CN108054225A - A kind of cuprous oxide solar cell based on nano structure membrane electrode and preparation method thereof - Google Patents
A kind of cuprous oxide solar cell based on nano structure membrane electrode and preparation method thereof Download PDFInfo
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- CN108054225A CN108054225A CN201711330388.1A CN201711330388A CN108054225A CN 108054225 A CN108054225 A CN 108054225A CN 201711330388 A CN201711330388 A CN 201711330388A CN 108054225 A CN108054225 A CN 108054225A
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- zinc
- film layer
- oxide
- layer
- cuprous oxide
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 66
- 239000012528 membrane Substances 0.000 title claims abstract description 28
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 156
- 239000010410 layer Substances 0.000 claims abstract description 141
- 239000011787 zinc oxide Substances 0.000 claims abstract description 78
- 229960001296 zinc oxide Drugs 0.000 claims abstract description 74
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011241 protective layer Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 27
- 238000004528 spin coating Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 150000003752 zinc compounds Chemical class 0.000 claims description 9
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 8
- 229940043237 diethanolamine Drugs 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 238000007650 screen-printing Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 238000005566 electron beam evaporation Methods 0.000 claims description 4
- 238000007738 vacuum evaporation Methods 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 238000000149 argon plasma sintering Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 108
- 239000010949 copper Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000002042 Silver nanowire Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IJRVLVIFMRWJRQ-UHFFFAOYSA-N nitric acid zinc Chemical compound [Zn].O[N+]([O-])=O IJRVLVIFMRWJRQ-UHFFFAOYSA-N 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000212941 Glehnia Species 0.000 description 1
- 241000209094 Oryza Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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
- Y02E10/541—CuInSe2 material 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention provides a kind of cuprous oxide solar cell based on nano structure membrane electrode and preparation method thereof, has been sequentially prepared from bottom to top on a glass substrate：Nano silver wire film layer, zinc oxide films film layer, zinc-oxide nano column layer, cuprous oxide layer, cuprous oxide protective layer, electrode layer.The present invention is using nano silver wire film layer and zinc-oxide nano column composite film layer; it has the function of multiple light scattering; heterojunction structure is formed with cuprous oxide, light absorpting ability is improved, uses p-type high molecular material as cuprous oxide protective layer; cuprous oxide can be effectively isolated to be combined with the water oxygen in air; cuprous oxide material lifetime can greatly be improved, the present invention has low cost, highly practical; it is easy to the advantages such as large-scale production, has broad application prospects.
Description
【Technical field】
The present invention relates to technical field of solar cell manufacturing, more particularly to a kind of oxygen based on nano structure membrane electrode
Change cuprous solar cell and preparation method thereof.
【Background technology】
In recent years, the mankind have been devoted to find energy saving, environmentally friendly novel photovoltaic material.Cuprous oxide (Cu2O it is) a kind of
Important inorganic, metal oxide is widely used in the fields such as semiconductor catalyst, solar energy conversion, raw material sources
It is abundant, nontoxic environmentally protective, and preparation method is simple, financial cost is cheap.In the system of cuprous oxide solar cell device
Some problems are remained during making：1st, current cuprous oxide solar cell uses ito thin film as electrically conducting transparent more
Film preparation solar cell device, ito thin film are expensive；2nd, moisture in air is easily absorbed for cuprous oxide and deliquescence.
Therefore, it is necessary to a kind of novel oxidized cuprous solar cell is researched and developed to solve the above problems.
【The content of the invention】
It is an object of the invention to provide a kind of cuprous oxide solar cell based on nano structure membrane electrode and its
Preparation method, to solve the above problems.
To solve the above-mentioned problems, according to an aspect of the present invention, the present invention provides a kind of based on nano structure membrane
The preparation method of the cuprous oxide solar cell of electrode, including：There is provided with first surface and with the first surface phase
The substrate of corresponding second surface cleans the substrate；Silver is prepared by the method for spin-coating on the first surface to receive
Rice noodles film layer；Zinc oxide films film layer is prepared in the nano silver wire film layer by the method for spin-coating；In the oxygen
Change and pass through Hydrothermal Growth zinc-oxide nano column layer in zinc film layer；By electrochemical deposition method in the zinc-oxide nano column layer
On prepare cuprous oxide film layer；On the cuprous oxide film layer p-type protective layer is prepared with the method for spin-coating；Pass through
Any one method in silk-screen printing, vacuum evaporation, vacuum sputtering or electron beam evaporation is prepared on the p-type protective layer
Top electrode forms electrode layer, completes the making of the cuprous oxide solar cell based on nano structure membrane electrode.
As the preferred embodiment of the present invention, the substrate is first cleaned with detergent, then using ethyl alcohol
It is cleaned by ultrasonic, then is cleaned by ultrasonic using deionized water, finally cleaned with deionized water, the substrate after cleaning is dried, puts substrate
It is maintained in nitrogen environment.
As the preferred embodiment of the present invention, silver is prepared by the method for spin-coating on the first surface
Nano wire film layer includes：The nano silver wire alcohol dispersion liquid of 1-10mg/ml is taken, the substrate is placed on whirler and is revolved
Transfer film forms nano silver wire film layer after to be dried, the thickness of the nano silver wire film layer is 200-1000nm.
As the preferred embodiment of the present invention, by the method for spin-coating in the nano silver wire film layer
Preparing zinc oxide films film layer includes：Zinc compound, diethanol amine and ethyl alcohol under 40-100 DEG C of temperature conditionss are mixed and gone forward side by side
Row reaction, ageing form zinc oxide colloidal sol afterwards for 24 hours, are aoxidized in the nano silver wire film layer with the method for spin-coating
Zinc film forms zinc oxide films film layer after drying, and the thickness of the zinc oxide films film layer is 10-200nm.
As the preferred embodiment of the present invention, the zinc compound is zinc acetate, zinc nitrate or zinc acetylacetonate
In one or more, zinc concentration is 0.01-1mol/L in the zinc compound, the amount of the substance of the diethanol amine and zinc
Than for 1:1.
As the preferred embodiment of the present invention, pass through Hydrothermal Growth zinc oxide in the zinc oxide films film layer
Nano-pillar layer includes：The zinc-oxide film level is put into beaker downward, zinc-oxide nano is obtained by Hydrothermal Growth
Column layer, the height of the zinc-oxide nano column layer is 500nm-2000nm.
As the preferred embodiment of the present invention, made by electrochemical deposition method on the zinc-oxide nano column layer
Standby cuprous oxide film layer includes：The cupric salt solution for being 0.01-0.2mol/L with distilled water configuration concentration adds in 10 times of copper
The lactic acid of salinity adjusts pH value to 12 with NaOH solution, electroplate liquid is obtained after being sufficiently stirred, the zinc-oxide nano column layer exists
Electro-deposition is carried out in the electroplate liquid, forms cuprous oxide film layer, the cupric salt is copper acetate, copper nitrate or copper sulphate
In one or more.
As the preferred embodiment of the present invention, the method system that spin-coating is used on the cuprous oxide film layer
Standby p-type protective layer includes：By PEDOT：The P3HT/ chlorobenzene solutions of PSS solution or 2-10mg/ml drop in the cuprous oxide film
On layer, 20min curings are heated under conditions of 150 DEG C after spin-coating, form p-type protective layer, the thickness of the p-type protective layer
It spends for 20-100nm.
As the preferred embodiment of the present invention, the thickness of the top electrode is 200-3000nm.
According to another aspect of the present invention, the present invention provides a kind of cuprous oxide based on nano structure membrane electrode too
Positive energy battery, from bottom to top includes successively：Substrate, nano silver wire film layer, zinc oxide films film layer, zinc-oxide nano column layer, oxygen
Change cuprous film layer, p-type protective layer, electrode layer.
Compared with prior art, in the present invention a kind of cuprous oxide solar cell based on nano structure membrane electrode and
Its preparation method, has the following advantages：1st, can be realized to the secondary of light using nano silver wire and zinc-oxide nano rod structure
Effectively scattering improves the light absorption of cuprous oxide cell；2nd, moisture in air is easily absorbed for cuprous oxide and the characteristics of deliquescence,
Using polymer P type conductive material or polymeric acceptor material, it can effectively protect cuprous oxide not by the water oxygen institute in air
Infringement, improves the cuprous oxide service life, cuprous oxide material over time can be made not hydrolyze, and realizes and extends battery life, while P
Type protective layer is also beneficial to the transmission of hole in the devices, and protection battery life improves device performance simultaneously, and cheap.
【Description of the drawings】
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, the accompanying drawings in the following description is only some embodiments of the present invention, for this
For the those of ordinary skill of field, without having to pay creative labor, it can also be obtained according to these attached drawings other
Attached drawing.Wherein：
Fig. 1 is the preparation method of the cuprous oxide solar cell based on nano structure membrane electrode in the present invention one
Flow chart in a embodiment；
Fig. 2 be the present invention in the cuprous oxide solar cell based on nano structure membrane electrode in one embodiment
Structure diagram.
【Specific embodiment】
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, it is below in conjunction with the accompanying drawings and specific real
Applying mode, the present invention is described in further detail.
" one embodiment " or " embodiment " referred to herein refers to may be included at least one realization method of the present invention
A particular feature, structure, or characteristic." in one embodiment " that different places occur in the present specification not refers both to same
A embodiment, nor the individual or selective embodiment mutually exclusive with other embodiment.
Referring to Fig. 1, Fig. 1 is the system of the cuprous oxide solar cell based on nano structure membrane electrode in the present invention
The flow chart of Preparation Method 100 in one embodiment.As shown in Figure 1, the manufacturing method 100 includes the following steps.
Step 110, the substrate with first surface and with the corresponding second surface of the first surface is provided, cleans institute
State substrate.
Specifically, the hard substrates such as quartz, glass, aluminium oxide (sapphire) may be employed in the substrate, can also use
The flexible substrates such as PET, PFN.The substrate is first cleaned with detergent, is then cleaned using EtOH Sonicate, then using go from
Sub- water is cleaned by ultrasonic, and is finally cleaned with deionized water, and the substrate after cleaning is dried, substrate is put and is maintained in nitrogen environment.
Step 120, nano silver wire film layer is prepared by the method for spin-coating on the first surface.
In one embodiment, the nano silver wire alcohol dispersion liquid of 1-10mg/ml is taken, the substrate is placed on spin-coating
Spin-coating on machine forms nano silver wire film layer after to be dried, the thickness of the nano silver wire film layer is 200-1000nm.
Step 130, zinc oxide films film layer is prepared in the nano silver wire film layer by the method for spin-coating.
In one embodiment, zinc compound, diethanol amine and ethyl alcohol are mixed simultaneously under 40-100 DEG C of temperature conditionss
It is reacted, the zinc compound is the one or more in zinc acetate, zinc nitrate or zinc acetylacetonate, in the zinc compound
Zinc concentration is 0.01-1mol/L, and the amount ratio of the substance of the diethanol amine and zinc is 1：1, it is molten that ageing forms zinc oxide afterwards for 24 hours
Glue obtains zinc-oxide film with the method for spin-coating in the nano silver wire film layer, forms zinc oxide films after drying
Film layer, the thickness of the zinc oxide films film layer is 10-200nm.The square electricity of above-mentioned nano silver wire film layer/zinc oxide films film layer
Resistance is less than 30 Ω/Sq.
Step 140, Hydrothermal Growth zinc-oxide nano column layer is passed through in the zinc oxide films film layer.
In one embodiment, the zinc-oxide film level is put into beaker downward, is obtained by Hydrothermal Growth
Zinc-oxide nano column layer, the height of the zinc-oxide nano column layer is 500nm-2000nm.
Step 150, cuprous oxide film layer is prepared on the zinc-oxide nano column layer by electrochemical deposition method.
Specifically, the cupric salt solution for being 0.01-0.2mol/L with distilled water configuration concentration, adds in 10 times of mantoquita concentration
Lactic acid, with NaOH solution adjust pH value to 12, electroplate liquid is obtained after being sufficiently stirred, the zinc-oxide nano column layer is in the electricity
Electro-deposition is carried out in plating solution, forms cuprous oxide film layer, the cupric salt is one in copper acetate, copper nitrate or copper sulphate
Kind is a variety of.
In one embodiment, the material of the p-type polymeric layer and p-type protective layer is PEDOT：PSS solution.
Step 160, on the cuprous oxide film layer p-type protective layer is prepared with the method for spin-coating.
Specifically, by PEDOT：The P3HT/ chlorobenzene solutions of PSS solution or 2-10mg/ml drop in the cuprous oxide film
On layer, 20min curings are heated under conditions of 150 DEG C after spin-coating, form p-type protective layer, the thickness of the p-type protective layer
It spends for 20-100nm.
Step 170, any one method in silk-screen printing, vacuum evaporation, vacuum sputtering or electron beam evaporation is passed through
Top electrode is prepared on the p-type protective layer, electrode layer is formed, completes the cuprous oxide sun based on nano structure membrane electrode
The making of energy battery.The p-type protective layer can be PEDOT：The polymeric acceptors material such as PSS solution or P3HT, PTB7, on
One kind in chlorobenzene or dichloro-benzenes can be selected by stating polymeric acceptor material solution.
Specifically, the electrode, may be employed metal or nonmetallic materials are served as, may be employed aluminum slurry, silver paste or
Prepared by Gold conductor silk-screen printing, non-metal carbon slurry silk-screen printing preparation can also be used.The electrode can also use vacuum to steam
It is prepared by the methods of plating, sputtering, electron beam evaporation.In one embodiment, metal or non-is prepared by the method for silk-screen printing
Metallic top electrode cures electrode in 30 minutes after film forming using 150 degrees Centigrade, and electrode sheet resistance is below 30 ohm after curing.
The vacuum methods such as vacuum evaporation or sputtering can also be used and prepare electrode.The top electrode thickness is 200-3000nm.
Structure through the cuprous oxide solar cell based on nano structure membrane electrode made from above-mentioned preparation method is such as
Under.
Referring to Fig. 2, Fig. 2 be the present invention in based on the cuprous oxide solar cell of nano structure membrane electrode one
Structure diagram in a embodiment.As shown in Fig. 2, the cuprous oxide solar-electricity based on nano structure membrane electrode
Pond from bottom to top includes successively：Substrate 7, nano silver wire film layer 6, zinc oxide films film layer 5, zinc-oxide nano column layer 4, oxidation
Cuprous film layer 3, p-type protective layer 2, electrode layer 1.
Two are introduced with reference to a kind of preparation method of the cuprous oxide solar cell based on nano structure membrane electrode
A embodiment that can fully demonstrate present invention：
Embodiment 1
(1) prepared by glass substrate cleaning and nano silver wire film layer
Glass substrate (40mm × 40mm × 1.1mm) is first cleaned with detergent, then with acetone be cleaned by ultrasonic 30 minutes, so
It is cleaned by ultrasonic 30 minutes with deionized water afterwards, after last deionized water rinsing is clean, is put into drying box drying, above-mentioned glass will be passed through
Glass substrate is placed on whirler, take concentration for 100 μ l drops of 6mg/ml nano silver wires solution on glass substrate, it is molten
Liquid uses 1000rpm/min speed to rotate 20s after being uniformly distributed, and using 160 DEG C of drying 10min, that is, forms glass substrate/Yin Na
Rice noodles film layer, the thickness of nano silver wire film layer is 200-300nm.
(2) prepared by zinc oxide films film layer
By zinc acetate (0.01mol), diethanol amine (0.01mol) and ethyl alcohol (100ml) are mixed at 60 DEG C and carried out anti-
Should, form zinc oxide colloidal sol (100ml), zinc concentration 0.1mol/L after being aged 20h.The glass that will be prepared in step (1)
Glass substrate/nano silver wire film layer is placed on whirler, by the zinc oxide precursor sol liquid 100ul drops of preparation in glass
On substrate/nano silver wire film layer, 30s is rotated using 2500rpm/min speed, using the 120 DEG C of scope dryings of 100Pa vacuum
10min forms glass substrate/nano silver wire film layer/zinc oxide films film layer, the thickness of zinc oxide films film layer is 60nm.
(3) zinc-oxide nano column layer is prepared：
The glass substrate being prepared in step (2)/nano silver wire film layer/zinc-oxide film is placed in Teflon
Water heating kettle is served as a contrast, film is face-down, and zinc nitrate is placed in water heating kettle：Hexa-methylene time amine (HMT)=1：1 deionized water solution,
Wherein nitric acid zinc concentration is 0.08mol/L, and water heating kettle is put into air dry oven, and 90 DEG C are heated 3h, and sample is taken out after natural cooling,
Obtain glass substrate/nano silver wire film layer/zinc oxide films film layer/zinc-oxide nano column layer, gained zinc-oxide nano column layer
Thickness be 1800nm.
(4) cuprous oxide film layer is prepared：
Electrolyte is configured with deionized water 200ml, wherein CuSO containing 0.4mol4, the mixed liquor of 4mol lactic acid mixing
NaOH is added in solution, solution pH value is adjusted to 12, is electrolysed to obtain Cu using permanent potential instrument2O, using three-electrode electro Chemical system
(working electrode, to electrode and reference electrode), using the upper AgNWs/ZnO/ZnO NR plural layers prepared as working electrode,
Cu2The chemical potential of O depositions is -0.4V, is used as to electrode using platinum piece, using Ag/AgCl as reference electrode, configured
Cuprous (the Cu of deposited oxide in good electrolyte2O) film layer carries out under 60 DEG C of depositing temperatures, and sedimentation time 60 minutes obtains
The cuprous oxide film layer of 2000nm, deposited samples are cleaned with deionized water, are heated the sample to 150 degrees Centigrades 30 and are divided
Clock.
(5) p-type protective layer is prepared：
Above-mentioned plural layers are put on whirler, take PEDOT：PSS solution 100ul drops on above-mentioned film,
Solution uses 3000rpm/min speed to rotate 30s after being uniformly distributed, and using 150 DEG C of drying 30min, that is, forms p-type protective layer.
(6) prepared by top electrode
By the method metallic silver top electrode of silk-screen printing, 100ul conductive silver pastes is taken to be positioned on halftone, sample is put
It is placed under halftone, is back and forth hung three times using knife is hung, take remaining silver paste away, that is, obtain silver-colored top electrode film, 150 are used after film forming
Degrees Centigrade cures electrode in 30 minutes, that is, forms the thick silver-colored top electrodes of 500nm.
Embodiment 2
(1) prepared by glass substrate cleaning and nano silver wire film layer
Glass substrate (30mm × 30mm × 1.1mm) is first cleaned with detergent, then with acetone be cleaned by ultrasonic 30 minutes, so
It is cleaned by ultrasonic 30 minutes with deionized water afterwards, after last deionized water rinsing is clean, is put into drying box drying, above-mentioned glass will be passed through
Glass substrate is placed on whirler, take concentration for 150 μ l drops of 4mg/ml nano silver wires solution on glass substrate, it is molten
Liquid uses 800rpm/min speed to rotate 10s after being uniformly distributed, and repeats spin-coating three times after film natural drying, uses
160 DEG C of drying 10min, that is, form glass substrate/nano silver wire film layer, and nano silver wire thin film layer thickness is 200-300nm.
(2) prepared by zinc oxide films film layer
By zinc acetate (0.08mol), diethanol amine (0.08mol) and ethyl alcohol (100ml) are mixed at 60 DEG C and carried out anti-
Should, ageing forms zinc oxide colloidal sol (100ml), zinc concentration 0.08mol/L afterwards for 24 hours.The glass that will be prepared in step (1)
Glass substrate/nano silver wire film layer is placed on whirler, by the zinc oxide precursor sol liquid 200ul drops of preparation in glass
On substrate/nano silver wire film layer, 20s is rotated using 2000rpm/min speed, using the 120 DEG C of scope dryings of 100Pa vacuum
10min forms glass substrate/nano silver wire film layer/zinc oxide films film layer, the thickness of zinc oxide films film layer is 40nm.
(3) zinc-oxide nano column layer is prepared：
The glass substrate being prepared in step (2)/nano silver wire film layer/zinc-oxide film is placed in Teflon
Water heating kettle is served as a contrast, film is face-down, and zinc nitrate is placed in water heating kettle:Hexa-methylene time amine (HMT)=1:1 deionized water solution,
Wherein nitric acid zinc concentration is 0.1mol/L, and water heating kettle is put into air dry oven, and 92 DEG C are heated 3h, and sample is taken out after natural cooling,
Obtain glass substrate/nano silver wire film layer/zinc oxide films film layer/zinc-oxide nano column layer, gained zinc-oxide nano column layer
Thickness be 2300nm.
(4) cuprous oxide film layer is prepared：
Electrolyte is configured with deionized water 200ml, wherein CuSO containing 0.4mol4, the mixed liquor of 4mol lactic acid mixing
NaOH is added in solution, solution pH value is adjusted to 12, is electrolysed to obtain Cu using permanent potential instrument2O, using three-electrode electro Chemical system
(working electrode, to electrode and reference electrode), using the upper AgNWs/ZnO/ZnO NR plural layers prepared as working electrode,
Cu2The chemical potential of O depositions is -0.5V, is used as to electrode using platinum piece, using Ag/AgCl as reference electrode, configured
Cuprous (the Cu of deposited oxide in good electrolyte2O) film layer carries out under 60 DEG C of depositing temperatures, and sedimentation time 50 minutes obtains
The cuprous oxide film layer of 2400nm, deposited samples are cleaned with deionized water, are heated the sample to 150 degrees Centigrades 30 and are divided
Clock.
(5) p-type protective layer is prepared：
Above-mentioned plural layers are put on whirler, prepare the chlorobenzene solution of P3HT, take 10mg P3HT materials, it is molten
In 1ml chlorobenzene solutions, magnetic agitation 10h under 60 degrees celsius is heated, takes solution 120ul drops on above-mentioned film, it is molten
Liquid uses 3500rpm/min speed to rotate 30s after being uniformly distributed, and using 150 DEG C of drying 30min, that is, forms p-type protective layer.
(6) prepared by top electrode
Silver-colored top electrode is prepared using vacuum deposition method, vacuum chamber is depressed into 10-4Pa using mechanical pump and molecular pump pumping
Under, using film thickness instrument monitoring evaporation thickness 200nm.
Those of ordinary skill in fields it should be appreciated that, the features of the present invention or the first purpose are：
Using nano silver wire film layer and zinc-oxide nano column composite film layer, there is multiple light scattering, with cuprous oxide shape
Into heterojunction structure, light absorpting ability is improved, uses p-type high molecular material that can be effectively isolated oxygen for cuprous oxide protective layer
Change the cuprous water oxygen with air to be combined, cuprous oxide material lifetime can greatly be improved, the present invention has low cost, practical
Property it is strong, be easy to large-scale production etc. advantages, have broad application prospects.
It is pointed out that any change that one skilled in the art does the specific embodiment of the present invention
All without departing from the scope of claims of the present invention.Correspondingly, the scope of claim of the invention is also not merely limited to
In previous embodiment.
Claims (10)
1. a kind of preparation method of the cuprous oxide solar cell based on nano structure membrane electrode, which is characterized in that including：
There is provided has first surface and the substrate with the corresponding second surface of the first surface, cleans the substrate；
Nano silver wire film layer is prepared by the method for spin-coating on the first surface；
Zinc oxide films film layer is prepared in the nano silver wire film layer by the method for spin-coating；
Pass through Hydrothermal Growth zinc-oxide nano column layer in the zinc oxide films film layer；
Cuprous oxide film layer is prepared on the zinc-oxide nano column layer by electrochemical deposition method；
On the cuprous oxide film layer p-type protective layer is prepared with the method for spin-coating；
It is protected by any one method in silk-screen printing, vacuum evaporation, vacuum sputtering or electron beam evaporation in the p-type
Top electrode is prepared on layer, electrode layer is formed, completes the making of the cuprous oxide solar cell based on nano structure membrane electrode.
2. the preparation method of the cuprous oxide solar cell according to claim 1 based on nano structure membrane electrode,
It is characterized in that：The substrate is first cleaned with detergent, is then cleaned using EtOH Sonicate, then using deionized water ultrasound
Cleaning, is finally cleaned with deionized water, and the substrate after cleaning is dried, substrate is put and is maintained in nitrogen environment.
3. the preparation method of the cuprous oxide solar cell according to claim 1 based on nano structure membrane electrode,
It is characterized in that, preparing nano silver wire film layer by the method for spin-coating on the first surface includes：Take 1-10mg/
The substrate is placed on spin-coating on whirler, silver nanoparticle is formed after to be dried by the nano silver wire alcohol dispersion liquid of ml
Line film layer, the thickness of the nano silver wire film layer is 200-1000nm.
4. the preparation method of the cuprous oxide solar cell according to claim 1 based on nano structure membrane electrode,
It is characterized in that, preparing zinc oxide films film layer in the nano silver wire film layer by the method for spin-coating includes：By zinc
Compound, diethanol amine and ethyl alcohol are mixed and reacted under 40-100 DEG C of temperature conditions, and ageing forms zinc oxide afterwards for 24 hours
Colloidal sol obtains zinc-oxide film with the method for spin-coating in the nano silver wire film layer, forms zinc oxide after drying
Film layer, the thickness of the zinc oxide films film layer is 10-200nm.
5. the preparation method of the cuprous oxide solar cell according to claim 4 based on nano structure membrane electrode,
It is characterized in that：The zinc compound be zinc acetate, zinc nitrate or zinc acetylacetonate in one or more, the zinc compound
Middle zinc concentration is 0.01-1mol/L, and the amount ratio of the substance of the diethanol amine and zinc is 1：1.
6. the preparation method of the cuprous oxide solar cell according to claim 1 based on nano structure membrane electrode,
It is characterized in that, included in the zinc oxide films film layer by Hydrothermal Growth zinc-oxide nano column layer：By the zinc oxide
Film layer is put into beaker down, and zinc-oxide nano column layer is obtained by Hydrothermal Growth, the zinc-oxide nano column layer
Highly it is 500nm-2000nm.
7. the preparation method of the cuprous oxide solar cell according to claim 1 based on nano structure membrane electrode,
It is characterized in that, preparing cuprous oxide film layer on the zinc-oxide nano column layer by electrochemical deposition method includes：With steaming
Distilled water configuration concentration is the cupric salt solution of 0.01-0.2mol/L, the lactic acid of 10 times of mantoquita concentration is added in, with NaOH solution tune
PH value is saved to 12, electroplate liquid is obtained after being sufficiently stirred, the zinc-oxide nano column layer carries out electro-deposition, shape in the electroplate liquid
Into cuprous oxide film layer, the cupric salt is the one or more in copper acetate, copper nitrate or copper sulphate.
8. the preparation method of the cuprous oxide solar cell according to claim 1 based on nano structure membrane electrode,
It is characterized in that, preparing p-type protective layer with the method for spin-coating on the cuprous oxide film layer includes：By PEDOT：
The P3HT/ chlorobenzene solutions of PSS solution or 2-10mg/ml are dropped on the cuprous oxide film layer, at 150 DEG C after spin-coating
Under conditions of heat 20min and cure, form p-type protective layer, the thickness of the p-type protective layer is 20-100nm.
9. the preparation method of the cuprous oxide solar cell according to claim 1 based on nano structure membrane electrode,
It is characterized in that：The thickness of the top electrode is 200-3000nm.
10. it is a kind of as made from claim 1-9 any one claim the methods based on nano structure membrane electrode
Cuprous oxide solar cell, which is characterized in that from bottom to top include successively：Substrate, nano silver wire film layer, zinc-oxide film
Layer, zinc-oxide nano column layer, cuprous oxide film layer, p-type protective layer, electrode layer.
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