CN110590181A - Preparation method of ZnO film and application of ZnO film in ultraviolet sensor - Google Patents
Preparation method of ZnO film and application of ZnO film in ultraviolet sensor Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 17
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 16
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 16
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000005660 hydrophilic surface Effects 0.000 claims abstract description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract 2
- 239000010408 film Substances 0.000 claims description 62
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 239000010409 thin film Substances 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 4
- 239000004697 Polyetherimide Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 4
- 229920002530 polyetherether ketone Polymers 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
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- 229910009112 xH2O Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 170
- 239000011787 zinc oxide Substances 0.000 description 85
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- 230000004044 response Effects 0.000 description 13
- 238000012512 characterization method Methods 0.000 description 10
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 230000004298 light response Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
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- 238000011084 recovery Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
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- 150000003751 zinc Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- -1 hydroxyl ions Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0085—Drying; Dehydroxylation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/216—ZnO
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention provides a preparation method of a ZnO film and application of the ZnO film in an ultraviolet sensor, wherein the method comprises the following steps: s1: preparing a precursor solution, wherein the precursor solution comprises a complex of zinc hydroxide and ammonia water; s2: providing a substrate, and carrying out hydrophilic treatment on the substrate to enable the substrate to have a hydrophilic surface; s3: coating the precursor liquid on the surface of the substrate; s4: and annealing the substrate coated with the precursor liquid to obtain the pure-phase continuous ZnO film on the surface of the substrate. According to the invention, the thickness of the ZnO film can be reduced and the density of the ZnO film can be improved by improving the preparation process of the ZnO film, and the sensitivity of the ultraviolet sensor is greatly improved; the flexible ultraviolet sensor prepared by the invention shows good flexible ultraviolet sensor characteristics.
Description
Technical Field
The invention belongs to the field of film preparation and sensors, and relates to a preparation method of a ZnO film and application of the ZnO film in an ultraviolet sensor.
Background
Compared with the traditional narrow-bandgap semiconductor based on silicon material, the semiconductor material with wide bandgap (Eg ≥ 3.2eV) has higher breakdown voltage, higher electron drift saturation velocity and stronger radiation resistance, so that the photoconductive ultraviolet sensor based on the semiconductor material with wide bandgap has more excellent performance. The materials currently used for the preparation of wide band gap uv sensors are: diamond, SiC, GaN, AlGaN, ZnO, ZnS, ZnSe, TiO2And the like. The biocompatibility of ZnO in the materials and the diversity of the nanometer structure make the materials ideal for preparing sensors. Compared with a bulk material, the high specific surface area of the nano material makes the nano material have unique advantages in the aspect of preparing an ultraviolet sensor. When a ZnO ultraviolet sensor based on a micro-nano structure is prepared, the key for improving the sensitivity of the sensor is to realize lower electron concentration and high electron mobility in ZnO under a dark condition. Since electrons inside ZnO can be depleted by adsorbed oxygen or modified metal particles with high work function on the surface, thereby forming a high-resistance depletion region inside ZnO near the surface, using nanostructures with high specific surface area helps to obtain lower dark current under dark conditions. Because of the high specific surface area, ZnO nanowires are widely applied to the preparation of ultraviolet sensors. Up to now, among the ultraviolet sensors based on ZnO nanowires, the sensors modified by means of Au nanoparticles have the highest sensitivity, at 1.3mW/cm2Has a value of 5X 10 under the ultraviolet light intensity6. In past work, since the size of the single crystal nanomaterial used to fabricate the ZnO-based ultraviolet sensor is larger than the width of its depletion region in the dark, the carriers inside the material are not sufficiently depleted. The sensitivity of the ZnO-based sensor is further improved if the carriers inside the ZnO can be sufficiently depleted in the dark. Besides single crystal nano materials, a ZnO network structure is another main material for preparing an ultraviolet sensor. Oxygen content relative to single crystal nanomaterialsThe carriers can be adsorbed to the grain boundaries and the interior of pores in the network structure, so that the carriers in the interior can be further depleted. An ultraviolet sensor prepared on the basis of a ZnO fluffy porous film with fully exhausted current carriers is 0.1mW/cm2Under the irradiation of ultraviolet light intensity, it has a luminous intensity of up to 3.4X 105The sensitivity of (2). But the 98% porosity of this structure inevitably reduces the mobility of electrons inside it. The high electron mobility can increase the photocurrent of the sensor when the ZnO is exposed to ultraviolet radiation. High electron mobility can be achieved by increasing the crystallinity of ZnO, increasing the grain size, reducing cracks and pores in the thin film.
Therefore, how to provide a ZnO material with high electron mobility and capable of sufficiently depleting its internal carriers in the dark to greatly improve the sensitivity of the uv sensor is an important technical problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for preparing a ZnO thin film and its application in an ultraviolet sensor, which is used to solve the problem that the sensitivity of the ZnO-based ultraviolet sensor in the prior art needs to be improved.
To achieve the above and other related objects, the present invention provides a method for preparing a ZnO film, referring to fig. 1, which is a process flow diagram of the method, comprising the steps of:
s1: preparing a precursor solution comprising zinc hydroxide (Zn (OH)2) A complex with ammonia;
s2: providing a substrate, and carrying out hydrophilic treatment on the substrate to enable the substrate to have a hydrophilic surface;
s3: coating the precursor liquid on the surface of the substrate;
s4: and annealing the substrate coated with the precursor liquid to obtain the pure-phase continuous ZnO film on the surface of the substrate.
Optionally, the preparation process of the zinc hydroxide comprises: and dropping the sodium hydroxide solution into the zinc nitrate solution to obtain flocculent liquid, and centrifuging to obtain zinc hydroxide precipitate.
It should be noted that although there are various zinc salts and alkaline solutions which can be used for preparing zinc hydroxide, in the process of the present invention for preparing zinc hydroxide, the zinc salt cannot be selected at will even if it has high solubility in aqueous solution, such as zinc chloride, and chlorine can replace Zn (OH)2OH-of (C) to form Zn5(OH)8Cl2.H2O, ZnOHCl, the presence of Cl elements lengthens the distance between OH groups, making these substances required to decompose at higher temperatures, contrary to the present invention which uses a low temperature process to make ZnO. The invention uses zinc nitrate (Zn (NO)3)2) Is due to (NO)3)-Although it will also react with Zn (OH)2Form a material such as Zn5(OH)8(NO3)2.2H2O, etc., but due to Zn2+Can polarize NO3 -Thereby lowering the bond level of the N-O bond and thus lowering its decomposition temperature. Also, the lye is not optional, e.g. Ca (OH)2Is not feasible because it is too weak in basicity to produce Zn (OH)2During the precipitation, a base with high molar weight is required to be slowly dripped to gradually replace NO3 -Ion to obtain Zn (OH) with higher purity2And (4) precipitating.
Optionally, the amount of the substance of hydroxyl ions dropped into the zinc nitrate solution is more than twice of the amount of the substance of zinc ions in the zinc nitrate solution, so as to ensure that all the zinc ions in the zinc nitrate solution generate the zinc hydroxide precipitate, otherwise, a pure-phase ZnO film cannot be obtained;
optionally, the method further comprises the steps of adding the zinc hydroxide precipitate into deionized water at least once, uniformly dispersing, and centrifuging again to obtain the zinc hydroxide precipitate. Through multiple centrifugal treatments, Na in the precipitate can be reduced+And NO3-The content of the ions is beneficial to obtaining the pure-phase ZnO film.
Optionally, the complex is of the formula Zn5(OH)8(NO3)2.(2-x)NH3.xH2O, wherein, 0<x<And 2, the concentration range of the complex in the precursor liquid is 0.3M-0.9M.
Optionally, the substrate is a rigid substrate or a flexible substrate, the rigid substrate is made of a material including but not limited to glass, and the flexible substrate is made of a material including but not limited to polyimide (Kapton), Polyetherimide (PEI), and Polyetheretherketone (PEEK).
It should be noted that the hydrophilization treatment of the substrate is critical, and the hydrophilization treatment can increase the wettability between the precursor solution and the substrate in the subsequent coating process, and is beneficial to obtaining a thinner continuous ZnO film with high quality.
Optionally, the substrate is a glass substrate or a polyimide substrate, and the hydrophilic treatment comprises the following steps:
(1) sequentially carrying out ultrasonic cleaning on the substrate by adopting acetone, ethanol and deionized water;
(2) drying the substrate with air or inert gas;
(3) drying the residual water vapor on the surface of the substrate;
(4) uniformly mixing concentrated sulfuric acid and a hydrogen peroxide solution to obtain a mixed solution, and placing the substrate in the mixed solution for treatment for a preset time, wherein the concentration of the concentrated sulfuric acid is more than 70 wt%, and preferably 98 wt%.
Alternatively, the concentration of the hydrogen peroxide solution is in the range of 10 wt% to 50 wt%, preferably 30 wt%. The volume ratio of the concentrated sulfuric acid to the hydrogen peroxide solution is 1.5: 1-5: 1, and preferably 3: 1. The predetermined time is 10 minutes to 10 hours, preferably 3 hours.
Optionally, the substrate is a polyetherimide substrate or a polyetheretherketone substrate, and the hydrophilic treatment comprises a step of plasma cleaning the substrate or a step of grafting a hydrophilic acrylate monomer-based coating on the surface of the substrate.
Optionally, the precursor solution is coated on the surface of the substrate by using a spin coating method.
Optionally, the annealing temperature range is 120 ℃ to 300 ℃, the annealing temperature range can be adjusted by combining the bearing capacity of the substrate, and the heat preservation time is more than 1 hour. Annealing after spin coating is performed to increase the crystallinity of the ZnO thin film.
Optionally, the ZnO thin film has a thickness in a range of 16nm to 25 nm.
The invention also provides an application of the ZnO film in an ultraviolet sensor, wherein the ZnO film is prepared by adopting any one of the methods, and the ZnO film is used for converting an ultraviolet signal into an electric signal. When the substrate adopts a rigid substrate, the obtained ultraviolet sensor is a rigid sensor, and when the substrate adopts a flexible substrate, the obtained ultraviolet sensor is a flexible sensor.
The detection mechanism and the design idea of the ultraviolet sensor are as follows: o is assumed to be present at the surface of the ZnO film under dark conditions2 -Has an area density of alpha, an electron concentration in a conduction band inside the material of n, and a thickness of d. And assuming that the device is exposed to ultraviolet light, O of the surface2 -All desorb. Based on the above assumptions, when the device is not irradiated by ultraviolet light, the free carrier concentration inside the device will be due to the surface O2 -Is reduced by the presence of n1N- α/d. At an applied voltage, if the mobility of the carriers is fixed, the current flowing through the device is proportional to the electron concentration inside the material. The sensitivity of the material can thus be expressed as n/n11/(1- α/(n × d)). Where α/n has a dimension of length which can be used as a characteristic value to characterize the device by O when not illuminated2 -Thickness of depletion layer generated by adsorption. As shown in fig. 2, which shows the sensitivity of the uv sensor as a function of film thickness, it can be seen that the sensitivity of the sensor increases dramatically as the device size approaches this characteristic thickness. The high-quality and ultrathin ZnO film prepared by the invention is used as a photoelectric conversion material of the ultraviolet sensor, and the sensitivity of the ultraviolet sensor can be effectively improved.
Optionally, the ultraviolet sensor is obtained by manufacturing an interdigital positive electrode and an interdigital negative electrode on the surface of the ZnO film. In the ultraviolet sensor, the thickness of the ZnO film is preferably 20 nm.
Optionally, the width of the fingers of the positive interdigital electrode or the negative interdigital electrode ranges from 0.1 mm to 0.5mm, and the inter-finger distance ranges from 0.5mm to 1.5 mm. The smaller the interdigital distance of the interdigital electrode is, the narrower the interdigital width is, and the better the effect is.
Optionally, the interdigital positive electrode and the interdigital negative electrode are made by a screen printing method.
Optionally, the interdigital positive electrode and the interdigital negative electrode are both made of carbon, or one of the interdigital positive electrode and the interdigital negative electrode is made of carbon, and the other electrode is made of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid).
The poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) PEDOT is called PSS for short, and consists of PEDOT and PSS, wherein the PEDOT is a polymer of EDOT (3, 4-ethylenedioxythiophene monomer), and the PSS is polystyrene sulfonate. According to the invention, the self-powered ultraviolet sensor based on the photovoltaic effect can be obtained by changing C of the interdigital electrode into C/PEDOT PSS.
As described above, the preparation method of the ZnO thin film and the application thereof in the ultraviolet sensor of the present invention have the following beneficial effects: according to the invention, by improving the preparation process of the ZnO film, the thickness of the ZnO film can be reduced, the density of the ZnO film can be improved, so that the ultraviolet sensor has lower dark current under the condition of no light irradiation and higher photocurrent under the condition of light irradiation, and the sensitivity of the ultraviolet sensor is greatly improved compared with the conventional ultraviolet sensor; the flexible ultraviolet sensor prepared by the invention can well maintain the mechanical property and the sensitivity under the condition that the substrate is bent to the curvature radius of 18.5mm, and shows good flexible ultraviolet sensor characteristics.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the ZnO thin film of the present invention.
FIG. 2 shows the sensitivity of the UV sensor as a function of film thickness.
Fig. 3 shows a two-dimensional plan view of an atomic force microscopy topography of a ZnO strip on a substrate.
Fig. 4 shows the step height of a ZnO stripe on a substrate.
Fig. 5 shows a three-dimensional view of an atomic force microscopy topography of a ZnO strip on a substrate.
Figure 6 shows XRD characterization patterns for ZnO films.
FIG. 7 is a schematic view showing the structure of an ultraviolet sensor prepared according to the present invention
FIG. 8 shows a rigid UV sensor made according to the present invention at a wavelength of 365nm and an intensity of 1mW/cm in the dark2I-V characteristics under ultraviolet irradiation.
FIG. 9 shows a rigid UV sensor prepared according to the present invention with a wavelength of 365nm and an intensity of 0.1mW/cm2The response curve of ultraviolet light.
FIG. 10 shows a flexible self-powered UV sensor made in accordance with the present invention at 1mW/cm in darkness2IV characteristics under uv irradiation.
FIG. 11 shows the UV sensor at a light intensity of 0.1mW/cm in the self-energized mode2Ultraviolet response under 365nm wavelength ultraviolet light.
FIG. 12 shows the UV sensor at a light intensity of 0.1mW/cm in the mode of applying 1V bias voltage2Ultraviolet response under 365nm wavelength ultraviolet light.
FIG. 13 shows the optical response of the sensor under UV illumination at different intensities at 365nm wavelength at a bias of 1V.
Fig. 14 is a partial enlarged view of fig. 13.
FIG. 15 shows the photocurrent and sensitivity of the sensor as a function of light intensity under UV irradiation at different light intensities at 365nm wavelength at a bias of 1V.
FIG. 16 shows the response of the sensor to UV light in the self-energized mode at different light intensities at 365 nm.
FIG. 17 shows the sensor photocurrent as a function of UV light intensity at different light intensities at 365nm wavelength in the self-energized mode.
FIG. 18 shows the dark current of the UV sensor in the initial flat state, in the bent state, and back to the flat state.
Fig. 19 shows the photoresponsive current in self-energized mode for the initial flat state, the bent state, and the return to the flat state.
FIG. 20 shows the photoresponse current in the 1V bias mode for the initial flat state, the bent state, and the return to the flat state.
Description of the element reference numerals
1 substrate
2 ZnO thin film
3 electrodes
S1-S4
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 3 to 20. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
Example one
Preparing a ZnO film:
(1) preparation of precursor solution
75mL of 0.5M zinc nitrate solution was added to a 200mL Erlenmeyer flask, a magneton was placed in the Erlenmeyer flask and placed on a magnetic stirrer, and 50mL of 2.5M sodium hydroxide solution was added dropwise to the stirring zinc nitrate solution. Placing the generated flocculent liquid in a centrifugal tube, centrifuging for 2min on the centrifugal machine at the rotating speed of 5000rpm, taking out the centrifugal tube, pouring out supernatant in the tube, adding deionized water, shaking until precipitates in the tube are uniformly dispersed, and placing the centrifugal tube in the centrifugal machine again for centrifuging according to the same parameters. After repeating this procedure for 5 times, the supernatant in the last centrifugation tube was poured out. The purpose of repeated centrifugation is to reduce the sodium and nitrate ion content of the precipitate. After the above procedure was complete, the resulting precipitate (zinc hydroxide) was added to 250mL of 6.6M aqueous ammonia. Magnetons were added and stirred until the precipitate was completely dissolved.
(2) Hydrophilic treatment of substrates
And ultrasonically cleaning the glass substrate for 20min by using acetone, ethanol and deionized water in sequence, drying the substrate by using air, then baking the substrate in an oven at 80 ℃ for 2h, and drying the residual water vapor on the surface. Mixing 98% concentrated sulfuric acid and 30% hydrogen peroxide solution according to the weight ratio of 3:1 and the baked substrate is placed in the solution and treated for 3 hours to increase the hydrophilicity of the substrate.
(3) Preparation of ZnO film by spin-coating method
Placing the substrate subjected to hydrophilization treatment on a table-type spin coater, and spin-coating the prepared precursor solution on the substrate, wherein the spin-coating parameters are as follows: rotating speed 1000rpm, spin-coating time 30s, drying the substrate on a glue drying table at 100 ℃, and then placing the substrate in a box-type annealing furnace for annealing, wherein the annealing parameters are as follows: raising the temperature from room temperature to 150 ℃ according to the heating rate of 2 ℃/min, preserving the temperature for 2h, and then naturally cooling to room temperature.
Thus, the ZnO film on the surface of the glass substrate is prepared.
As an example, the morphology of the prepared ZnO film is characterized by using an atomic force microscope, and the characterization results are shown in fig. 3, fig. 4 and fig. 5, where fig. 3 is a two-dimensional plane view of the atomic force microscope morphology of the ZnO strip on the substrate, fig. 4 is a step height of the ZnO strip on the substrate, and fig. 5 is a three-dimensional perspective view of the atomic force microscope morphology of the ZnO strip on the substrate. It can be seen from fig. 4 that the ZnO thin film has a thickness of about 20nm and a relatively flat surface. It can be concluded from fig. 5 that the roughness of the entire ZnO stripe was about 2nm and no cracks were generated on the surface of the thin film.
As an example, the ZnO thin film prepared was structurally characterized using an X-ray diffraction (XRD) instrument. Because the prepared ZnO film is thin, a grazing incidence method is adopted in XRD characterization. As shown in fig. 6, the XRD characterization pattern of the ZnO film is shown, and the straight line in the pattern is the standard XRD spectrum of wurtzite structure ZnO, and the peak position of the prepared ZnO film corresponds well to the peak position in the standard card, which proves that the synthesized film is indeed zinc oxide in wurtzite phase. In addition, the weak signal quantity in the figure can further prove that the prepared ZnO film is really thin.
Example two
Preparing an ultraviolet sensor based on the ZnO ultrathin film:
in this embodiment, an electrode is fabricated on the ZnO film prepared in the first embodiment, so as to obtain an ultraviolet sensor. Fig. 7 is a schematic structural diagram of the ultraviolet sensor, and includes a substrate 1, a ZnO film 2 formed on a surface of the substrate 1, and a pair of electrodes 3 formed on a surface of the ZnO film 2, where one of the electrodes is a positive electrode and the other electrode is a negative electrode. In this embodiment, the sensor electrodes preferably employ an interdigital positive electrode and an interdigital negative electrode.
As an example, the preparation procedure is as follows: the method comprises the steps of using carbon paste as a coating, transferring an electrode to a substrate with a ZnO film through a screen printing technology, then baking a device printed with the electrode on a glue drying table at 80 ℃ for 1h to fully volatilize an organic solvent in the carbon paste, and finally leading out leads at two ends of an interdigital electrode for testing. As an example, the parameters of the interdigitated electrodes on the screen printing plate are: the width of the interdigital is 0.5mm, and the distance between the interdigital is 1.5 mm.
The ultraviolet sensor in this embodiment is a rigid ultraviolet sensor because a glass substrate is used. The following are performance characterizations for the rigid uv sensor:
(1) I-V characteristic characterization: as shown in FIG. 8, the rigid UV sensor was shown to be in darkness (dark) and at a wavelength of 365nm and an intensity of 1mW/cm2I-V characteristics under ultraviolet irradiation. As can be seen from the figure, the contact type of ZnO with the carbon electrode is ohmic contact. Under dark conditions, when the external voltage is 1V, the current is 2.6 pA. Such low dark current also laterally confirms that the free electrons in the ZnO film have been substantially surface adsorbed by O2 -Is fully exhausted when being subjected to the intensity of 1mW/cm2The current of the ultraviolet light was increased to 93.9. mu.A. Under the light intensity, the sensitivity of the device reaches 3.6 multiplied by 107。
(2) Light response curve: as shown in FIG. 9, the rigid UV sensor showed 365nm wavelength and 0.1mW/cm intensity2The response curve of ultraviolet light. As can be seen from the graph, the intensity was 0.1mW/cm at a wavelength of 365nm2The photocurrent of the device was 3.49 muA under the irradiation of ultraviolet light. The sensitivity of the sensor reaches 1.3 multiplied by 106The value is the highest value of the sensitivity of the ultraviolet sensor reported by the literature under the same light intensity, namely 3.4 multiplied by 1053 times of the total weight of the product. In addition to sensitivity, the response and recovery time of the sensor is also characterized in this embodiment. Wherein the response time of the sensor is defined as: the time required for the photocurrent to reach 90% of its saturation value from the start of irradiation with ultraviolet light; the recovery time of the sensor is defined as: the irradiation from the ultraviolet light was stopped for a time required to reach 10% of its saturation current value. As can be calculated from fig. 9, the response time and the recovery time are 62.6s and 30.1s, respectively.
EXAMPLE III
Preparing a flexible ultraviolet sensor based on a ZnO ultrathin film:
when a Schottky junction formed by the ZnO film and a p-type conducting polymer poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) is irradiated by ultraviolet light, electron-hole pairs generated in a potential barrier region of the ZnO film move in opposite directions under the action of an internal electric field, and electrons and holes in motion generate photocurrent in an external circuit. In this example, on the basis of the first and second examples, the substrate is changed from a glass sheet to a flexible Kapton film (polyimide film), and the interdigital electrodes are changed from carbon interdigital electrodes to C/PEDOT: the PSS interdigital electrode (one of the pair of interdigital electrodes is made of C, and the other electrode is made of PEDOT: PSS), and the flexible self-powered ultraviolet sensor can be obtained.
The following is a performance characterization of the flexible self-powered uv sensor:
(1) I-V characteristic characterization: as shown in FIG. 10, the flexible self-powered UV sensor was shown to be in darkness and at 1mW/cm2IV characteristics under uv irradiation. As can be seen from the graph, under dark conditions, when the applied voltage was 1V, the current was 0.785 pA. The current is linear to the voltage due to the enormous resistance of the ZnO film when it is not irradiated with uv light. The potential difference dropped between the schottky junction formed by ZnO and PEDOT: PSS is smaller than the potential difference dropped inside ZnO due to the huge resistance of the ZnO film in the dark. Thus, although the presence of the schottky junction may cause the current to exhibit an exponential relationship with the voltage, the voltage dropped across the schottky junction is so low that, to a first approximation, the current and voltage exhibit a linear relationship. When the ZnO film is irradiated with ultraviolet light, desorption of surface adsorbed oxygen greatly reduces the resistance of the ZnO film (about 6 orders of magnitude), so that the voltage dropped inside the ZnO is reduced. At this time, the applied voltage basically falls on two ends of a Schottky junction formed between ZnO and PEDOT and PSS, and the I-V curve shows rectification characteristic.
(2) Light response curve: as shown in FIG. 11 and FIG. 12, the light response curve of the flexible self-powered UV sensor is shown, wherein FIG. 11 shows that the UV sensor has a light intensity of 0.1mW/cm in the self-powered mode2Ultraviolet response under 365nm ultraviolet light, FIG. 12 shows the ultraviolet sensor at 0.1mW/cm light intensity under 1V bias mode2Ultraviolet response under 365nm wavelength ultraviolet light. As can be seen, the ultraviolet sensor is subjected to the light with the wavelength of 365nm and the light intensity of 0.1mW/cm2The device can generate a photocurrent of 1nA when irradiated with ultraviolet light (FIG. 11), and the device can generate a photocurrent under the condition of applying a 1V bias voltageA photocurrent of 204nA was generated (fig. 12). Under the bias of 1V, the sensitivity of the device under the light intensity can reach 2.6 multiplied by 105。
(3) And (3) characterizing the ultraviolet performance of the sensor under different light intensities under fixed bias: the sensitivity of the sensor and the linear relationship between photocurrent and uv light intensity are necessary to detect and correct the uv light intensity. As shown in fig. 13 and 14, the optical response of the sensor under the irradiation of ultraviolet light with different light intensities having a wavelength of 365nm is shown under the bias of 1V, wherein fig. 14 is a partial enlarged view of fig. 13. As shown in fig. 15, the photocurrent and sensitivity of the sensor under uv light irradiation at different light intensities with a wavelength of 365nm are shown as a function of light intensity under a bias of 1V. As can be seen, the lowest UV detection intensity was 100nW/cm in the 1V bias mode2Under the irradiation of ultraviolet light of this intensity, the photocurrent and the sensitivity of the sensor were 430pA and 548, respectively.
(4) The ultraviolet performance characterization of the sensor under different light intensities under the self-powered mode is as follows: FIG. 16 shows the response of the sensor to UV light in the self-energized mode at different light intensities at 365 nm. FIG. 17 shows the sensor photocurrent as a function of UV light intensity at different light intensities at 365nm wavelength in the self-energized mode. In the self-powered mode, the lowest UV light intensity used is 10 μ W/cm2. The value of the saturated photocurrent was varied with the intensity of the ultraviolet light irradiated on the ultraviolet sensor as shown in fig. 16. The saturation current increases linearly with increasing uv light intensity. The obtained implementation data is subjected to linear regression analysis (figure 17) to obtain a certainty coefficient R of the implementation data2Is 0.993. Such a large certainty factor indicates that there is indeed a good linear relationship between the maximum photocurrent of the sensor and the intensity of the uv light irradiated.
(5) Flexible characterization of the uv sensor: when the device is bent, both the substrate and the electrodes can maintain their topography intact. In addition to its mechanical flexibility, the electro-optical properties of a flexible sensor are also maintained in a bent state. To verify whether the device retains its optoelectronic properties in the bent state. First, in the dark state, the dark current of the device in the flat state, the bent state with a radius of curvature of 18.5cm, and the dark current returning from the bent state to the flat state were measured, respectively, and the test results are shown in fig. 18, which shows that the I-V curves of the device in the three states substantially coincide, which can indicate that the dark current of the device in the bent state does not change as the substrate is bent. Next, the sensor operated in the self-power mode was tested in the above three states, and as a result, as shown in fig. 19, the photocurrent of the sensor in the bending state was 97.2% of the value in the flat state. When the device reverts from the bent state to the flat state, the photocurrent value of the sensor was 96.0% of the initial flat state value. Finally, the photocurrent of the sensor was tested under a bias of 1V, and the result is shown in fig. 20, where the saturated photocurrent of the sensor in the bent state was 99.1% of the value in the initial flat state. When the uv sensor reverts from the bent state to the flat state, the photocurrent value of the sensor was 97.9% of the initial flat state value. The results show that the mechanical property and the sensitivity of the ultraviolet sensor are well maintained in the bending process, and the good flexible ultraviolet sensor characteristic is shown.
In conclusion, the preparation method of the ZnO film can reduce the thickness of the ZnO film and improve the density of the ZnO film by improving the preparation process of the ZnO film, so that the ultraviolet sensor has lower dark current under the condition of no light irradiation and higher photocurrent under the condition of light irradiation, thereby ensuring that the sensitivity of the ultraviolet sensor is greatly improved compared with the conventional ultraviolet sensor; the flexible ultraviolet sensor prepared by the invention can well maintain the mechanical property and the sensitivity under the condition that the substrate is bent to the curvature radius of 18.5mm, and shows good flexible ultraviolet sensor characteristics. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (17)
1. A preparation method of a ZnO film is characterized by comprising the following steps:
preparing a precursor solution, wherein the precursor solution comprises a complex of zinc hydroxide and ammonia water;
providing a substrate, and carrying out hydrophilic treatment on the substrate to enable the substrate to have a hydrophilic surface;
coating the precursor liquid on the surface of the substrate;
and annealing the substrate coated with the precursor liquid to obtain the pure-phase continuous ZnO film on the surface of the substrate.
2. The method for preparing a ZnO thin film according to claim 1, characterized in that: the preparation process of the zinc hydroxide comprises the following steps: and dropping the sodium hydroxide solution into the zinc nitrate solution to obtain flocculent liquid, and centrifuging to obtain zinc hydroxide precipitate.
3. The method for producing a ZnO film according to claim 2, characterized in that: the amount of the hydroxyl ion substances dripped into the zinc nitrate solution is more than twice of the amount of the zinc ion substances in the zinc nitrate solution, so as to ensure that all the zinc ions in the zinc nitrate solution generate the zinc hydroxide precipitate.
4. The method for producing a ZnO film according to claim 2, characterized in that: and the method also comprises the steps of adding the zinc hydroxide precipitate into deionized water at least once, uniformly dispersing, and centrifuging again to obtain the zinc hydroxide precipitate.
5. The method for preparing a ZnO thin film according to claim 1, characterized in that: the complex has the chemical formula of Zn5(OH)8(NO3)2.(2-x)NH3.xH2O, wherein, 0<x<And 2, the concentration range of the complex in the precursor liquid is 0.3M-0.9M.
6. The method for preparing a ZnO thin film according to claim 1, characterized in that: the substrate is a rigid substrate or a flexible substrate.
7. The method for preparing the ZnO film according to claim 1, wherein the substrate is a glass substrate or a polyimide substrate, and the hydrophilic treatment comprises the following steps:
sequentially carrying out ultrasonic cleaning on the substrate by adopting acetone, ethanol and deionized water;
drying the substrate with air or inert gas;
drying the residual water vapor on the surface of the substrate;
uniformly mixing concentrated sulfuric acid and a hydrogen peroxide solution to obtain a mixed solution, and placing the substrate in the mixed solution for a preset time, wherein the concentration of the concentrated sulfuric acid is more than 70 wt%.
8. The method for producing a ZnO film according to claim 7, wherein: the concentration range of the hydrogen peroxide solution is 10-50 wt%, the volume ratio range of the concentrated sulfuric acid to the hydrogen peroxide solution is 1.5: 1-5: 1, and the preset time range is 10 minutes-10 hours.
9. The method for preparing the ZnO film according to claim 1, wherein the substrate is a polyetherimide substrate or a polyetheretherketone substrate, and the hydrophilic treatment comprises a step of plasma cleaning the substrate or a step of implanting a hydrophilic acrylate monomer-based coating on the surface of the substrate.
10. The method for preparing a ZnO thin film according to claim 1, characterized in that: the coating adopts a spin coating method.
11. The method for preparing a ZnO thin film according to claim 1, characterized in that: the annealing temperature range is 120-300 ℃, and the heat preservation time is more than 1 hour.
12. The method for preparing a ZnO thin film according to claim 1, characterized in that: the thickness range of the ZnO film is 16 nm-25 nm.
13. The application of the ZnO film in the ultraviolet sensor is characterized in that: the ZnO film is prepared by the method of any one of claims 1 to 12, and is used for converting ultraviolet signals into electric signals.
14. Use according to claim 13, characterized in that: and manufacturing an interdigital positive electrode and an interdigital negative electrode on the surface of the ZnO film to obtain the ultraviolet sensor.
15. Use according to claim 14, characterized in that: the width range of the interdigital positive electrode or the interdigital negative electrode is 0.1 mm-0.5 mm, and the distance range of the interdigital is 0.5 mm-1.5 mm.
16. Use according to claim 14, characterized in that: and manufacturing the interdigital positive electrode and the interdigital negative electrode by adopting a screen printing method.
17. Use according to claim 14, characterized in that: the interdigital positive electrode and the interdigital negative electrode are made of carbon, or one of the interdigital positive electrode and the interdigital negative electrode is made of carbon, and the other electrode is made of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid).
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