CN109148688A - A kind of efficient perovskite solar battery and preparation method thereof - Google Patents
A kind of efficient perovskite solar battery and preparation method thereof Download PDFInfo
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- CN109148688A CN109148688A CN201810756629.7A CN201810756629A CN109148688A CN 109148688 A CN109148688 A CN 109148688A CN 201810756629 A CN201810756629 A CN 201810756629A CN 109148688 A CN109148688 A CN 109148688A
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- H—ELECTRICITY
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- H—ELECTRICITY
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- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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- 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
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Abstract
The invention belongs to semiconductor photoelectronic device field, specially a kind of efficient perovskite solar battery and preparation method thereof.The structure of perovskite solar battery of the present invention is from the bottom up successively are as follows: transparent substrates, first transparency electrode layer, translucent functional layer, the second electrode lay.Wherein translucent functional layer is followed successively by electron transfer layer, potassium halogen salt deposit, perovskite light absorbing layer, hole transmission layer from the bottom to top, or is hole transmission layer, potassium halogen salt deposit, perovskite light absorbing layer, electron transfer layer.The preparation method of this perovskite solar battery includes: spin coating potassium haloid on the electron transport layer, pass through the annealing of perovskite, potassium haloid is diffused into calcium titanium ore bed, it initiatively can effectively be passivated calcium titanium ore bed, enhance the crystallinity of perovskite, light absorption is improved, and finally improves the efficiency of solar battery.Preparation method of the present invention is relatively simple, and tool has significant practical applications.
Description
Technical field
The invention belongs to semiconductor photoelectronic device technical fields, and in particular to perovskite solar battery and its preparation side
Method.
Background technique
Nowadays, solar energy has become the important component of renewable energy.Perovskite battery is due to its preparation cost
The low, many advantages such as preparation process is simple, incident photon-to-electron conversion efficiency is high, it is considered to be most promising photovoltaic solar-electricity of new generation
Pond.By fast-developing in recent years, incident photon-to-electron conversion efficiency is promoted from 3.8% in 2009 in July, 2017
22.7%.The efficiency has been able to compare favourably with silica-based solar cell.
The quality of perovskite absorbed layer will will have a direct impact on the photoelectric characteristic of perovskite solar battery.Perovskite solar energy
There are many defect states for battery, these mainly play Carrier recombination center by the defect state that volume defect and surface defect are constituted
Effect.Surface defect is present in the grain boundary and perovskite absorbed layer interface of perovskite, by surface dangling bonds and unsaturation
Atom generates.Volume defect is present in perovskite crystal, is made of vacancy and interstitial atom.The surface topography of perovskite absorbed layer
It also will affect defect state density with material property.The performance of device will effectively be promoted by reducing defect state density.
Summary of the invention
The purpose of the present invention is to provide a kind of low costs, efficient perovskite solar battery and preparation method thereof.
Efficient perovskite solar battery provided by the invention, by lamination, preparation process is prepared, and structure is under
Supreme successively includes: transparent substrates, first transparency electrode layer, translucent functional layer, the second electrode lay；Wherein:
The transparent substrates are quartz material rigid glass substrates or flexibility PET or flexibility PEN substrate.Quartz material hard glass
Substrate high temperature resistant, light transmittance are high.
The first transparency electrode layer is located on transparent substrates, material be metal oxide, for example, ITO or FTO,
It is with a thickness of 100-200nm, and square resistance is less than 10 Ω/.
The translucent functional layer is located on first transparency electrode layer, and translucent functional layer is followed successively by electronics from the bottom to top
Transport layer, potassium halogen salt deposit, perovskite light absorbing layer, hole transmission layer, or be hole transmission layer, potassium halogen salt deposit, calcium titanium
Mine light absorbing layer, electron transfer layer；
The material of electron transfer layer can be but be not limited to TiO2、SnO2, ZnO, PCBM or C60, with a thickness of 25-200 nm；
The material of potassium halogen salt deposit is KF, KCl, KBr or KI, with a thickness of 30-300nm；
The material of perovskite light absorbing layer can be but be not limited to FA0.85MA0.15Pb(I0.85Br0.15)3、MAPbI3Or MAPbI3- xClx, thickness is less than 350 nm, for example, 100-350 nm；
The material of hole transmission layer can be but be not limited to Spiro-OMeTAD, PEDOT:PSS, NiOx, P3HT or PTAA, it is thick
Degree is 40-200 nm；
The second electrode lay is located on semitransparent electrode layer, and material is gold or silver.With a thickness of 40-150nm.
The preparation method of perovskite solar battery of the present invention, the following steps are included:
(1) transparent conductive substrate is cleaned, dry and surface hydrophilicity improve；
(2) first transparency electrode layer is prepared on substrate；
(3) electron transfer layer is prepared on first transparency electrode layer in ultra-clean chamber, later spin coating potassium halogen on the electron transport layer
Plain salt deposit is sequentially prepared perovskite using solwution method in the glove box that water oxygen content is below 1 ppm on the electron transport layer
Light absorbing layer, hole transmission layer；
Or hole transmission layer is prepared on first transparency electrode layer in ultra-clean chamber, spin coating potassium halogen on the hole transport layer later
Plain salt deposit is sequentially prepared perovskite using solwution method in the glove box that water oxygen content is below 1 ppm on the hole transport layer
Light absorbing layer, electron transfer layer；
(4) substrate prepared is put into vacuum evaporating coating machine rapidly, vapor deposition forms the second electrode lay, completes perovskite too
The preparation of positive energy battery.
Efficient perovskite solar battery provided by the invention, its working principle is that: when solar irradiation is mapped on electrode, calcium
Titanium ore absorbed layer absorbs visible light, ultraviolet light, and exciton, excitonic motion to light-absorption layer, charge (electronics, sky are generated in light-absorption layer
Cave) transmission bed boundary, under the action of built-in field, electrons and holes separation, electron transfer layer transmits electronics to cathode, hole
Transport layer transporting holes reach anode, form series connection photoelectric current.Charge transport layer includes electron transfer layer and hole transmission layer.
Compared with prior art, the invention has the following advantages that
(1) compared to the perovskite solar battery of no potassium haloid, perovskite solar battery according to the present invention
Light absorption is remarkably reinforced, and the crystal grain of calcium titanium ore bed will increase, and the crystallinity of perovskite can be remarkably reinforced.Meanwhile potassium haloid meeting
It is diffused into calcium titanium ore bed in annealing process, the defects of passivation calcium titanium ore bed state is final to promote perovskite solar-electricity
The performance in pond；
(2) perovskite solar battery preparation process according to the present invention uses solwution method, the simple, cost with preparation process
Low advantage.It can effectively improve the photoelectric conversion efficiency of perovskite solar battery and make it have bigger market potential.
The present invention is a kind of efficient perovskite solar battery, and potassium haloid can be spread in the annealing process of perovskite
Into perovskite light absorbing layer, enhance the crystallinity of perovskite, enhance the light absorption of perovskite, is slightly reduced the forbidden band of perovskite
Width, and it is passivated the defect state of perovskite light absorbing layer, the final efficiency for promoting perovskite solar battery.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of efficient perovskite solar battery in the embodiment of the present invention 1.
Figure label: 101 be transparent substrates, and 102 be first transparency electrode layer, and 103 be electron transfer layer, and 104 be potassium halogen
Plain salt deposit, 105 perovskite light absorbing layers, 106 be hole transmission layer, and 107 be the second electrode lay.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.
Embodiment 1
A kind of structure of efficient perovskite solar battery 101 is as shown in Figure 1: transparent substrates, 102 is first transparency electrode
Layer, 103 be electron transfer layer, 104 be potassium halogen salt deposit, 105 be perovskite light absorbing layer, 106 be hole transmission layer, 107 be
The second electrode lay.Transparent substrates are quartz glass；First transparency electrode layer is ITO, with a thickness of 100 nm；Electron transfer layer is
SnO2, with a thickness of 25 nm；Potassium halogen salt deposit is KCl, with a thickness of 15 nm；Calcium titanium ore bed is MAPbI3-xClx, with a thickness of 300
nm；Hole transmission layer is Spiro-OMeTAD, with a thickness of 50nm；The second electrode lay is gold, with a thickness of 50 nm.
Perovskite solar battery in embodiment 1 the preparation method is as follows:
ITO electro-conductive glass is successively cleaned with ethyl alcohol, acetone, deionized water, is removed after dry with UV ozone cleaning machine remaining
Organic matter；The SnO for being 2.67% by concentration2Nano sol is spin-coated to clean transparent conductive glass surface, and at 180 DEG C
Lower annealing 30min obtains the SnO with a thickness of 25nm2Electron transfer layer.The KCl aqueous solution that concentration is 25mg/ml is spin-coated to electricity
In sub- transport layer, uniform KCl film is formed, 130 DEG C of annealing 15min in vacuum obtain KCl layers；It is 7:3's in volume ratio
Lead iodide, lead chloride and iodine methylamine, the lead iodide, lead chloride are added in the mixed solution of gamma-butyrolacton and dimethyl sulfoxide
Molar ratio with iodine methylamine is 1:0.1:1.2, and 50 DEG C of constant temperature stir 12h in glove box, forms the calcium of the 40wt% of yellow homogeneous
Titanium ore precursor solution；Resulting perovskite precursor solution is spin-coated on KCl layer with anti-solwution method, is formed uniform
MAPbI3-xClxFilm, anneal 14min at 100 DEG C, obtains fine and close perovskite light absorbing layer.It is added in 1ml chlorobenzene
Spiro-OMeTAD 72.3mg, two (trifluoro methylsulfonyl) imine lithiums (Li-TFSI), 17.5 15 μ l, 4- tert-butyl pyrrole of μ l, FK209
29 μ l of pyridine is stirred at room temperature 3h and forms hole transport layer material solution；By resulting hole transport layer material solution spin coating calcium
On titanium ore light absorbing layer, hole transmission layer is formed.Finally, gold electrode is deposited on the hole transport layer by thermal evaporation deposition, complete
The preparation of perovskite solar battery.
Embodiment 2
The structure of perovskite solar battery is from the bottom up successively are as follows: transparent substrates, first transparency electrode layer, hole transmission layer,
Potassium halogen salt deposit, perovskite light absorbing layer, electron transfer layer, the second electrode lay.Transparent substrates are quartz glass；First transparent electricity
Pole layer is ITO, with a thickness of 100nm；Hole transmission layer is NiOx, with a thickness of 40 nm；Potassium halogen salt deposit is KCl, with a thickness of
15nm；Calcium titanium ore bed is MAPbI3-xClx, with a thickness of 300nm；Electron transfer layer is PCBM, with a thickness of 50nm；The second electrode lay
For silver, with a thickness of 80 nm.
Perovskite solar battery in embodiment 1 the preparation method is as follows:
ITO electro-conductive glass is successively cleaned with ethyl alcohol, acetone, deionized water, is removed after dry with UV ozone cleaning machine remaining
Organic matter；By the ethanol solution of nickel nitrate, it is spin-coated to clean transparent conductive glass surface, and is annealed at 280 DEG C
30min obtains the NiO with a thickness of 40 nmxHole transmission layer.The KCl aqueous solution that concentration is 25mg/ml is spin-coated to hole to pass
On defeated layer, uniform KCl film is formed, 130 DEG C of annealing 15min in vacuum obtain KCl layers；In γ-fourth that volume ratio is 7:3
Lead iodide, lead chloride and iodine methylamine, the lead iodide, lead chloride and iodine first are added in the mixed solution of lactone and dimethyl sulfoxide
The molar ratio of amine is 1:0.1:1.2, and 50 DEG C of constant temperature stir 12h in glove box, before forming the perovskite of the 40wt% of yellow homogeneous
Drive liquid solution；Resulting perovskite precursor solution is spin-coated on KCl layer with anti-solwution method, forms uniform MAPbI3-xClx
Film, anneal 14min at 100 DEG C, obtains fine and close perovskite light absorbing layer.PCBM20 mg is added in 1ml chlorobenzene,
Stirring 3h forms electron transport layer materials solution at room temperature；By resulting electron transport layer materials solution spin coating perovskite light absorption
On layer, electron transfer layer is formed.Finally, gold electrode is deposited on the electron transport layer by thermal evaporation deposition, the perovskite sun is completed
The preparation of energy battery.
The energy conversion efficiency of perovskite solar battery according to the present invention can achieve 19.4%.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and not limits, although reference
Preferred embodiment describes the invention in detail, those skilled in the art should understand that, it can be to of the invention
Technical solution is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered
In scope of the presently claimed invention.
Claims (6)
1. a kind of efficient perovskite solar battery, which is characterized in that its structure is from the bottom to top successively are as follows: transparent substrates, first
Transparent electrode layer, translucent functional layer, the second electrode lay；Wherein:
The first transparency electrode layer is located on transparent substrates, and material is metal oxide；
The translucent functional layer is located on first transparency electrode layer, and translucent functional layer is followed successively by electron-transport from the bottom to top
Layer, potassium halogen salt deposit, perovskite light absorbing layer, hole transmission layer, or be hole transmission layer, potassium halogen salt deposit, perovskite light
Absorbed layer, electron transfer layer；
The top the second electrode lay is located above translucent function, is metallic gold or metallic silver.
2. efficient perovskite solar battery according to claim 1, which is characterized in that the first transparency electrode layer
Material uses metal oxide ITO or FTO, and with a thickness of 100-200 nm, square resistance is less than 10 Ω/.
3. efficient perovskite solar battery according to claim 1 or 2, which is characterized in that the hole transmission layer material
Material is Spiro-OMeTAD, PEDOT:PSS, NiOx, P3HT or PTAA, with a thickness of 40-200 nm；Electron transport layer materials are
TiO2、SnO2, ZnO, PCBM or C60, with a thickness of 25-200 nm；
Potassium haloid layer material is KF, KCl, KBr or KI, with a thickness of 30-300nm；
Perovskite light absorption layer material is FA0.85MA0.15Pb(I0.85Br0.15)3、MAPbI3Or MAPbI3-xClx, with a thickness of 200-
350 nm。
4. efficient perovskite solar battery according to claim 3, which is characterized in that the second electrode lay is semi-transparent
It is metallic gold or metallic silver, thickness 40-150nm above bright functional layer.
5. efficient perovskite solar battery according to claim 1,2 or 4, which is characterized in that the transparent substrates material
Material is quartz material rigid glass substrates or flexibility PET or flexibility PEN substrate.
6. a kind of preparation method of the efficient perovskite solar battery as described in one of claim 1-5, which is characterized in that tool
Body step are as follows:
(1) transparent conductive substrate is cleaned, dry and surface hydrophilicity improve；
(2) first transparency electrode layer is prepared on substrate；
(3) electron transfer layer is prepared on first transparency electrode layer in ultra-clean chamber, later spin coating potassium halogen on the electron transport layer
Plain salt deposit is sequentially prepared perovskite using solwution method in the glove box that water oxygen content is below 1 ppm on the electron transport layer
Light absorbing layer, hole transmission layer；
Or hole transmission layer is prepared on first transparency electrode layer in ultra-clean chamber, spin coating potassium halogen on the hole transport layer later
Plain salt deposit is sequentially prepared perovskite using solwution method in the glove box that water oxygen content is below 1 ppm on the hole transport layer
Light absorbing layer, electron transfer layer；
(4) substrate prepared is put into vacuum evaporating coating machine rapidly, vapor deposition forms the second electrode lay, completes perovskite too
The preparation of positive energy battery.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110504362A (en) * | 2019-07-17 | 2019-11-26 | 浙江浙能技术研究院有限公司 | A kind of SnO2The method of modifying of electronic selection transport layer |
| CN111162179A (en) * | 2019-12-30 | 2020-05-15 | 电子科技大学 | High-reflection-film-coverage semitransparent perovskite solar cell and preparation method thereof |
| CN111477745A (en) * | 2020-04-08 | 2020-07-31 | 天合光能股份有限公司 | Solar cell and manufacturing method thereof |
| CN112820832A (en) * | 2021-02-08 | 2021-05-18 | 珠海复旦创新研究院 | Efficient perovskite solar cell and preparation method thereof |
| WO2023143207A1 (en) * | 2022-01-27 | 2023-08-03 | 西安隆基乐叶光伏科技有限公司 | Solar cell and preparation method therefor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110504362A (en) * | 2019-07-17 | 2019-11-26 | 浙江浙能技术研究院有限公司 | A kind of SnO2The method of modifying of electronic selection transport layer |
| CN111162179A (en) * | 2019-12-30 | 2020-05-15 | 电子科技大学 | High-reflection-film-coverage semitransparent perovskite solar cell and preparation method thereof |
| CN111477745A (en) * | 2020-04-08 | 2020-07-31 | 天合光能股份有限公司 | Solar cell and manufacturing method thereof |
| CN111477745B (en) * | 2020-04-08 | 2023-09-22 | 天合光能股份有限公司 | Solar cell and manufacturing method thereof |
| CN112820832A (en) * | 2021-02-08 | 2021-05-18 | 珠海复旦创新研究院 | Efficient perovskite solar cell and preparation method thereof |
| WO2023143207A1 (en) * | 2022-01-27 | 2023-08-03 | 西安隆基乐叶光伏科技有限公司 | Solar cell and preparation method therefor |
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