CN109713137A - Element gas phase doping method for perovskite solar cell transport layer - Google Patents
Element gas phase doping method for perovskite solar cell transport layer Download PDFInfo
- Publication number
- CN109713137A CN109713137A CN201811646007.5A CN201811646007A CN109713137A CN 109713137 A CN109713137 A CN 109713137A CN 201811646007 A CN201811646007 A CN 201811646007A CN 109713137 A CN109713137 A CN 109713137A
- Authority
- CN
- China
- Prior art keywords
- solar cell
- perovskite solar
- doping
- gas phase
- transport layer
- 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
Links
Classifications
-
- 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
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of novel element gas phase doping methods, the in particular to preparation method applied to the element gas phase doping electron transfer layer of perovskite solar cell.The element gas phase doping method is easy to operate, is easy to repeat, and doped chemical wide variety is, it can be achieved that Quick uniform adulterates.It is reacted it is characterized by: sample is put into heat in the cavity containing element-specific gas, doping is effectively adjusted by the concentration of element-specific in control heating time, temperature and cavity.This method can carry out the doping of multiple element to the electron transfer layer in perovskite solar cell, including fluorine element, chlorine element, nitrogen etc., N doping electron transfer layer is successfully prepared by this method, and be applied in perovskite solar cell, the current density and photoelectric conversion efficiency of perovskite solar cell are improved significantly.
Description
Technical field
The invention discloses a kind of novel element gas phase doping methods, in particular to applied to perovskite solar cell
The preparation method of element gas phase doping electron transfer layer.
Background technique
With the development of economy and society, demand of the people to the energy is higher and higher.In order to better solve fossil energy
Exhausted problem and the living environment for improving us, developing and utilizing the renewable energy such as solar energy becomes a kind of inevitable choice,
Perovskite solar cell is current one of research hotspot.2009, perovskite solar cell was reported for the first time, and transfer efficiency is
3.8%, as researcher continues to optimize perovskite solar cell material therefor and battery structure, by short ten years
Less than time, transfer efficiency has had been raised to 23.2%, and also shows the trend of rising.With traditional silicon substrate sun
Battery is compared, and perovskite solar cell development potentiality and application prospect are preferable, and research and development perovskite solar cell has very much must
It wants.
In general, the perovskite solar cell of common plate hetero-junctions is mainly made of six parts, from bottom to top successively
Are as follows: substrate of glass, transparent electrode, electron transfer layer, perovskite absorbed layer, hole transmission layer, metal electrode.Wherein electron-transport
There are commonly titanium dioxide, tin oxide etc. for layer.In perovskite solar cell, electron transfer layer can both transmit electronics or can
Hole is stopped to have the performance of perovskite solar cell to Guan Chong so electron transfer layer is also referred to as hole blocking layer
The influence wanted.Reasonably optimize electron transfer layer, photo-generated carrier in perovskite solar cell can be promoted to separate, promote battery
Carrier collection ability, and then improve battery photoelectric conversion efficiency.The method of optimization electron transfer layer common at present has
" interface engineering " and " doping engineering ".Electron transfer layer conduction electricity can be effectively improved by " interface engineering " passivation interface defect
The ability of son.Such method is usually that one layer of decorative material is introduced between perovskite absorbed layer and electron transfer layer, is come with this
It is passivated the surface defect of electron transfer layer, improves carrier transmission performance.It can be targetedly to electronics by " doping engineering "
Transport layer optimizes modification, and some specific elements are mixed in electron transfer layer to be efficiently reduced in electron transfer layer
Defect, improve its conductive capability.
In order to simplify the doping method of electron transfer layer and expand the range of doped chemical, the present invention provides a kind of novel
Element gas phase doping method suitable for the doping of multiple element, and is suitable for various film samples, including perovskite sun electricity
Electron transfer layer in pond.The method simply easily repeats, it can be achieved that Quick uniform adulterates, in raising electron-transport effectively
Sample will not be polluted while layer performance.
Summary of the invention
The present invention provides a kind of doping methods of electron transfer layer applied to perovskite solar cell, mainly provide
A kind of method and technology of element gas phase doping.Element gas phase doping method disclosed by the invention utilizes liquid vapour in airtight cavity
Change and generate high pressure, while uniformly being contacted with sample surfaces, is reacted under conditions of high pressure.The method is easy to operate, is easy to adjust
Control, suitable for doping of multiple element, including fluorine element, nitrogen, chlorine element etc., method parameter adjustability is high, can pass through
Reaction temperature, solution concentration and reaction time are adjusted to adjust doping.Element gas phase doping method is successfully passed through herein to exist
Nitrogen is mixed in tin oxide transport layer, obtains N doping tin oxide transport layer, and be applied in perovskite solar cell,
Effectively improve the current density and photoelectric conversion efficiency of perovskite solar cell.It is described to be based on N doping tin oxide transport layer
Perovskite solar cell structure from bottom to top successively are as follows: substrate of glass, ito transparent electrode, electron transfer layer, calcium titanium ore bed,
Hole transmission layer, gold electrode.
Gas phase element doping method disclosed by the invention is applied widely, doped chemical multiplicity, including fluorine element, nitrogen member
Element, chlorine element etc..Below with nitrogen-doping tin oxide transport layer, uses reaction kettle as airtight cavity, illustrate
The step of gas phase element doping method.Steps are as follows for the specific method of gas phase nitrogen-doping tin oxide transport layer:
A. clean ITO electro-conductive glass substrate, prepare one layer of SnO 2 thin film in clean substrate, film thickness 10nm~
Between 100nm；
B. certain volume ratio weak ammonia is pressed, the ratio of NH3H2O:H2O is between 1:0~1:50.Benefit of the invention
It is vaporized with ammonium hydroxide and is uniformly contacted with sample surfaces, reacted under conditions of high pressure, to sample adulteration.In order to reasonably adjust doping
It measures and sample is protected by high pressure alkalinity gas attack, not need reasonably to adjust the volume ratio of ammonium hydroxide and water；
C. the ammonium hydroxide diluted is instilled in reaction kettle, liquor capacity accounts for the 5%~75% of reaction kettle capacity.In order to reasonable
Ground adjusts doping, it would be desirable to strictly control liquor capacity, and then control reaction pressure, reach to sample Uniform Doped
Effect；
D. the ITO electro-conductive glass substrate for being prepared for SnO 2 thin film is put into reaction kettle, substrate is kept when being put into
It is prepared with the one side of SnO 2 thin film upward, the distance between sample and solution are maintained between 1cm~5cm.In order to guarantee sample
Product surface and gas uniformly contact, and sample is avoided to be directly exposed to the surface of liquid, sample to be kept with solution it is certain away from
From being placed on specimen face side；
E. reaction kettle is put into heater box, heating temperature is between 60 DEG C~200 DEG C, and heating time is in 0.5h~for 24 hours
Between.In order to reasonably adjust doping, it would be desirable to strictly control reaction temperature and reaction time, reach uniform to sample
The effect of doping.
Specific embodiment
The raw materials used in the present invention is all made of commercially available chemically pure reagent, is the present invention into one below with reference to specific implementation case
Step is described in detail.In the case where not violating purport of the invention, the present invention should be not limited to the content that following embodiment is specifically expressed.
Case study on implementation one:
It prepares N doping tin oxide transport layer using element gas phase doping method and prepares and transmitted based on N doping tin oxide
The perovskite solar cell of layer, steps are as follows:
A. ITO electro-conductive glass substrate is cleaned: with by the ITO electro-conductive glass of the dust-free paper wiping 1.2*1.8cm2 of alcohol dampening
Then ITO electro-conductive glass substrate is successively used deionized water, ethyl alcohol to rinse, is dried with nitrogen, obtains cleaning bright ITO by substrate
Electro-conductive glass substrate is placed in 60 DEG C of kept dries in drying box；
B. it prepares tin oxide transport layer: preparing tin oxide solution.The ITO electro-conductive glass substrate cleaned up is placed on ultraviolet
Ozone treatment 30min under ozone surface processing equipment UV ultraviolet lamp forms water-wetted surface.With the method for spin coating by the oxidation of preparation
Solution of tin is spin-coated in the ITO electro-conductive glass substrate handled well, revolving speed 5000rpm, time 15s, the good tin oxide of spin coating
The ITO electro-conductive glass of solution is placed on warm table, and 30min is heated at 180 DEG C, forms the oxygen of even compact on ITO electro-conductive glass
Change tin thin film；
C. N doping tin oxide transport layer: suitable deionized water being added dropwise into reaction kettle, then NH by volume3·
H2O:H2Ammonium hydroxide is added dropwise into reaction kettle for the dilution ratio of O=1:1, then the ITO that the surface handled well is coated with SnO 2 thin film is led
Electric glass is put into reaction kettle, and SnO 2 thin film not allowed to directly contact the solution in reaction kettle when paying attention to being put into, and is protected
Hold SnO 2 thin film surface cleaning.Finally reaction kettle is put into heater box, 2h is kept the temperature at 110 DEG C, is taken out after natural cooling；
D. perovskite thin film is prepared: by a certain percentage by PbI2, MAI (methylamine iodine) and FAI (carbonamidine iodine) be dissolved in DMSO (two
Methyl sulfoxide) in, the solution prepared is placed on magnetic stirring apparatus and stirs 8h, is uniformly mixed it, it is spare to have stirred filtering.With
Prepared perovskite solution is spun on fine and close N doping SnO 2 thin film surface (revolving speed 4000rpm, the time by spin-coating method
For 30s), the ITO electro-conductive glass of the good perovskite thin film of spin coating is placed on warm table, heats 15min at 150 DEG C, obtained uniformly
Fine and close perovskite thin film；
E. it prepares hole transmission layer (Spiro-OMeTAD film): preparing Spiro-OMeTAD solution by a certain percentage, so
Prepared Spiro-OMeTAD solution (80mg/mL) is spun on the perovskite thin film prepared afterwards, spin speed is
6000rpm, spin-coating time 30s；
F. it prepares gold electrode: preparing gold electrode with the method for vacuum evaporation, gold electrode thickness is about 60nm.
So far, a kind of perovskite solar cell based on N doping tin oxide transport layer, which is just prepared, completes.
The present invention is not polluting SnO 2 thin film and is not changing tin oxide by a kind of novel element gas phase doping method
Nitrogen is successfully mixed in the case where film surface appearance in SnO 2 thin film, is obtained a kind of novel based on N doping oxygen
Change tin transport layer perovskite solar cell, successfully prepare low cost, high electron mobility, high-photoelectric transformation efficiency calcium
Titanium ore solar cell.
Detailed description of the invention
Fig. 1 is the XPS figure of N doping SnO 2 thin film, and SnO 2 thin film is prepared on ITO electro-conductive glass；
Fig. 2 is the perovskite solar cell structural schematic diagram based on N doping tin oxide transport layer；
Fig. 3 is the J-V figure based on N doping tin oxide transport layer perovskite solar cell.
Claims (5)
1. being used for the element gas phase doping method of perovskite solar cell transport layer, it is characterised in that: using containing doped chemical
Liquid vaporized in airtight cavity and generate high pressure, while gas is uniformly contacted with sample surfaces, is reacted, to sample progress
Doping, the method have solution concentration, and reaction temperature, pressure adjustable are easy to operate, applied widely, doped chemical type
Quick uniform doping can be achieved in the advantage of multiplicity under the premise of not contaminated samples, wherein the solution that airtight cavity is added can be with
It is diluted solution, the 5%~75% of airtight cavity volume can also be accounted for not diluted direct use, liquor capacity.
2. one kind prepared by the element gas phase doping method according to claim 1 for perovskite solar cell transport layer
The electron-transports layer films such as the tin oxide or titanium dioxide of the doping of the multiple elements such as nitrogen, it is characterised in that: the electronics such as tin oxide pass
The element dopings such as the nitrogen of defeated layer film.
3. according to claim 1 with the element gas phase doping side as claimed in claim 2 for perovskite solar cell transport layer
Method prepares a kind of perovskite solar cell based on the electron transfer layers such as the element dopings such as nitrogen tin oxide or titanium dioxide, feature
Be: prepared perovskite solar cell structure is from bottom to top successively are as follows: substrate of glass, ito transparent electrode, element doping oxygen
Change the electron transfer layers such as tin or titanium dioxide, calcium titanium ore bed, hole transmission layer, gold electrode.
4. the element gas phase doping method according to claim 1 for perovskite solar cell transport layer, feature exist
In: this method can also adulterate other element-specifics, such as chlorine element, fluorine element etc. other than can be with nitrogen doped, can also
To adulterate other ions, such as iodide ion, bromide ion, ammonium ion, it can also be some other small organic molecules.
5. the element gas phase doping method according to claim 1 for perovskite solar cell transport layer, feature exist
In: this method, can also be to others one other than it can be doped to tin oxide or titanic oxide electronic transmission layer film
A little two-dimensional materials and three-dimensional material are doped, such as the sky in graphene film, zinc-oxide film, perovskite solar cell
Cave transport layer etc..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811646007.5A CN109713137A (en) | 2018-12-30 | 2018-12-30 | Element gas phase doping method for perovskite solar cell transport layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811646007.5A CN109713137A (en) | 2018-12-30 | 2018-12-30 | Element gas phase doping method for perovskite solar cell transport layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109713137A true CN109713137A (en) | 2019-05-03 |
Family
ID=66260427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811646007.5A Pending CN109713137A (en) | 2018-12-30 | 2018-12-30 | Element gas phase doping method for perovskite solar cell transport layer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109713137A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110176539A (en) * | 2019-05-16 | 2019-08-27 | 浙江大学 | A kind of preparation method of the stable efficient perovskite solar battery of full spectrum light |
| CN113421934A (en) * | 2021-06-16 | 2021-09-21 | 青岛科技大学 | Perovskite light absorption layer material and method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033082A (en) * | 2007-04-18 | 2007-09-12 | 大连理工大学 | Method of preparing titanium dioxide, stannum dioxide and doping composite fiber material thereof |
| CN101279251A (en) * | 2008-02-27 | 2008-10-08 | 浙江大学 | One-dimensional embedded with hetero-junction photocatalyst intermingle with TiO2 and preparation and use thereof |
| CN104248967A (en) * | 2014-06-17 | 2014-12-31 | 扬州大学 | Vapor phase method for preparation of porous carrier supported nitrogen doped titanium dioxide |
| CN205028929U (en) * | 2015-08-19 | 2016-02-10 | 辽宁工业大学 | Perovskite type solar cell |
-
2018
- 2018-12-30 CN CN201811646007.5A patent/CN109713137A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033082A (en) * | 2007-04-18 | 2007-09-12 | 大连理工大学 | Method of preparing titanium dioxide, stannum dioxide and doping composite fiber material thereof |
| CN101279251A (en) * | 2008-02-27 | 2008-10-08 | 浙江大学 | One-dimensional embedded with hetero-junction photocatalyst intermingle with TiO2 and preparation and use thereof |
| CN104248967A (en) * | 2014-06-17 | 2014-12-31 | 扬州大学 | Vapor phase method for preparation of porous carrier supported nitrogen doped titanium dioxide |
| CN205028929U (en) * | 2015-08-19 | 2016-02-10 | 辽宁工业大学 | Perovskite type solar cell |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110176539A (en) * | 2019-05-16 | 2019-08-27 | 浙江大学 | A kind of preparation method of the stable efficient perovskite solar battery of full spectrum light |
| CN113421934A (en) * | 2021-06-16 | 2021-09-21 | 青岛科技大学 | Perovskite light absorption layer material and method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108470835B (en) | Perovskite solar battery and preparation method thereof based on two-dimentional transition metal carbide or nitride | |
| CN104250723B (en) | Chemical method for in-situ large-area controlled synthesis of perovskite type CH3NH3PBI3 membrane material based on lead simple-substance membrane | |
| CN104022185B (en) | Perovskite membrane and preparation and application method thereof | |
| CN106953015B (en) | A kind of preparation method of high efficiency large area perovskite solar battery | |
| CN104993058B (en) | A kind of laminated perovskite structure material and the application in methylamine lead iodine perovskite thin film solar cell | |
| CN108832002A (en) | A kind of perovskite solar battery based on PVA modification hole transmission layer | |
| CN107154460A (en) | A kind of complete carbon-based perovskite solar cell and its preparation technology | |
| CN106191775A (en) | A kind of transparent conductive film and its preparation method and application | |
| CN106058060A (en) | Method for preparing high-quality perovskite crystal thin film | |
| CN108493340A (en) | A kind of method that steam auxiliary prepares perovskite solar cell | |
| CN103145345B (en) | Chemical method for synthesising silver selenide semiconductor photoelectric film material in situ at room temperature | |
| CN106340587A (en) | Perovskite film preparation method and perovskite solar cell | |
| CN108767117A (en) | A kind of perovskite solar cell and preparation method thereof being passivated grain boundary defects based on carbon quantum dot doping anti-solvent | |
| CN109755394A (en) | A method of perovskite solar battery is prepared using air knife coating | |
| CN104953030A (en) | Interface-modified perovskite-type solar cell and preparation method thereof | |
| CN104393177A (en) | Perovskite phase organic metal halide-based solar cell and manufacturing method thereof | |
| CN108767121A (en) | A kind of preparation method of the electron-transport layer film of meso-hole structure | |
| CN105304820A (en) | Perovskite solar cell with enhanced graphene and preparation method thereof | |
| CN107093669A (en) | A kind of perovskite solar cell light absorption layer | |
| CN109713137A (en) | Element gas phase doping method for perovskite solar cell transport layer | |
| CN109888108A (en) | A kind of perovskite solar battery and preparation method thereof of large biological molecule modification | |
| CN105280818B (en) | A kind of planar heterojunction perovskite solar cell of stabilization and preparation method thereof | |
| CN107369768A (en) | A kind of preparation method of the perovskite solar cell based on new Organic leadP source | |
| CN111029470B (en) | Perovskite solar cell based on nano grass-shaped mesoporous layer and preparation method thereof | |
| CN104934490B (en) | A kind of method that large area in situ synthesizes stannous oxide semiconductor optoelectronic thin-film material |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190503 |
|
| RJ01 | Rejection of invention patent application after publication |