of perovskite solar cell
WO2015092397A1 (en) * 2013-12-17 2015-06-25 Isis Innovation Limited Photovoltaic device comprising a metal halide perovskite and a passivating agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013171518A1 (en) * 2012-05-18 2013-11-21 Isis Innovation Limited Optoelectronic device comprising porous scaffold material and perovskites
WO2015092397A1 (en) * 2013-12-17 2015-06-25 Isis Innovation Limited Photovoltaic device comprising a metal halide perovskite and a passivating agent
CN204029873U (en) * 2014-08-12 2014-12-17 中国乐凯集团有限公司 A kind of planar heterojunction perovskite solar cell
CN104576930A (en) * 2015-01-06 2015-04-29 宁波大学 Perovskite solar cell and manufacturing method of perovskite solar cell

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107304167A (en) * 2016-04-25 2017-10-31 松下知识产权经营株式会社 Light absorbing material and the solar cell using the light absorbing material
CN107304167B (en) * 2016-04-25 2021-05-25 松下知识产权经营株式会社 Light absorbing material and solar cell using the same
CN105932164B (en) * 2016-04-27 2019-02-22 上海交通大学 The method of sulphuring treatment raising perovskite film stability
CN105932164A (en) * 2016-04-27 2016-09-07 上海交通大学 Method for improving stability of perovskite film through sulphuring treatment
CN109148687A (en) * 2017-06-16 2019-01-04 韩国化学研究院 Perovskite series solar battery and its manufacturing method comprising broad-band gap
CN107833970B (en) * 2017-10-19 2020-04-28 华中科技大学鄂州工业技术研究院 Surface modification method of perovskite film
CN107833970A (en) * 2017-10-19 2018-03-23 华中科技大学鄂州工业技术研究院 A kind of surface modification method of perovskite thin film
CN109994608A (en) * 2017-12-29 2019-07-09 比亚迪股份有限公司 A kind of perovskite battery and preparation method thereof
WO2019128864A1 (en) * 2017-12-30 2019-07-04 杭州纤纳光电科技有限公司 Ion stabilizer-doped perovskite film, preparation method therefor and application thereof
CN108649119A (en) * 2018-04-08 2018-10-12 中国石油大学(华东) A kind of perovskite thin film hydrophobic modification method based on fatty amine hydriodate type organic
CN113105882A (en) * 2020-12-14 2021-07-13 中国计量大学上虞高等研究院有限公司 CsPbI for improving stability3Nanocrystalline composite material and preparation method thereof
CN113105882B (en) * 2020-12-14 2022-05-24 中国计量大学上虞高等研究院有限公司 CsPbI for improving stability3Nanocrystalline composite material and preparation method thereof
CN112909184A (en) * 2021-01-15 2021-06-04 邵阳学院 Low-grain-boundary perovskite crystal thin film, battery and preparation method of thin film
CN112909184B (en) * 2021-01-15 2022-07-22 邵阳学院 Low-crystal-boundary perovskite crystal film, battery and preparation method of low-crystal-boundary perovskite crystal film

Similar Documents

Publication Publication Date Title
CN105470397A (en) Preparation method of organic and inorganic hybrid perovskite film possessing high moisture stability and photoelectric conversion efficiency
Tian et al. PVP treatment induced gradient oxygen doping in In2S3 nanosheet to boost solar water oxidation of WO3 nanoarray photoanode
Yun et al. New-generation integrated devices based on dye-sensitized and perovskite solar cells
Yan et al. Choline chloride-modified SnO2 achieving high output voltage in MAPbI3 perovskite solar cells
Mali et al. Ultrathin atomic layer deposited TiO2 for surface passivation of hydrothermally grown 1D TiO2 nanorod arrays for efficient solid-state perovskite solar cells
Bi et al. Efficient and stable CH 3 NH 3 PbI 3-sensitized ZnO nanorod array solid-state solar cells
Sadasivuni et al. Flexible, biodegradable and recyclable solar cells: a review
Bella et al. Interfacial effects in solid–liquid electrolytes for improved stability and performance of dye-sensitized solar cells
Liu et al. Enhanced photoelectrochemical water-splitting performance of semiconductors by surface passivation layers
Ciro et al. Self-functionalization behind a solution-processed NiO x film used as hole transporting layer for efficient perovskite solar cells
Mali et al. Bio-inspired carbon hole transporting layer derived from aloe vera plant for cost-effective fully printable mesoscopic carbon perovskite solar cells
Haque et al. Flexible dye sensitised nanocrystalline semiconductor solar cells
Sun et al. One-step preparation of mirror-like NiS nanosheets on ITO for the efficient counter electrode of dye-sensitized solar cells
Xu et al. Perovskite Films Regulation via Hydrogen‐Bonded Polymer Network for Efficient and Stable Perovskite Solar Cells
Sun et al. Growth of single-crystalline rutile TiO 2 nanowire array on titanate nanosheet film for dye-sensitized solar cells
Andoshe et al. A wafer-scale antireflective protection layer of solution-processed TiO 2 nanorods for high performance silicon-based water splitting photocathodes
Fu et al. Synergistic effects of interfacial energy level regulation and stress relaxation via a buried interface for highly efficient perovskite solar cells
Tian et al. All-in-one additive enables defect passivated, crystallization modulated and moisture resisted perovskite films toward efficient solar cells
Sekimoto et al. Influence of a hole-transport layer on light-induced degradation of mixed organic–inorganic halide perovskite solar cells
Singh et al. New biodegradable polymer electrolyte for dye sensitized solar cell
Barichello et al. The effect of water in Carbon-Perovskite Solar Cells with optimized alumina spacer
Gao et al. Interface modification effects of 4-tertbutylpyridine interacting with N3 molecules in quasi-solid dye-sensitized solar cells
Wang et al. Full-scale chemical and field-effect passivation: 21.52% efficiency of stable MAPbI 3 solar cells via benzenamine modification
CN101694814A (en) Electrochemistry preparation method of dye sensibilization solar cell nanometer conductive polymer counter electrode
CN108807677A (en) A kind of composite electron transport layer perovskite solar cell and preparation method thereof prepared using atomic layer deposition method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20160406

RJ01 Rejection of invention patent application after publication