CN109326718A - A kind of double-buffering layer perovskite method for manufacturing solar battery - Google Patents

A kind of double-buffering layer perovskite method for manufacturing solar battery Download PDF

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Publication number
CN109326718A
CN109326718A CN201811108564.1A CN201811108564A CN109326718A CN 109326718 A CN109326718 A CN 109326718A CN 201811108564 A CN201811108564 A CN 201811108564A CN 109326718 A CN109326718 A CN 109326718A
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layer
perovskite
solar battery
double
manufacturing solar
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王伟红
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Beijing Hengxin Zhuo Yuan Technology Co Ltd
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Beijing Hengxin Zhuo Yuan Technology Co Ltd
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    • 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
    • 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
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • H10K85/30—Coordination compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention discloses a kind of double-buffering layer perovskite preparation method of solar battery.This method mainly includes sequentially forming hearth electrode, electron transfer layer, perovskite absorbed layer, hole transmission layer, nanometer double-buffering layer, top electrode and anti-reflecting layer.By forming nano-TiO between hole transmission layer2/MoO2Buffer layer structure can preferably protect electron transfer layer/perovskite absorbed layer/hole transmission layer perovskite solar battery main structure, so as to realize large area perovskite solar battery manufacture.

Description

A kind of double-buffering layer perovskite method for manufacturing solar battery
Technical field
The invention belongs to perovskite area of solar cell, are related specifically to a kind of double-buffering layer perovskite solar battery Manufacturing method.
Background technique
With the continuous consumption of the non-renewable energy resources such as fossil fuel, the energy crisis of facing mankind is increasingly heavy.Therefore, may be used Renewable sources of energy solar energy is increasingly valued by people.Solar energy is renewable as a kind of inexhaustible cleaning The energy receives the extensive concern of people.Tradition is exactly that (light is converted into common solar water heater using the method for solar energy Heat), however this mode scope of application for generating efficiency is limited to very much.With Switzerland scientist MichealSaying, It is about 32 × 10 that the sun irradiates energy at the earth's surface every year24J is equivalent to 10,000 times of the annual consumption energy in the whole world at present, It is enough if the solar battery for being 10% with energy conversion efficiency gets up the energy utilization of 0.1% area of earth surface full The demand of the current energy of foot.Therefore the best method using solar energy be then to be generated electricity using solar energy, this be one very It is worth the thing explored.
Solar battery is the device for directly luminous energy being converted to by photoelectric effect or photochemical effect electric energy, also known as For photovoltaic cell.As third generation solar cell, the active layer of perovskite solar battery (PSCs) has high delustring Coefficient, the performances such as biggish carrier diffusion length and bipolarity carrier transport become research hotspot.Perovskite material from It is used for solar battery within 2009, has reached nearly 20% to current efficiency, 5 times of battery efficiency when being initial, dye Material sensitization solar battery, the novel thin films solar cell such as organic solar batteries are got rid of behind, perovskite solar battery It is to develop very fast inexpensive thin-film solar cells over nearly 3 years.
Perovskite solar battery generally comprises multiple layers, including transparent substrates, the bottom transparent conductive oxide (TCO) electricity Pole, electron transfer layer (N-shaped ETL) are situated between and see oxide/perovskite composite layer (optional), plane calcium titanium ore bed, hole transmission layer (p Type HTL) and top metal electrode.Perovskite solar battery structure core is that have the organic metal of perovskite crystal form (ABX) Halide light absorbent.In this perovskite ABX structure, A be methylamino (CHNH), B be metal lead atom, X be chlorine, bromine, The halogen atoms such as iodine.At present in efficient Ca-Ti ore type solar battery, the most common perovskite material is lead iodide methylamine (CHNHPbI), its band gap is about 1.5eV, and extinction coefficient is high, and several hundred nanometers of thick films can fully absorb 800nm or less Sunlight.Moreover, this material preparation is simple, the solution containing PbI and CHNHI can be obtained by spin coating at normal temperature Obtain uniform film.Above-mentioned characteristic, which makes perovskite structure CHNHPbI not only, may be implemented to visible light and part near infrared light Absorption, and generated photo-generated carrier is not easy compound, and energy loss is small, this is that Ca-Ti ore type solar battery can be real Existing efficient basic reason.
Although current perovskite synthesis achieves significant progress, most of researchs be all using small area (< 0.2cm2) perovskite completion, the PSC for only having a few studies to attempt preparation large area at present, and the conversion in the case of large area Efficiency far lags behind the 22% of laboratory.Efficient small is tested in being solved using double-buffering layer structure for the invention The production of room battery is amplified to production more large area perovskite solar battery to keep its efficient problem.
Summary of the invention
Perovskite can not only absorb solar spectrum extensively, and have splendid charge transport properties.In order to sufficiently sharp With these properties, the invention proposes a kind of perovskite solar batteries using double-buffering layer, can be to electrically conducting transparent electricity Pole carries out the destruction that not will cause calcium titanium ore bed when high energy depositing operation, so as to realize the perovskite solar-electricity of large area The manufacture in pond.
The specific technical solution of the present invention is as follows:
(1) hearth electrode is formed
Transparent conducting glass is successively used to acetone, ethyl alcohol, deionized water ultrasonic cleaning, then is handled through UV ozone, is obtained Clean transparent conducting glass is as hearth electrode, and the thickness of transparent conducting glass is between 100-150nm.Transparent conducting glass can To select indium tin oxide (ITO), fluorine tin-oxide (FTO) or aluminium zinc oxide (AZO).
(2) electron transfer layer is formed
One layer of electron transfer layer is formed on the buffer layer, and electron transfer layer is one or more following inorganic compounds, packet Include TiO, ZnSnO, CsCO, BaTiO, SrTiO, MgTiO, BaSnO, SnO, ZnO or CdS.
(3) perovskite absorbed layer is formed
Spin coating perovskite thin film on the electron transport layer, and film is placed in vacuum chamber 3 seconds with remaining molten by removing Agent promotes perovskite to be nucleated, and carries out spin coating proceeding in surrounding air；Rotate 50 seconds with the revolving speed of 4000rpm, then with The speed of 2000rpm rotates 18 seconds, 150 DEG C at a temperature of anneal 15 minutes, form perovskite absorbed layer.
(4) hole transmission layer is formed
Hole transmission layer is formed on perovskite absorbed layer, hole transmission layer is one or more following inorganic compounds, Including doped or undoped NiO (doped chemical be selected from Cu, Li, Ca, Mg or Sr one or more), CuO, PbS, VO, The doped or undoped AMO type semiconductor material of MoO, CuSCN, CuI or p-type delafossite structure is formed, wherein A is selected from Cu Or Ag, M are selected from Cr, Ga, Al, Sc, In, Y or Fe, doped chemical is selected from one of Mg, Ca or Ga or a variety of.
(5) nanometer buffer layer is formed
Using sol-gal process, spin coating forms titanium dioxide nanoparticle on transparent conducting glass substrate, using room temperature Dry removal excess of solvent, is then formed on one layer of titanium dioxide molybdenum layer by hydro-thermal method, and is to slowly warm up to 60 DEG C of progress Drying and processing forms nano-TiO2/MoO2Buffer layer.
(6) top electrode is formed
Using evaporation coating method, silver electrode layer is deposited on above-mentioned multilayer film, top electrode can be using with higher work-functions Material, such as gold, silver, copper, aluminium metal and conductive carbon material can be using the production such as vacuum coating and solution film forming Method.
(7) anti-reflecting layer is formed
One layer of anti-reflecting layer is formed on top electrode using evaporation.
The present invention between hole transmission layer by forming nano-TiO2/MoO2Buffer layer structure can preferably protect electricity Sub- transport layer/perovskite absorbed layer/hole transmission layer perovskite solar battery main structure, so as to realize large area Perovskite solar battery manufacture.
Detailed description of the invention:
Fig. 1: double-buffering layer perovskite structure schematic diagram；
Fig. 2: double-buffering layer perovskite manufacturing method flow diagram；
Specific embodiment
Embodiment 1
FTO transparent conducting glass is successively used into acetone, ethyl alcohol, deionized water ultrasonic cleaning, then is handled through UV ozone, is obtained To clean 100nm transparent conducting glass as hearth electrode 101.The TiO electronics that a layer thickness is 80nm is formed on hearth electrode Transport layer 102, subsequent spin coating perovskite thin film on the electron transport layer, and film is placed in 3 seconds in vacuum chamber and is removed with passing through Residual solvent promotes perovskite to be nucleated, and carries out spin coating proceeding in surrounding air；With revolving speed rotation 50 seconds of 4000rpm, so Rotated 18 seconds with the speed of 2000rpm afterwards, 150 DEG C at a temperature of anneal 15 minutes, form 30nm perovskite absorbed layer 103.
The NiO hole transmission layer 104 that 80nm is formed on perovskite absorbed layer, is then formed on upper T iO2/MoO2 The step of nanometer buffer layer 105/106, the forming step of nanometer buffer layer is with lower part nanometer buffer layer, is consistent.
Using evaporation coating method, evaporation thickness is the silver electrode layer 107 of 60nm on above-mentioned multilayer film, and is existed using evaporation The anti-reflecting layer 108 that a layer thickness is 50nm is formed on top electrode.
Embodiment 2
Transparent electro-conductive glass is successively used into acetone, ethyl alcohol, deionized water ultrasonic cleaning, then is handled through UV ozone, is obtained To clean 100nm transparent conducting glass as hearth electrode 101.The ZnO electron transfer layer of one layer of 20nm is formed on hearth electrode (104), subsequent spin coating perovskite thin film on the electron transport layer, and film is placed in vacuum chamber 3 seconds with remaining by removing Solvent promotes perovskite to be nucleated, and carries out spin coating proceeding in surrounding air；Rotate 50 seconds with the revolving speed of 4000rpm, then with The speed of 2000rpm rotates 18 seconds, 150 DEG C at a temperature of anneal 15 minutes, form 50nm perovskite absorbed layer 103.
MoO hole transmission layer 104 is formed on perovskite absorbed layer, is then formed on upper T iO2/MoO2Nanometer is slow Rush layer 105/106, the step of forming step of nanometer buffer layer is with lower part nanometer buffer layer is consistent.
Using evaporation coating method, the silver electrode layer 107 of 80nm thickness is deposited on above-mentioned multilayer film, and using evaporation in top electricity The anti-reflecting layer 108 that a layer thickness is 70nm is formed on extremely.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art For, without departing from the concept of the premise of the invention, various modifications and improvements can be made, these belong to the present invention Protection scope.

Claims (7)

1. a kind of double-buffering layer perovskite method for manufacturing solar battery, it is characterised in that the following steps are included:
(1) hearth electrode is formed
Transparent conducting glass is successively used to acetone, ethyl alcohol, deionized water ultrasonic cleaning, then is handled through UV ozone, cleaning is obtained Transparent conducting glass substrate；
(2) electron transfer layer is formed
One layer of electron transfer layer is formed on the buffer layer；
(3) perovskite absorbed layer is formed
Spin coating perovskite thin film on the electron transport layer, and by film be placed in vacuum chamber 3 seconds with by remove residual solvent come Promote perovskite nucleation, spin coating proceeding is carried out in surrounding air；It is rotated 50 seconds with the revolving speed of 4000rpm, then with 2000rpm Speed rotate 18 seconds, 150 DEG C at a temperature of anneal 15 minutes, formed perovskite absorbed layer.
(4) hole transmission layer is formed
Hole transmission layer is formed on perovskite absorbed layer；
(5) nanometer buffer layer is formed
Using sol-gal process, spin coating forms titanium dioxide nanoparticle on transparent conducting glass substrate, using drying at room temperature Excess of solvent is removed, one layer of titanium dioxide molybdenum layer is then formed on by hydro-thermal method, and be to slowly warm up to 60 DEG C and dried Processing forms nano-TiO2/MoO2Buffer layer；
(6) top electrode is formed
Using evaporation coating method, top electrode layer is deposited on above-mentioned multilayer film；
(7) anti-reflecting layer is formed
One layer of anti-reflecting layer is formed on top electrode using evaporation.
2. double-buffering layer perovskite method for manufacturing solar battery as described in claim 1, which is characterized in that described transparent to lead Electric glass is selected from indium tin oxide (ITO), fluorine tin-oxide (FTO) or aluminium zinc oxide (AZO), and thickness is in 100nm- Between 150nm.
3. double-buffering layer perovskite method for manufacturing solar battery as described in claim 1, which is characterized in that the electronics passes Defeated layer choosing is from TiO, ZnSnO, CsCO, BaTiO, SrTiO, MgTiO, BaSnO, SnO, ZnO or CdS.
4. double-buffering layer perovskite method for manufacturing solar battery as described in claim 1, which is characterized in that the hole passes Defeated layer choosing auto-dope or undoped NiO, CuO, PbS, VO, MoO, CuSCN or CuI.
5. double-buffering layer perovskite method for manufacturing solar battery as described in claim 1, which is characterized in that the hole passes Defeated layer be p-type delafossite structure doped or undoped AMO type semiconductor material, wherein A be selected from Cu or Ag, M be selected from Cr, Ga, Al, Sc, In, Y or Fe, doped chemical are selected from one of Mg, Ca or Ga or a variety of.
6. double-buffering layer perovskite method for manufacturing solar battery as described in claim 1, which is characterized in that top electrode is selected from Gold, silver, copper, aluminium or conductive carbon material.
7. double-buffering layer perovskite method for manufacturing solar battery as described in claim 1, which is characterized in that the top electrode It is prepared by vacuum coating and solution film-forming method.
CN201811108564.1A 2018-09-21 2018-09-21 A kind of double-buffering layer perovskite method for manufacturing solar battery Withdrawn CN109326718A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110190193A (en) * 2019-06-06 2019-08-30 中节能万润股份有限公司 A kind of perovskite solar battery and preparation method thereof containing protective layer
CN114843354A (en) * 2022-04-21 2022-08-02 福州大学 Flexible CZTSSe solar cell based on ultrathin CdS/ZTO double buffer layers and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110190193A (en) * 2019-06-06 2019-08-30 中节能万润股份有限公司 A kind of perovskite solar battery and preparation method thereof containing protective layer
CN110190193B (en) * 2019-06-06 2022-11-15 中节能万润股份有限公司 Perovskite solar cell containing protective layer and preparation method thereof
CN114843354A (en) * 2022-04-21 2022-08-02 福州大学 Flexible CZTSSe solar cell based on ultrathin CdS/ZTO double buffer layers and preparation method thereof

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