CN105742505A - High-performance perovskite solar cell and preparation method thereof - Google Patents
High-performance perovskite solar cell and preparation method thereof Download PDFInfo
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- CN105742505A CN105742505A CN201610243807.7A CN201610243807A CN105742505A CN 105742505 A CN105742505 A CN 105742505A CN 201610243807 A CN201610243807 A CN 201610243807A CN 105742505 A CN105742505 A CN 105742505A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920000144 PEDOT:PSS Polymers 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims abstract description 23
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 71
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 65
- 229910021529 ammonia Inorganic materials 0.000 claims description 48
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims description 47
- -1 ammonia modified graphene Chemical class 0.000 claims description 32
- 230000005540 biological transmission Effects 0.000 claims description 28
- 229910021389 graphene Inorganic materials 0.000 claims description 17
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 16
- 238000004528 spin coating Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 1
- 230000005525 hole transport Effects 0.000 abstract 6
- 239000002131 composite material Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 239000010409 thin film Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XXWFDPVOXNJASB-UHFFFAOYSA-N ethanol;phenol Chemical compound CCO.OC1=CC=CC=C1 XXWFDPVOXNJASB-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Classifications
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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
- 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
-
- 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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- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a high-performance perovskite solar cell. The high-performance perovskite solar cell comprises an indium tin oxide electrode layer, a hole transport layer PEDOT:PSS, a perovskite layer CH<3>NH<3>PbI<3-x>Cl<x>, an electron transport layer PCBM, a silver electrode layer and an amino-modified graphene oxide layer GO:NH<3>, wherein the indium tin oxide electrode layer, the hole transport layer PEDOT:PSS, the perovskite layer CH<3>NH<3>PbI<3-x>Cl<x>, the electron transport layer PCBM and the silver electrode layer are sequentially arranged; and the amino-modified graphene oxide layer GO:NH<3> is arranged between the hole transport layer PEDOT:PSS and the perovskite layer CH<3>NH<3>PbI<3-x>Cl<x>. The invention further provides a preparation method of the high-performance perovskite solar cell. The amino-modified graphene oxide layer GO:NH<3> is formed on the hole transport layer PEDOT:PSS, and a composite hole transport layer is formed by synergistic action of the amino-modified graphene oxide layer GO:NH<3> and the hole transport layer PEDOT:PSS, so that the device performance and stability of the perovskite solar cell can be effectively improved.
Description
Technical field
The present invention relates to area of solar cell, relate more specifically to a kind of high performance calcium titanium ore solar-electricity
Pond and preparation method thereof.
Background technology
Solaode is paid close attention to by people due to its environmental protection.Wherein, perovskite solar-electricity
Show one's talent due to the device performance of its excellence in pond, between a few years, and the opto-electronic conversion effect of this type of battery
Rate is increased to current about 20.3% by 3.1% originally, and theoretical conversion efficiencies can reach more than 25%,
And the preparation method of this battery can use the processing of low temperature complete molten journey and inkjet technology face quick, big
Preparing device, cost of manufacture is cheap long-pendingly, has huge business potential.Thus U.S.'s " science " is miscellaneous
Perovskite solar battery technology is elected as one of 2013 year ten big technological breakthroughs by will.Generally, perovskite
Solaode includes indium tin oxide electrode layer ITO/ hole transmission layer PEDOT:PSS/ calcium titanium ore bed
CH3NH3PbI3-xClx/ electron transfer layer PCBM/ metal electrode layer Al or Ag, wherein, PEDOT:PSS
For polystyrolsulfon acid/poly-3,4-ethylene dioxythiophene, PCBM is poly-[6,6] phenyl-carbon 61-methyl butyrate,
X is 0,1 or 2.
Document (Wu, Z.；Bai,S.；Xiang,J.；Yuan,Z.；Yang,Y.；Cui,W.；Gao,X.；Liu,Z.；
Jin,Y.；Sun,B.,Efficient Planar Heterojunction Perovskite Solar Cells Employing
Graphene Oxide as Hole Conductor.Nanoscale 2014,6 (18), 10505-10510) report
A kind of perovskite solaode, it includes indium tin oxide electrode layer ITO/ graphene oxide layer GO/ calcium
Titanium ore layer CH3NH3PbI3-xClx/ electron transfer layer PCBM/ aluminum electrode layer Al, it passes through graphene oxide
Layer GO replaces existing hole transmission layer PEDOT:PSS, to improve the conversion efficiency of device.But,
Experiment shows, device performance and the stability of this solaode are the most to be improved.
Summary of the invention
In order to improve device performance and the stability of perovskite solaode, it is desirable to provide a kind of
High performance calcium titanium ore solaode and preparation method thereof.
The present invention provides a kind of high performance calcium titanium ore solaode, and it includes the tin indium oxide set gradually
Electrode layer, hole transmission layer PEDOT:PSS, calcium titanium ore bed CH3NH3PbI3-xClx, electron transfer layer
PCBM and silver electrode layer, this high performance calcium titanium ore solaode is additionally included in hole transmission layer
PEDOT:PSS and calcium titanium ore bed CH3NH3PbI3-xClxBetween arrange ammonia modified graphene oxide layer
GO:NH3。
This ammonia modified graphene oxide layer GO:NH3Thickness be 1-3nm.It is preferably 2nm.
This high performance calcium titanium ore solaode is additionally included between electron transfer layer PCBM and silver electrode layer
It is provided as the phenol layer of boundary layer.
The present invention also provides for the preparation method of a kind of high performance calcium titanium ore solaode, and it includes step S1,
Indium tin oxide electrode layer is provided；S2, provides hole transmission layer PEDOT:PSS in indium tin oxide electrode layer；
S3, spin coating ammonia modified graphene oxide aqueous solution on hole transmission layer PEDOT:PSS, 110-130 DEG C
Lower annealing 5-15min obtains ammonia modified graphene oxide layer GO:NH3, wherein, ammonia modified graphene oxide
Aqueous solution is graphene oxide GO and ammonia spirit NH3Mixed solution；S4, at the modified oxidized stone of ammonia
Ink alkene layer GO:NH3Upper offer calcium titanium ore bed CH3NH3PbI3-xClx；S5, at calcium titanium ore bed
CH3NH3PbI3-xClxUpper offer electron transfer layer PCBM；S6, provides on electron transfer layer PCBM
Silver electrode layer.
Described step S1 is specially and cleans tin indium oxide with detergent, ultrasonic in acetone and ethanol, then
Dry up with nitrogen and obtain indium tin oxide electrode layer ITO.
Described step S2 is specially the UV ozone etc. that indium tin oxide electrode layer ITO carries out 10-20min
Gas ions processes, and turns/30-50s spin coating PEDOT:PSS thin film with spin-coating method at 4000-5000,110-130 DEG C
Lower annealing 5-15min obtains hole transmission layer PEDOT:PSS.
Graphene oxide GO in mixed solution in described step S3 and ammonia spirit NH3Mol ratio
For 1:0-1:0.5.Preferably, this mol ratio is 1:0.3 or 1:0.4.
The concentration of the graphene oxide GO in mixed solution is 0.2mg/ml.
The mass concentration of the ammonia in mixed solution is 70%.
Described graphene oxide is prepared from as raw material by Hummer method scale expanded graphite.
Described step S4 is specially at ammonia modified graphene oxide layer GO:NH3On turn with 3000-5000
The perovskite precursor solution of the rotating speed spin coating 20-40% mass fraction of/30-50s, left at room temperature
The 50-70min that anneals at 10-20min, 90-110 DEG C obtains calcium titanium ore bed CH3NH3PbI3-xClx。
Described step S5 is included in hole transmission layer calcium titanium ore bed CH3NH3PbI3-xClxOn with 1000-3000
Turn/the PCBM chlorobenzene solution of the rotating speed spin coating 10-30mg/ml of 30-50s obtains electron transfer layer PCBM.
Described step S5 is additionally included in the phenol ethanol of spin coating 0.4-0.6mg/ml on electron transfer layer PCBM
Solution obtains phenol layer.
It is 2 × 10 that described step S6 is specially at air pressure-6By mask plate by 90-110nm in the environment of torr
Thick Ag film heat deposition is on electron transfer layer PCBM or phenol layer.
The present invention is by forming ammonia modified graphene oxide layer on hole transmission layer PEDOT:PSS
GO:NH3, both mutual synergism form a compound hole transmission layer, it is possible to be effectively improved calcium titanium
The device performance of ore deposit solaode and stability.Wherein, the ammonia of the perovskite solaode of the present invention
Modified graphene oxide layer GO:NH3Simply form by the way of spin coating, perovskite solaode
Conversion efficiency reaches 16.11%, and open-circuit voltage is 1.03V, and short-circuit current density is 22.06mA/cm2, fill out
Filling the factor is 71%.
Accompanying drawing explanation
Fig. 1 a is the SEM shape appearance figure of graphene oxide layer GO；
Fig. 1 b is ammonia modified graphene oxide layer GO:NH3SEM shape appearance figure；
Fig. 1 c is the calcium titanium ore bed directly formed on hole transmission layer PEDOT:PSS
CH3NH3PbI3-xClxSEM shape appearance figure；
Fig. 1 d is at ammonia modified graphene oxide layer GO:NH3Upper formation calcium titanium ore bed CH3NH3PbI3-xClx
SEM shape appearance figure；
Fig. 2 is the interface electronic structure figure of the high performance calcium titanium ore solaode according to the present invention；
Fig. 3 a is the calcium titanium ore bed directly formed on hole transmission layer PEDOT:PSS
CH3NH3PbI3-xClxTwo-dimentional diffraction structure；
Fig. 3 b is at ammonia modified graphene oxide layer GO:NH3Upper formation calcium titanium ore bed CH3NH3PbI3-xClx
Two-dimentional diffraction structure；
Fig. 4 is the device performance schematic diagram of perovskite solaode according to the second embodiment of the present invention；
Fig. 5 is the device of the perovskite solaode according to the present invention and traditional perovskite solaode
Part performance comparison schematic diagram；
What Fig. 6 a was perovskite solaode according to the present invention with traditional perovskite solaode is steady
Determine performance comparison schematic diagram；
The knot that Fig. 6 b is perovskite solaode according to the present invention before and after being exposed to air 96 hours
Structure evolution schematic diagram；
The structure evolution that Fig. 6 c is traditional perovskite solaode before and after being exposed to air 96 hours
Schematic diagram.
Detailed description of the invention
Below in conjunction with the accompanying drawings, provide presently preferred embodiments of the present invention, and be described in detail.
Fig. 1 a is the SEM shape appearance figure of graphene oxide layer GO, and Fig. 1 b is ammonia modified graphene oxide layer
GO:NH3SEM shape appearance figure, it is clear that the present invention is by spin coating ammonia modified graphene oxide aqueous solution
The ammonia modified graphene oxide layer GO:NH that method obtains3For the dispersion layer of homogenizing, wherein, Fig. 1 b sees
The bright distribution of particles observed is due to ammonia NH3Absorption induces table on graphene oxide GO surface
Caused by the change of surface conductivity, it can finally improve calcium titanium ore bed CH3NH3PbI3-xClxGrowth and knot
Crystalline substance degree.
Fig. 1 c is the calcium titanium ore bed directly formed on hole transmission layer PEDOT:PSS
CH3NH3PbI3-xClxSEM shape appearance figure, Fig. 1 d is at ammonia modified graphene oxide layer GO:NH3On
Form calcium titanium ore bed CH3NH3PbI3-xClxSEM shape appearance figure, it is clear that at ammonia modified graphene oxide
Layer GO:NH3The calcium titanium ore bed CH of upper growth3NH3PbI3-xClxShow the distribution of obvious crystal grain.
Fig. 2 is the interface electronic structure figure of the high performance calcium titanium ore solaode according to the present invention, wherein,
Ammonia modified graphene oxide layer GO:NH3For 5.37eV, higher than hole transmission layer PEDOT:PSS's
5.1eV, can realize level-density parameter well with indium tin oxide electrode layer ITO (4.8eV), simultaneously and calcium
Titanium ore layer CH3NH3PbI3-xClx(5.4eV) form homogeneous active layer, thus improve indium-tin oxide electrode
The electric charge transmission of layer ITO and the ability of collection.
Fig. 3 a is the calcium titanium ore bed directly formed on hole transmission layer PEDOT:PSS
CH3NH3PbI3-xClxTwo-dimentional diffraction structure, Fig. 3 b is at ammonia modified graphene oxide layer GO:NH3On
Form calcium titanium ore bed CH3NH3PbI3-xClxTwo-dimentional diffraction structure, it is clear that at ammonia modified graphene oxide
Layer GO:NH3The calcium titanium ore bed CH of upper growth3NH3PbI3-xClxShow preferable crystalline property, its
Diffraction spot is more limpid in sight.Therefore, ammonia modified graphene oxide layer GO:NH3Contribute to being formed high-quality
The perovskite thin film of amount, it has the structure of high-sequential and preferably absorbs, thus bringing preferably
Device performance.
Embodiment 1
Tin indium oxide is cleaned with detergent, ultrasonic in acetone and ethanol, then dry up with nitrogen and obtain oxygen
Change indium tin electrode layer ITO.Indium tin oxide electrode layer ITO is carried out the UV ozone plasma of 15min
Processing, with spin-coating method at 4500 turns/40s spin coating PEDOT:PSS thin film, the 10min that anneals at 120 DEG C obtains
To hole transmission layer PEDOT:PSS.Oxygen is prepared as raw material by Hummer method scale expanded graphite
Functionalized graphene.According to graphene oxide GO and ammonia spirit NH3Mol ratio be 1:0 formed ammonia modification oxygen
Functionalized graphene aqueous solution.Spin coating ammonia modified graphene oxide aqueous solution on hole transmission layer PEDOT:PSS,
The 10min that anneals at 120 DEG C obtains ammonia modified graphene oxide layer GO:NH3.At ammonia modified graphene oxide
Layer GO:NH3On with the perovskite precursor solution of rotating speed spin coating 30% mass fraction of 4000 turns/40s,
Left at room temperature 15min, the 60min that anneals at 100 DEG C obtain calcium titanium ore bed CH3NH3PbI3-xClx, thin film
Color become dark-brown.At hole transmission layer calcium titanium ore bed CH3NH3PbI3-xClxOn with 2000 turns/40s
The PCBM chlorobenzene solution of rotating speed spin coating 20mg/ml obtain electron transfer layer PCBM.In electric transmission
On layer PCBM, the phenol ethanol solution of spin coating 0.5mg/ml obtains phenol layer, it is not necessary to extra annealing.?
Air pressure is 2 × 10-6Mask plate is passed through by Ag film heat deposition thick for 100nm to electric transmission in the environment of torr
On layer PCBM or phenol layer.
The device performance of test perovskite solaode, its conversion efficiency reaches 14.42%, and open-circuit voltage is
0.96V, short-circuit current density is 21.80mA/cm2, fill factor, curve factor is 69%.
Embodiment 2
Method with reference to embodiment 1 prepares perovskite solaode, except for the difference that, in mixed solution
Graphene oxide GO and ammonia spirit NH3Mol ratio be 1:0.3.
The device performance of test perovskite solaode, its conversion efficiency reaches 16.11%, and open-circuit voltage is
1.03V, short-circuit current density is 22.06mA/cm2, fill factor, curve factor is 71%, as shown in Figure 4.
Embodiment 3
Method with reference to embodiment 1 prepares perovskite solaode, except for the difference that, in mixed solution
Graphene oxide GO and ammonia spirit NH3Mol ratio be 1:0.4.
The device performance of test perovskite solaode, its conversion efficiency reaches 14.49%, and open-circuit voltage is
1.01V, short-circuit current density is 20.90mA/cm2, fill factor, curve factor is 69%.
Embodiment 4
Method with reference to embodiment 1 prepares perovskite solaode, except for the difference that, in mixed solution
Graphene oxide GO and ammonia spirit NH3Mol ratio be 1:0.5.
The device performance of test perovskite solaode, its conversion efficiency reaches 12.95%, and open-circuit voltage is
0.96V, short-circuit current density is 19.63mA/cm2, fill factor, curve factor is 69%.
Fig. 5 is the device of the perovskite solaode according to the present invention and traditional perovskite solaode
Part performance comparison schematic diagram, wherein, includes indium tin oxide electrode layer ITO/ hole transmission layer with traditional
PEDOT:PSS/ calcium titanium ore bed CH3NH3PbI3-xClxThe calcium of/electron transfer layer PCBM/ aluminum electrode layer Al
Titanium ore solaode is compared, according to the perovskite solaode of the present invention due at hole transmission layer
PEDOT:PSS and calcium titanium ore bed CH3NH3PbI3-xClxIn be provided with ammonia modified graphene oxide layer
GO:NH3And there is excellent attribute.Wherein, when the graphite oxide in ammonia modified graphene oxide aqueous solution
Alkene GO and ammonia spirit NH3Mol ratio when being 1:0.3, perovskite solaode has best property
Can, its conversion efficiency reaches 16.11%, and open-circuit voltage is 1.03V, and short-circuit current density is 22.06mA/cm2,
Fill factor, curve factor is 71%.It is true that according to the perovskite solaode of the present invention at all of aspect all
It is better than conventional batteries, this is because: (1) calcium titanium ore bed CH3NH3PbI3-xClxThere is the crystallization of improvement
Property and preferred orientation；(2) due to hole transmission layer PEDOT:PSS and calcium titanium ore bed CH3NH3PbI3-xClx
Between level-density parameter, more carrier can be collected easily；(3) calcium titanium ore bed
CH3NH3PbI3-xClxForm good pattern, coverage rate and show big crystal grain distribution.
What Fig. 6 a was perovskite solaode according to the present invention with traditional perovskite solaode is steady
Determine performance comparison schematic diagram.Behind under the environmental condition of encapsulation 96 hours, according to the perovskite of the present invention
The conversion efficiency of solaode is only dropped to 72.2% (from 15.1% to 10.9%) of initial value, and passes
The perovskite solaode of system drops to 65.6% (from 12.5% to 8.2%) of initial value.Obviously, root
Ammonia modified graphene oxide layer GO:NH is passed through according to the perovskite solaode of the present invention3Calcium can be improved
The stability of titanium ore solaode, this be the perovskite structure due to high-sequential formation so that
Perovskite thin film is more stable.
The knot that Fig. 6 b is perovskite solaode according to the present invention before and after being exposed to air 96 hours
Structure evolution schematic diagram, Fig. 6 c is that traditional perovskite solaode is before and after being exposed to air 96 hours
Structure evolution schematic diagram.After ingress of air 96 hours, traditional calcium in perovskite solaode
Titanium ore decomposes with water molecule reaction so that demonstrate obvious lead iodide peak (001) in diffraction pattern.Phase
Accordingly, according in the diffraction pattern of the perovskite solaode of the present invention, lead iodide peak does not occur
(001), i.e. the present invention is by ammonia modified graphene oxide layer GO:NH3Moisture can be effectively prevented from enter
Calcium titanium ore bed CH3NH3PbI3-xClx, improve the stability of device.
Above-described, only presently preferred embodiments of the present invention, it is not limited to the scope of the present invention,
The above embodiment of the present invention can also make a variety of changes.The most every right according to the present patent application is wanted
Ask change simple, equivalent and modification that book and description made, fall within the right of patent of the present invention
Claimed scope.The most detailed description of the present invention be routine techniques content.
Claims (10)
1. a high performance calcium titanium ore solaode, it indium tin oxide electrode layer including setting gradually,
Hole transmission layer PEDOT:PSS, calcium titanium ore bed CH3NH3PbI3-xClx, electron transfer layer PCBM and silver
Electrode layer, it is characterised in that this high performance calcium titanium ore solaode is additionally included in hole transmission layer
PEDOT:PSS and calcium titanium ore bed CH3NH3PbI3-xClxBetween arrange ammonia modified graphene oxide layer
GO:NH3。
High performance calcium titanium ore solaode the most according to claim 1, it is characterised in that this ammonia
Modified graphene oxide layer GO:NH3Thickness be 1-3nm.
High performance calcium titanium ore solaode the most according to claim 1, it is characterised in that this height
Performance perovskite solaode is additionally included between electron transfer layer PCBM and silver electrode layer the work arranged
Phenol layer for boundary layer.
4. the preparation method of a high performance calcium titanium ore solaode, it is characterised in that include step:
S1, it is provided that indium tin oxide electrode layer；
S2, provides hole transmission layer PEDOT:PSS in indium tin oxide electrode layer；
S3, spin coating ammonia modified graphene oxide aqueous solution on hole transmission layer PEDOT:PSS,
The 5-15min that anneals at 110-130 DEG C obtains ammonia modified graphene oxide layer GO:NH3, wherein, ammonia is modified
Graphene oxide water solution is the mixed solution of graphene oxide and ammonia spirit；
S4, at ammonia modified graphene oxide layer GO:NH3Upper offer calcium titanium ore bed CH3NH3PbI3-xClx；
S5, at calcium titanium ore bed CH3NH3PbI3-xClxUpper offer electron transfer layer PCBM；
S6, provides silver electrode layer on electron transfer layer PCBM.
Preparation method the most according to claim 4, it is characterised in that the graphite oxide in mixed solution
The mol ratio of alkene and ammonia spirit is 1:0-1:0.5.
Preparation method the most according to claim 4, it is characterised in that the graphite oxide in mixed solution
The mol ratio of alkene and ammonia spirit is 1:0.3 or 1:0.4.
Preparation method the most according to claim 4, it is characterised in that the graphite oxide in mixed solution
The concentration of alkene is 0.2mg/ml.
Preparation method the most according to claim 4, it is characterised in that the matter of the ammonia in mixed solution
Amount concentration is 70%.
Preparation method the most according to claim 4, it is characterised in that described step S5 is additionally included in
On electron transfer layer PCBM, the phenol of spin coating 0.4-0.6mg/ml obtains phenol layer.
Preparation method the most according to claim 9, it is characterised in that silver electricity is provided on phenol layer
Pole layer.
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| CN106159102A (en) * | 2016-09-28 | 2016-11-23 | Tcl集团股份有限公司 | Lamination QLED device and preparation method thereof |
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| CN106684247A (en) * | 2017-03-15 | 2017-05-17 | 中南大学 | Perovskite solar cell and preparation method thereof |
| CN107732016A (en) * | 2017-11-20 | 2018-02-23 | 苏州黎元新能源科技有限公司 | A kind of high stability perovskite solar cell |
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| CN110010769A (en) * | 2019-03-26 | 2019-07-12 | 浙江大学 | A kind of preparation method of oriented growth organic inorganic hybridization perovskite thin film |
| CN110828177A (en) * | 2019-10-28 | 2020-02-21 | 宁波大学 | Photosensitive capacitor based on halide perovskite and preparation method thereof |
| CN110828177B (en) * | 2019-10-28 | 2021-10-01 | 宁波大学 | Photosensitive capacitor based on halide perovskite and preparation method thereof |
| CN113955748A (en) * | 2020-07-21 | 2022-01-21 | 国家纳米科学中心 | Preparation method of aminated graphene oxide nanosheet and application of aminated graphene oxide nanosheet in organic solar cell |
| CN113955748B (en) * | 2020-07-21 | 2023-08-22 | 国家纳米科学中心 | Preparation method of aminated graphene oxide nanosheets and application of aminated graphene oxide nanosheets in organic solar cells |
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