CN108807687A - A kind of preparation method of nickel oxide film - Google Patents
A kind of preparation method of nickel oxide film Download PDFInfo
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- CN108807687A CN108807687A CN201810611518.7A CN201810611518A CN108807687A CN 108807687 A CN108807687 A CN 108807687A CN 201810611518 A CN201810611518 A CN 201810611518A CN 108807687 A CN108807687 A CN 108807687A
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- nickel oxide
- oxide film
- nickel
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- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 69
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 43
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 33
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000011282 treatment Methods 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 18
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000006228 supernatant Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000004528 spin coating Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229940031098 ethanolamine Drugs 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 238000010422 painting Methods 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229940012017 ethylenediamine Drugs 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 10
- 239000011521 glass Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 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 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 238000004630 atomic force microscopy Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007737 ion beam deposition Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 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
- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Electromagnetism (AREA)
- Sustainable Energy (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Sustainable Development (AREA)
- Chemically Coating (AREA)
Abstract
The present invention relates to a kind of preparation methods of nickel oxide film.It includes the following steps successively：（1）Configure precursor solution：Nickel hydroxide, amine and alcohol organic solvent, ammonium hydroxide, progress is taken repeatedly to be dissolved to nickel hydroxide and be completely dissolved respectively, gained clear liquid is precursor solution；（2）Prepare film：The film that a layer thickness is 20~50nm is coated in the substrate surface that cleaning treatment is crossed in advance with precursor solution, substrate is placed in 250~450 DEG C of heat treatments later.The method of the present invention is of low cost, easy to operate, and the nickel oxide film of excellent combination property can be made.
Description
Technical field
The present invention relates to organic/inorganic photoelectric devices, are related to a kind of preparation method of nickel oxide film.
Background technology
Nickel oxide (NiOx) as a kind of excellent hole mobile material, organic/inorganic photoelectric device boundary layer and
There is important application in photochromic field.Especially in field of photoelectric devices, constructing for nickel oxide film can improve device inside
The transmission performance of level structure and charge, and then enhance the photoelectric conversion capacity of device.
Currently, the preparation of nickel oxide film mainly has physics and chemical two class means, such as vacuum vapour deposition, magnetron sputtering
Method, ion beam deposition, epitaxial film sedimentation, chemical/electrochemical sedimentation and sol-gel method etc..These preparation methods
The advantages of having itself and disadvantage, structure even compact, the pattern of the film as obtained by physical deposition means are excellent, but required set
It is standby general all more expensive and be difficult to prepare the film of large area.The chemistry or electrochemical techniques of use, equipment is less expensive,
But film quality generally requires high-temperature post-treatment and obtains oxidation film film compared with the difference of Physical.
Currently, sol-gel method is to prepare a kind of common method of nickel oxide film, it is by with soluble acetic acid
Source of the nickel salts such as nickel, nickel chloride, nickel nitrate as colloid nickel hydroxide is passed through using alcohols material as solvent and stabilizer
Uniformly mixing, a series of complex processes such as hydrolysis, condensation chemical reaction, forms stable transparent nickel hydroxide sol system,
Colloidal sol is aged again, slowly polymerize between micelle, forms the gel of three-dimensional net structure, and gel is applied by means such as spin coating or sprayings
It is overlying on substrate surface, nickel oxide film material is obtained using high temperature drying, sintering curing.But at present it is existing these
In preparation method, prepared nickel oxide film generally existing uniformity is not good enough, and microfissure is more.For example, using soluble
Source of the nickel acetate as nickel hydroxide, it is thin according to the nickel oxide film that above-mentioned conventional sol-gel method is prepared
Film pattern and atomic force microscopy phasor, respectively as shown in figure 1 and 2, phasor is presented as that graininess, roughness are about 2.3.
Invention content
The purpose of the present invention is to provide a kind of preparation method of nickel oxide film, the preparation method is of low cost, operates
Simply, and the nickel oxide film of excellent combination property can be made.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of nickel oxide film, which is characterized in that include the following steps successively：
(1) precursor solution is configured
Take nickel hydroxide viscous as dissolving and enhancing solution as the source of nickel oxide, amine and alcohol organic solvent respectively
The solvent of degree, ammonium hydroxide are repeatedly dissolved to nickel hydroxide and are completely dissolved as complexing solvent, progress, and gained clear liquid is used as and prepares oxygen
Change the precursor solution of nickel film；
(2) film is prepared
The film that a layer thickness is 20~50nm is coated in the substrate surface that cleaning treatment is crossed in advance with precursor solution, it
Substrate is placed in 250~450 DEG C of heat treatments afterwards, obtains nickel oxide film.
As further clear, in above-mentioned steps (1), nickel hydroxide, amine and alcohol organic solvent, ammonium hydroxide, four
Dosage is respectively according to 0.001~0.1g:0.1~10ml:0.1~10ml:1~10ml is configured.When precursor solution dosage is big, it can press
This ratio enlargement.
As further clear, above-mentioned amine organic solvent can be selected as ethylenediamine, ethanol amine, isopropanolamine etc., above-mentioned
Alcohol organic solvent can be selected as methanol, ethyl alcohol, ethylene glycol, ethylene glycol monomethyl ether etc..
As further clear, the painting method in above-mentioned steps (2), optional spin coating, inkjet printing or spraying etc. are normal
Rule method.
As further defining, the heat treatment time in above-mentioned steps (2) is 30 minutes.
As further defining, the multiple dissolving step in above-mentioned steps (1) can specifically be carried out according to following operation：
Nickel hydroxide and part amine, alcohol organic solvent are first sufficiently mixed dissolving, it is abundant that partial ammonia water is then added
Stir, stand 12 hours or more, take supernatant；It is organic that remaining undissolved nickel hydroxide continues first addition part amine, alcohols
Solvent is sufficiently mixed dissolving, and partial ammonia water is then added and is sufficiently stirred, stands 12 hours or more, then takes supernatant；And so on,
Until after nickel hydroxide is completely dissolved, merge each supernatant.
As further defining, the advance cleaning treatment of substrate surface in above-mentioned steps (2) specifically can be according to following operation
It carries out：
Substrate (such as electro-conductive glass ITO) is placed in ultrasound 10 minutes in deionized water, is gently rubbed with non-dust cloth and removes dirt, later
Ultrasound 10 minutes in deionized water are placed in, substrate are then sequentially placed into acetone, chloroform, isopropanol each ultrasonic 10 minutes, finally
Substrate is placed in baking oven and is dried for standby.Certainly, the advance cleaning treatment of substrate surface can also be used other conventional modes into
Row.
As further clear, above-mentioned ammonium hydroxide, aqueous solution containing ammonia 25%~28% is used, in terms of mass percentage.
It is found in inventor's research：Size, network structure of nickel hydroxide micelle etc. be vulnerable to former soluble nickel salt the moon from
The influence of sub (acetate, chlorion, nitrate anion etc.), and negative shadow is generated to the nickel oxide film pattern of high temperature sintering, structure
It rings, and then the final performance for influencing nickel oxide film.And the present invention uses amine directly using nickel hydroxide as the source of nickel oxide
It dissolves and disperses with alcohols solvent, be the solubility that complex compound enhances nickel source with ammonium hydroxide, it is conventional using spin coating or spraying etc.
The mode of painting method and high-temperature process directly avoids soluble nickel salt anionic (acetate, chlorion, nitrate anion
Deng) negative effect to the size of nickel hydroxide micelle, network structure etc., and then avoid the nickel oxide to high temperature sintering
Film morphology, structure have a negative impact, and finally ensure and optimize the comprehensive performance of nickel oxide film.
The invention has the advantages that：
The present invention provides a kind of preparation methods of nickel oxide film, and the preparation method is of low cost, easy to operate, especially
It is it directly using nickel hydroxide as the source of nickel oxide, is dissolved and disperseed with amine and alcohols solvent, be complexing with ammonium hydroxide
Object enhances the solubility of nickel source, using the mode of the conventional application methods such as spin coating or spraying and high-temperature process in substrate
The nickel oxide film for obtaining excellent combination property avoids soluble nickel salt anionic (acetate, chlorion, nitrate anion etc.)
Negative effect to the size of nickel hydroxide micelle, network structure etc., and then avoid thin to the nickel oxide of high temperature sintering
Film pattern, structure have a negative impact, and finally ensure and optimize the comprehensive performance of nickel oxide film.Using the method for the present invention institute
The nickel oxide film being prepared has following excellent characteristic：
(1) light transmission rate is high：
The product of nickel oxide film is coated on substrate I TO using the method for the present invention, through close red using ultraviolet-visible-
Outer absorption spectrometer detection (when test on the basis of air, first surveys the transmitance of ito glass, then surveys and be coated with nickel oxide ito glass
Transmitance), measure its light transmission rate the sections 400~800nm be 76.0%~84.6%, 516nm at maximum transmission
It is 84.6%.
(2) charge transfer efficiency is high, film conductivity is good：
The product of nickel oxide film is coated on substrate I TO using the method for the present invention, through being examined using four-point probe
It surveys, it is about 13.5~14.2 ohm (sheet resistance of used ito glass is about 13 ohm) to measure its sheet resistance.
(3) film is fine and close, uniformity is good, purity is high, free from admixture particle.
The nickel oxide film can be used as interface hole transport layer material, be applied to organic solar batteries, organic electroluminescence is sent out
The organic/inorganics field of photoelectric devices such as optical device, perovskite battery, perovskite luminescent device, to improving device performance with aobvious
Write help.
Description of the drawings
Fig. 1 is the source as nickel oxide using soluble nickel acetate, is prepared according to conventional sol-gel method
Nickel oxide film scanning electron microscopy picture.
Fig. 2 is the source as nickel oxide using soluble nickel acetate, is prepared according to conventional sol-gel method
Nickel oxide film atomic force microscopy phasor.
Fig. 3 is the scanning electron microscopy picture of nickel oxide film prepared in the embodiment of the present invention 1.
Fig. 4 is the detection of content of element figure of nickel oxide film prepared in the embodiment of the present invention 1.
Fig. 5 is the atomic force microscopy phasor of nickel oxide film prepared in the embodiment of the present invention 1.
Fig. 6 is the light for being coated with nickel oxide film product in the embodiment of the present invention 1 on substrate I TO using the method for the present invention
Learn transmitance detection figure.
Fig. 7 is the J-V figures of the organic photovoltaic devices containing nickel oxide film prepared in the embodiment of the present invention 1.
Specific implementation mode：
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.
Embodiment 1
A kind of preparation method of nickel oxide film, includes the following steps successively：
(1) it cleans, dry substrate
Substrate (electro-conductive glass ITO) is placed in deionized water ultrasound 10 minutes, is gently rubbed with non-dust cloth and removes dirt, postposition
Ultrasound 10 minutes, are then sequentially placed into acetone, chloroform, isopropanol each ultrasonic 10 minutes by substrate in deionized water, finally will
Substrate is placed in baking oven and is dried for standby；
(2) precursor solution is configured
Nickel hydroxide, ethanol amine and ethylene glycol monomethyl ether, ammonium hydroxide is taken (to contain ammonia 25%) respectively, four according to 0.1g:2ml:
2ml:The ratio of 2ml carries out dispensing；Nickel hydroxide and part ethanol amine and ethylene glycol monomethyl ether are first sufficiently mixed dissolving, then added
Enter partial ammonia water to be sufficiently stirred, stand 12 hours or more, takes supernatant；Part is first added in remaining undissolved nickel hydroxide continuation
Ethanol amine and ethylene glycol monomethyl ether are sufficiently mixed dissolving, and partial ammonia water is then added and is sufficiently stirred, stands 12 hours or more, then takes
Clear liquid；And so on, until after nickel hydroxide is completely dissolved, merge each supernatant, it is thin that gained clear liquid as prepares nickel oxide
The precursor solution of film.
(3) film is prepared
In the substrate surface that area is 1.5cm × 1.5cm, it is molten that 80 microlitres of forerunner is drawn using conventional spin coating method
Substrate is placed in by liquid, the spin coating 30 seconds under conditions of rotating speed 3000rpm, the film that coating a layer thickness is 20~30nm later
It is handled 30 minutes in 300 DEG C of thermal station.
3,4 and 5 it is found that nickel oxide film obtained in this example is fine and close, careful bulk, uniformity with reference to the accompanying drawings
Well, porosity defects are less, purity is high, free from admixture particle, and it is about 2.1 to measure its roughness using atomic force microscope.
In this example, following detection experiment has also been carried out：
Respectively with substrate I TO, and the method for the present invention is used to be coated with the product of nickel oxide film on substrate I TO as in fact
Object is tested, light transmission rate and electric conductivity detection are carried out：
(1) light transmission rate detects
It is measured using UV-visible-near infrared absorption instrument, the transmitance of substrate I TO is in the sections 400~800nm
Maximum transmission at 78.2%~84.7%, 516nm is 84.7%；It is coated on substrate I TO using the method for the present invention aerobic
Change nickel film product transmitance the sections 400~800nm be 76.0%~84.6%, 516nm at maximum transmission be
84.6%, referring specifically to attached drawing 6.As it can be seen that high using the preparation-obtained nickel oxide film light transmission rate of the method for the present invention.
(2) electric conductivity detects
It is measured using four-point probe, the sheet resistance of substrate I TO is about 13 ohm；Using the method for the present invention in substrate I TO
The sheet resistance of the upper product coated with nickel oxide film is about at 13.5~14.2 ohm.
In addition, also having carried out following application test in this example：
The product that nickel oxide film is coated on substrate I TO that will be prepared in this example, is transferred to spin coating in glove box
(1000r/min, 20s) P3HT:PC61BM mixed solutions (dissolve P3HT with o-dichlorohenzene solvent:PC61BM, mass ratio 1:1,
The two concentration is 20mg/ml) slow curing acquisition photosensitive layer, later in P3HT:PC61Spin coating polyfluorene class is conjugated high score on BM photosensitive layers
Sub- PFN electron transfer layers, then it is transferred to deposited metal aluminium electrode in vacuum coating equipment, obtain ITO/NiO/P3HT:PC61BM/
PFN/Al device architectures.
To determine that the effect of nickel oxide, the preparation method in being tested according to above application are also separately prepared for ITO/P3HT:
PC61BM/PFN/Al device architectures, to analyze.As a result, it has been found that the former short circuit current is 9.22mA/cm2, open-circuit voltage is
624mV, fill factor 0.58, efficiency 3.35% are 8.67mA/cm compared with the latter's short circuit current2, open-circuit voltage 517mV,
Fill factor is 0.41, efficiency 1.75%, the former efficiency improves nearly 1 times of performance, test result such as Fig. 7 institutes compared with the latter
Show.As it can be seen that making the height of the charge transfer efficiency in device, film lead using the preparation-obtained nickel oxide film of the method for the present invention
It is electrically good.
According to the above as can be seen that the method for the present invention improve nickel oxide film charge transport layer appearance structure,
Transfer and charge of the enhancing charge between active layer and nickel oxide have important in nickel oxide layer to the transmission between electrode ITO
Benefit；Meanwhile contributing to reduce the blocking to solar energy using nickel oxide layer transparent made from this method, hardly
Weaken absorption of the active layer to light.
Embodiment 2
A kind of preparation method of nickel oxide film, includes the following steps successively：
(1) it cleans, dry substrate
Substrate (electro-conductive glass ITO) is placed in deionized water ultrasound 10 minutes, is gently rubbed with non-dust cloth and removes dirt, postposition
Ultrasound 10 minutes, are then sequentially placed into acetone, chloroform, isopropanol each ultrasonic 10 minutes by substrate in deionized water, finally will
Substrate is placed in baking oven and is dried for standby；
(2) precursor solution is configured
Nickel hydroxide, ethylenediamine and ethylene glycol, ammonium hydroxide is taken (to contain ammonia 28%) respectively, four according to 0.01g:1ml:1ml:
The ratio of 2ml carries out dispensing；Nickel hydroxide and part ethylenediamine and ethylene glycol are first sufficiently mixed dissolving, part ammonia is then added
Water is sufficiently stirred, stands 12 hours or more, takes supernatant；Remaining undissolved nickel hydroxide continue first to be added part ethylenediamine and
Ethylene glycol is sufficiently mixed dissolving, and partial ammonia water is then added and is sufficiently stirred, stands 12 hours or more, then takes supernatant；With such
It pushes away, until after nickel hydroxide is completely dissolved, merges each supernatant, the forerunner that gained clear liquid as prepares nickel oxide film is molten
Liquid.
(3) film is prepared
The substrate surface for being 1.5cm × 1.5cm in area with precursor solution, use conventional spray-on process setting procedure for
The period of 1cm, spray velocity 25mm/s, air pressure speed 10L/min, spraying are 1, and coating a layer thickness is the thin of 30~50nm
Substrate is placed in 300 DEG C of thermal station handles 30 minutes later, obtains nickel oxide film by film.
Embodiment 3
A kind of preparation method of nickel oxide film, includes the following steps successively：
(1) it cleans, dry substrate
Deionized water, acetone, chloroform, isopropanol is successively respectively adopted in substrate (electro-conductive glass ITO), is respectively cleaned by ultrasonic 2
It is secondary, after be put into baking oven and be dried for standby；
(2) precursor solution is configured
Nickel hydroxide, ethanol amine and ethyl alcohol, ammonium hydroxide is taken (to contain ammonia 26%) respectively, four according to 0.02g:2ml:4ml:4ml
Ratio carry out dispensing；Nickel hydroxide and part ethanol amine and ethyl alcohol are first sufficiently mixed dissolving, partial ammonia water is then added and fills
Divide stirring, stand 12 hours or more, take supernatant；Remaining undissolved nickel hydroxide continues that part ethanol amine and ethyl alcohol is first added
It is sufficiently mixed dissolving, partial ammonia water is then added and is sufficiently stirred, stands 12 hours or more, then takes supernatant；And so on, until
After nickel hydroxide is completely dissolved, merge each supernatant, gained clear liquid is the precursor solution for preparing nickel oxide film.
(3) film is prepared
In the substrate surface that area is 1.5cm × 1.5cm, it is molten that 80 microlitres of forerunner is drawn using conventional spin coating method
Substrate is placed in by liquid, the spin coating 30 seconds under conditions of rotating speed 3000rpm, the film that coating a layer thickness is 20~30nm later
It is handled 25 minutes in 400 DEG C of thermal station, obtains nickel oxide film.
Claims (7)
1. a kind of preparation method of nickel oxide film, which is characterized in that include the following steps successively：
（1）Configure precursor solution
Nickel hydroxide, amine and alcohol organic solvent, ammonium hydroxide, progress is taken repeatedly to be dissolved to nickel hydroxide and be completely dissolved respectively, institute
It is precursor solution to obtain clear liquid；
（2）Prepare film
The film that a layer thickness is 20~50nm is coated in the substrate surface that cleaning treatment is crossed in advance with precursor solution, later will
Substrate is placed in 250~450 DEG C of heat treatments.
2. the preparation method of nickel oxide film as described in claim 1, it is characterised in that：The step（1）In, nickel hydroxide,
Amine and alcohol organic solvent, ammonium hydroxide, four dosage is respectively according to 0.001~0.1g:0.1~10ml:0.1~10ml:1~
10ml is configured.
3. the preparation method of nickel oxide film as claimed in claim 1 or 2, it is characterised in that：The amine organic solvent is selected
For ethylenediamine, ethanol amine or isopropanolamine；It is methanol, ethyl alcohol, ethylene glycol or ethylene glycol monomethyl ether that the alcohol organic solvent, which is selected,.
4. the preparation method of nickel oxide film as described in claim 1-3 is any, it is characterised in that：The step（2）In painting
Coating method selects spin coating, inkjet printing or spraying；The step（2）In heat treatment time be 30 minutes.
5. the preparation method of nickel oxide film as described in claim 1-4 is any, which is characterized in that the step（1）In it is more
Secondary dissolving step is specifically carried out according to following operation：
Nickel hydroxide and part amine, alcohol organic solvent are first sufficiently mixed dissolving, then addition partial ammonia water be sufficiently stirred,
Stand 12 hours or more, take supernatant；Remaining undissolved nickel hydroxide continues first addition part amine, alcohol organic solvent and fills
Divide mixed dissolution, partial ammonia water is then added and is sufficiently stirred, stands 12 hours or more, then takes supernatant；And so on, until hydrogen
After nickel oxide is completely dissolved, merge each supernatant.
6. the preparation method of nickel oxide film as described in claim 1-5 is any, which is characterized in that the step（2）Middle substrate
The advance cleaning treatment on surface is specifically carried out according to following operation：
Substrate is placed in deionized water ultrasound 10 minutes, is gently rubbed with non-dust cloth and removes dirt, be placed in deionized water it is ultrasonic
10 minutes, substrate is then sequentially placed into acetone, chloroform, isopropanol each ultrasonic 10 minutes, finally substrate is placed in baking oven and is dried
It is dry spare.
7. the preparation method of nickel oxide film as described in claim 1-6 is any, which is characterized in that the ammonium hydroxide, which uses, contains ammonia
25%~28% aqueous solution, in terms of mass percentage.
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| CN110491599A (en) * | 2019-08-05 | 2019-11-22 | 重庆文理学院 | A kind of preparation method of composite conductive thin film |
| CN111239203A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Preparation method of copper oxide film |
| CN112186107A (en) * | 2020-09-27 | 2021-01-05 | 武汉大学 | Tin-based perovskite solar cell with hole transport layer and preparation method thereof |
| CN112624214A (en) * | 2020-12-28 | 2021-04-09 | 苏州大学张家港工业技术研究院 | Magnetic nickel oxide film and preparation method thereof |
| CN113227452A (en) * | 2018-11-21 | 2021-08-06 | 亨特钙钛矿技术有限责任公司 | Nickel oxide sol-gel inks |
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| US11713396B2 (en) | 2018-11-21 | 2023-08-01 | Cubicpv Inc. | Nickel oxide sol-gel ink |
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| CN111239203A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Preparation method of copper oxide film |
| CN111239203B (en) * | 2018-11-29 | 2022-05-17 | 中国科学院大连化学物理研究所 | Preparation method of copper oxide film |
| CN110491599A (en) * | 2019-08-05 | 2019-11-22 | 重庆文理学院 | A kind of preparation method of composite conductive thin film |
| CN112186107A (en) * | 2020-09-27 | 2021-01-05 | 武汉大学 | Tin-based perovskite solar cell with hole transport layer and preparation method thereof |
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| CN112624214A (en) * | 2020-12-28 | 2021-04-09 | 苏州大学张家港工业技术研究院 | Magnetic nickel oxide film and preparation method thereof |
| CN112624214B (en) * | 2020-12-28 | 2023-06-23 | 苏州大学张家港工业技术研究院 | Magnetic nickel oxide film and preparation method thereof |
| CN114405304B (en) * | 2022-02-17 | 2023-08-08 | 河北科技大学 | Composition for dispersing nickel oxide in organic solvent and dispersing method |
| CN114405304A (en) * | 2022-02-17 | 2022-04-29 | 河北科技大学 | Composition for dispersing nickel oxide in organic solvent and dispersing method |
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