CN109273612A - CsPbBr3The continuous gas-phase deposition process for preparing of perovskite battery - Google Patents
CsPbBr3The continuous gas-phase deposition process for preparing of perovskite battery Download PDFInfo
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Abstract
The invention belongs to field of semiconductor photoelectron technique, specially a kind of package technique of chemical gas-phase deposition process for preparing perovskite solar battery, FTO film institute on the whole deposition compact layer NiO of the battery structure in FTO electro-conductive glass2Film or PEDOT:PSS film are as hole transmission layer；Perovskite light absorbing layer film is prepared by continuous chemical vapour deposition method on the hole transport layer；It is absorbed in perovskite and prepares electron transfer layer on layer film；Ag electrode is finally deposited on the electron transport layer as top electrode.To improve perovskite light absorbing layer film quality, substrate spreadability, stability and repeatability, Carrier recombination is reduced.Meanwhile this preparation method is simple, and it is low in cost, new thinking is provided for the commercial applications of perovskite solar battery.
Description
Technical field
The invention belongs to the technical field of thin-film solar cells preparation, in particular to a kind of continuous vapor deposition prepares calcium
Titanium ore light-absorption layer and its battery assembly technology.
Background technique
With the rapid development of human civilization being constantly progressive with social economy, the mankind constantly increase the demand of the energy
It is long.Meanwhile the fossil fuels such as petroleum, coal, natural gas are all non-renewable resources and storage level is limited, therefore for new energy
Research especially to the research of solar energy at the focus of world attention.However silicon substrate and thin-film solar cells it is high at
This, the unstability of the poor efficiency of organic solar batteries, dye-sensitized solar cells makes the development prospect of solar battery
It allows of no optimist.Perovskite solar battery is since 2009 report for the first time, and energy conversion efficiency is maked rapid progress, by initial
3.8% is promoted to 23.3%.Being announced to the world splendidly for perovskite solar battery brings new hope for the development of solar battery.
Among the research boom of perovskite battery, mainly report two major classes preparation process: vacuum thermal evaporation technique and
Solwution method technique.Solwution method technique leads to problems such as film coarse, porous and be not completely covered because of ultrafast reaction rate.Together
When, the poor perovskite thin film material of film quality is generally very unstable in air, thus needs in glove box or ultra-low humidity
It is operated in the environment of degree, thus further limits the industrialization large-area applications of perovskite solar cell.Compare and
Speech, continuous gas phase deposition technology is more reliable, even if equipment is relatively complex and costly, but this is still to increase the big rule of perovskite thin film
One promising candidate of mould industrial application.
Summary of the invention
It is an object of the invention to overcome above-mentioned existing technical deficiency, perovskite is prepared using continuous gas phase deposition technology
Light-absorption layer.Technology itself is intended to invent a kind of new perovskite battery preparation technology, is different from past solwution method preparation.
The invention discloses a kind of technology of preparing of perovskite solar battery light-absorption layer, the battery structure from bottom to up according to
Secondary is first transparency electrode substrate, hole transmission layer, light-absorption layer, electron transfer layer, top electrode.
Above-mentioned light-absorption layer is by ABX3Type perovskite material is formed, and wherein A is selected from Cs+, B is selected from Pb2+, X is selected from Br-, by continuous
Vapour deposition process preparation.
Above-mentioned first transparency electrode substrate is the transparent conductive electrodes such as ITO, FTO, and cave transport layer is MoO3, NiO or CuI etc.
Semiconductor material, with a thickness of 10nm.
Above-mentioned electron transfer layer is inorganic TiO2, ZnO or organic PCBM etc.；Top electrode is Ag electrode, with a thickness of 50nm.
The present invention has abandoned that original solution method film is coarse, porous deficiency using completely new continuous gas phase deposition technology,
Simple technique, the performance of optimization and stable structure provide new think of for the commercial applications of perovskite solar battery
Road.
The present invention also provides a kind of package techniques of translucent perovskite solar battery, the specific steps are as follows:
(1) FTO transparent conducting glass is cut into the strip of 1.5cm, then sticks the adhesive tape of 1cm wide, then with zinc powder and
The dilute hydrochloric acid that concentrated hydrochloric acid and water volume ratio are 1:3 etches 15 minutes, remaining zinc powder is cleaned with dilute hydrochloric acid, the glass etched
Be cut into 1.5 × 1.5cm rectangle, with lye be cleaned by ultrasonic 30-40min, then with alcohol be cleaned by ultrasonic 30min, finally spend from
Sub- water is cleaned by ultrasonic 30min, is then placed in drying box and is dried to obtain first transparency electrode substrate；
(2) in above-mentioned first transparency electrode substrate surface spin coating hole transmission layer precursor liquid, and in quick anneal oven into
Row annealing obtains the transparent electrode substrate of surface coating hole transmission layer；
(3) substrate obtained by step (2) is transferred in vacuum vapor plating instrument chamber, vapor deposition PbBr2Film, thickness
200nm, evaporation rate areChange evaporation source again, CsBr film, thickness 350nm is deposited, evaporation rate isIt is made annealing treatment again, obtains perovskite light-absorption layer.
(4) substrate obtained by step (3) is transferred in glove box, spin coating electron transfer layer.
(5) substrate for taking out step (4) preparation transfers in vacuum vapor plating instrument chamber, with vacuum thermal evaporation plated film
Ag electrode, thickness 50nm is deposited in instrument, and evaporation rate isAs conductive layer；
Further, in step (2), the hole transmission layer precursor liquid is NiOXSolution or organic PEDOT:PSS
Solution, the annealing temperature are 100-450 DEG C, annealing time 15-70min；
Further, in step (4), the electron transfer layer precursor liquid be PCBM solution, concentration 20mg/ml,
The annealing temperature is 80 DEG C~120 DEG C, and annealing time is 20min~50min；
The invention belongs to field of semiconductor photoelectron technique, the technology of preparing and calcium titanium of specially a kind of perovskite light-absorption layer
Mine solar battery assembles technology, which sequentially consists of first transparency electrode substrate, hole transmission layer, calcium titanium
Mine light-absorption layer, electron transfer layer, top electrode, wherein perovskite light-absorption layer uses continuous gas phase deposition technology, improves the cause of film
Close property, reduces the compound of carrier, reduces the series resistance of battery entirety, so improve battery photoelectric conversion efficiency,
Stability etc..Meanwhile it abandoning solwution method and having prepared perovskite light-absorption layer, simple technique, the performance of optimization and stable knot
Structure provides new thinking for the commercial applications of perovskite solar battery.
Detailed description of the invention
Fig. 1 provides continuous vapour deposition process for the present invention and prepares perovskite extinction layer film schematic diagram.
Specific embodiment
The contents of the present invention are described in further detail combined with specific embodiments below, but the present invention is not limited to following
The specific examples of act:
Embodiment 1
(1) FTO transparent conducting glass is cut into the strip of 1.5cm, then sticks the adhesive tape of 1cm wide, then with zinc powder and
The dilute hydrochloric acid that concentrated hydrochloric acid and water volume ratio are 1:3 etches 15 minutes, remaining zinc powder is cleaned with dilute hydrochloric acid, the glass etched
Be cut into 1.5 × 1.5cm rectangle, with lye be cleaned by ultrasonic 30-40min, then with alcohol be cleaned by ultrasonic 30min, finally spend from
Sub- water is cleaned by ultrasonic 30min, is then placed in drying box and is dried to obtain first transparency electrode substrate；
(2) in above-mentioned first transparency electrode substrate surface spin coating NiOXPrecursor liquid, and 400 DEG C are carried out in quick anneal oven
Annealing, annealing time 60min obtain surface and coat NiOXThe first transparency electrode substrate of hole transport film；
(3) substrate obtained by step (2) is transferred in vacuum vapor plating instrument chamber, taking molar ratio is the PbBr of 1:12
It is respectively placed in two groups of evaporation depressed place boats with CsBr solid powder, carries out staged gas phase deposition；Firstly, deposition PbBr2Film, evaporation
Rate isFilm thickness 200nm；Change evaporation source, deposit CsBr film, evaporation rate isFilm thickness is
After plated film, substrate is transferred in glove box by 350nm, carries out 200-300 DEG C of annealing.It obtains surface and passes through company
The ABX of continuous gas phase deposition technology3Extinction laminar substrate.
(4) PCBM be dissolved in chlorobenzene stir 12 hours obtain PCBM precursor liquid, concentration 20mg/ml, in gloves
Using substrate surface spin coating BCPM solution obtained by step (3) as electron transfer layer in case, revolving speed 3000rpm/s, the time is
30s。
(5) Ag electrode, thickness 50nm is deposited with vacuum thermal evaporation plated film instrument, evaporation rate isAs conduction
Layer completes the preparation of perovskite solar battery.
Embodiment 2
(1) the present embodiment is same as Example 1, the difference is that step (2) PEDOT:PSS is spun on it is above-mentioned transparent
Electrode base board surface, revolving speed 4000rpm/s, time 40s, 135 DEG C of annealing in air, annealing time 15min obtain table
The first transparency electrode substrate of face coating PEDOT:PSS hole transport film.
3) substrate obtained by step (2) is transferred in vacuum vapor plating instrument chamber, taking molar ratio is the PbBr of 1:12
It is respectively placed in two groups of evaporation depressed place boats with CsBr solid powder, carries out staged gas phase deposition；Firstly, deposition PbBr2Film, evaporation
Rate isFilm thickness 200nm；Change evaporation source, deposit CsBr film, evaporation rate isFilm thickness is
After plated film, substrate is transferred in glove box by 350nm, carries out 200-300 DEG C of annealing.It obtains surface and passes through company
The ABX of continuous gas phase deposition technology3Extinction laminar substrate.
(4) PCBM be dissolved in chlorobenzene stir 12 hours obtain PCBM precursor liquid, concentration 20mg/ml, in gloves
Using substrate surface spin coating BCPM solution obtained by step (3) as electron transfer layer in case, revolving speed 3000rpm/s, the time is
30s。
(5) Ag electrode, thickness 50nm is deposited with vacuum thermal evaporation plated film instrument, evaporation rate isAs conduction
Layer completes the preparation of perovskite solar battery.
Embodiment 3
The present embodiment is same as Example 1, the difference is that substrate obtained by step (3) is transferred to vacuum by step (4)
In evaporation coating instrument chamber, both hole and electron transport layer PCBM, thickness 10nm is deposited, evaporation rate is
(5) change evaporation source, Ag electrode, thickness 50nm is deposited with vacuum thermal evaporation plated film instrument, evaporation rate isAs conductive layer, the preparation of perovskite solar battery is completed.
It finally illustrates that personal view, above example are only preferred embodiments of the invention, is not intended to restrict the invention, in every case
Any modifications, equivalent replacements, and improvements etc. done within the spirit and principles in the present invention, should be included in guarantor of the invention
Within the scope of shield.
Claims (5)
1. a kind of perovskite solar battery, which is characterized in that the battery structure sequentially consists of electrode base board, hole passes
Defeated layer, light-absorption layer, electron transfer layer, top electrode, the light-absorption layer are ABX3Type perovskite material, wherein A is selected from Cs-, B is selected from
Pb+, X is selected from Br-, using the continuous gas phase deposition technology of two steps, first by PbBr2It is deposited on and is coated with NiOXOr PEDOT:PSS
FTO substrate, then by CsBr in order layer by layer deposition at the top of film.
2. perovskite solar battery as described in claim 1, which is characterized in that the electrode base board is ITO, FTO etc.
Transparent conductive electrode, hole transmission layer MoO3、NiOXOr the semiconductor materials such as PEDOT:PSS.
3. perovskite solar battery as claimed in claim 1 or 2, which is characterized in that the electron transfer layer is inorganic
TiO2, ZnO or organic PCBM, top electrode are metal Ag.
4. about the package technique of translucent perovskite solar battery a kind of, specific step is as follows:
(1) FTO transparent conducting glass is cut into the strip of 1.5cm, then sticks the adhesive tape of 1cm wide, then uses zinc powder and dense salt
Acid etches 15 minutes with the dilute hydrochloric acid that water volume ratio is 1:3, and remaining zinc powder is cleaned with dilute hydrochloric acid, the glass etched is cut into
1.5 × 1.5cm square is cleaned by ultrasonic 30-45min with lye, then is cleaned by ultrasonic 30min with alcohol, finally uses deionized water
It is cleaned by ultrasonic 30min, is then placed in drying box and is dried to obtain FTO transparent electrode substrate；
(2) it in above-mentioned first transparency electrode substrate surface spin coating hole transmission layer precursor liquid, and is moved back in quick anneal oven
Fire processing obtains the transparent electrode substrate of surface coating hole transmission layer；
(3) substrate obtained by step (2) is transferred in vacuum vapor plating instrument chamber, vapor deposition PbBr2 film, thickness
200nm, evaporation rate areChange evaporation source again, CsBr film, thickness 350nm is deposited, evaporation rate isIt is made annealing treatment again, obtains perovskite light-absorption layer.
(4) substrate obtained by step (3) is transferred in glove box, spin coating electron transfer layer.
(5) substrate for taking out step (4) preparation transfers in vacuum vapor plating instrument chamber, is steamed with vacuum thermal evaporation plated film instrument
Ag electrode, thickness 60nm are plated, evaporation rate isAs conductive layer.
5. preparation method as claimed in claim 4, which is characterized in that in step (2), the hole transmission layer is
MoO3、NiOXOr the semiconductor materials such as PEDOT:PSS.In step (3), the BX2Molar ratio with AX is 1:1, the annealing
Treatment temperature is 200 DEG C -350 DEG C, and annealing time is 30min~60min；In step (4), the electron transfer layer is inorganic
TiO2, ZnO or organic PCBM, annealing temperature is 80 DEG C~120 DEG C, and annealing time is 20min~50min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111403539A (en) * | 2020-03-19 | 2020-07-10 | 华中科技大学 | All-inorganic perovskite photoelectric detector and preparation method thereof |
| CN112331740A (en) * | 2020-10-27 | 2021-02-05 | 华中科技大学 | Preparation method of inorganic perovskite solar cell adopting spin coating-evaporation two-step method |
| CN113192843A (en) * | 2021-04-06 | 2021-07-30 | 电子科技大学 | Preparation method and application of novel non-lead-based perovskite film |
| CN113192821A (en) * | 2021-04-20 | 2021-07-30 | 电子科技大学 | All-inorganic CsPbI3Preparation method and application of perovskite thin film |
| CN113284980A (en) * | 2021-05-13 | 2021-08-20 | 中山艾尚智同信息科技有限公司 | Defect eliminating method for all-inorganic perovskite solar cell |
| CN113785408A (en) * | 2019-06-03 | 2021-12-10 | 马卡罗有限公司 | Preparation method of perovskite solar cell absorption layer based on chemical vapor deposition method |
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| CN107068866A (en) * | 2016-12-27 | 2017-08-18 | 济南大学 | A kind of translucent perovskite solar cell and its package technique |
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| CN107452886A (en) * | 2017-08-12 | 2017-12-08 | 西南大学 | A kind of laminated film and Organic Light Emitting Diode and preparation method thereof |
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| CN107075657A (en) * | 2014-07-09 | 2017-08-18 | 牛津大学科技创新有限公司 | Two step sedimentations |
| CN106887520A (en) * | 2015-12-15 | 2017-06-23 | 北京大学 | A kind of perovskite solar cell of additive auxiliary and preparation method thereof |
| CN107068866A (en) * | 2016-12-27 | 2017-08-18 | 济南大学 | A kind of translucent perovskite solar cell and its package technique |
| CN107452886A (en) * | 2017-08-12 | 2017-12-08 | 西南大学 | A kind of laminated film and Organic Light Emitting Diode and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113785408A (en) * | 2019-06-03 | 2021-12-10 | 马卡罗有限公司 | Preparation method of perovskite solar cell absorption layer based on chemical vapor deposition method |
| CN111403539A (en) * | 2020-03-19 | 2020-07-10 | 华中科技大学 | All-inorganic perovskite photoelectric detector and preparation method thereof |
| CN112331740A (en) * | 2020-10-27 | 2021-02-05 | 华中科技大学 | Preparation method of inorganic perovskite solar cell adopting spin coating-evaporation two-step method |
| CN113192843A (en) * | 2021-04-06 | 2021-07-30 | 电子科技大学 | Preparation method and application of novel non-lead-based perovskite film |
| CN113192821A (en) * | 2021-04-20 | 2021-07-30 | 电子科技大学 | All-inorganic CsPbI3Preparation method and application of perovskite thin film |
| CN113284980A (en) * | 2021-05-13 | 2021-08-20 | 中山艾尚智同信息科技有限公司 | Defect eliminating method for all-inorganic perovskite solar cell |
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Application publication date: 20190125 |