CN103343335A - Preparation methods for boron-doped zinc oxide film - Google Patents
Preparation methods for boron-doped zinc oxide film Download PDFInfo
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- CN103343335A CN103343335A CN2013102275593A CN201310227559A CN103343335A CN 103343335 A CN103343335 A CN 103343335A CN 2013102275593 A CN2013102275593 A CN 2013102275593A CN 201310227559 A CN201310227559 A CN 201310227559A CN 103343335 A CN103343335 A CN 103343335A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 40
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052796 boron Inorganic materials 0.000 claims abstract description 33
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000011701 zinc Substances 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 90
- 229960001296 zinc oxide Drugs 0.000 claims description 48
- 239000010409 thin film Substances 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 9
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical group O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000009997 thermal pre-treatment Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000085 borane Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052810 boron oxide Inorganic materials 0.000 description 9
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 238000005201 scrubbing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000005355 Hall effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000005361 soda-lime glass Substances 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the field of films, and discloses two preparation methods for a boron-doped zinc oxide film. The preparation methods mainly comprise the following steps: mixing a zinc source, a stabilizing agent and a boron source in an organic solvent, preparing a gel, making the gel to undergo processes of filming and drying to obtain a precursor film, heat processing the precursor film, and cooling to obtain the boron-doped zinc oxide film. Compared with the conventional vacuum method, the two preparation methods of the invention helps to improve utilization rate of the raw materials, reduce production cost and guarantee the film quality.
Description
Technical field
The present invention relates to the film field, be specifically related to the preparation method of boron-doping zinc-oxide film.
Background technology
Transparent conductive oxide film (TCO) excellent properties transparent because of it, conduction is used widely.That at present, research is more is SnO
2Base, In
2O
3Base and zno-based material.Zinc oxide (ZnO) is a kind of multi-functional oxidation thing material, has hexagonal wurtzite structure, and its energy gap at room temperature is 3.37eV, has good transparent conductivity.ZnO film and other two kinds of material compared, production cost is low, aboundresources, nontoxic, good stability, in the TCO of two component system material, doping zinc-oxide is considered to one of the most promising transparent conductive oxide film material, is widely used in fields such as electrode of solar battery, photoelectric device, gas sensor, advanced luminescent material, buffer layer.
For satisfying the various requirement, particularly requirement photoelectricity aspect of ZnO on using, various elements are applied to the doping vario-property of ZnO, and behind other elements that mix, its optical property and electric property can be highly improved.The impurity atoms ionization that these mix can provide unbound electron or free hole, and the electric conductivity of material is got a promotion.That doping is studied for the n type at present is III family element (B, Al, Ga, In) the most widely.Wherein mix ZnO film research the most deep of Al and Ga, the zinc oxide of mixing B also has many progress.
As far back as Wenas in 1991, WilsonW etc. adopted chemical Vapor deposition process with zinc ethyl, H
2O, B
2H
6Being raw material, is that 150 ℃ of resistivity that prepare the B:ZnO film of 2 μ m are 10 Ω cm in temperature.Employing spray pyrolysis such as calendar year 2001 B.J.Lokhande have prepared the B:ZnO film, and its transmitance is greater than 90%, resistivity 10～4 Ω cm.People such as Y.Hagiwara are applied to B:ZnO and Al:ZnO film the Window layer of CIGS thin-film solar cells, and contrasted the two influence to battery efficiency, the result shows that the battery efficiency of use B:ZnO film is higher, and this mainly is because carrier concentration and the mobility of B:ZnO film will be higher than the Al:ZnO film.
As seen, the boron-doping zinc-oxide film has excellent photoelectric properties, has broad application prospects, and especially in area of solar cell, can be used as Window layer and the electrode materials of battery.Use in this field at present maximum be the AZO film, BZO is a kind of novel Window layer material, has many documents to contrast the influence of AZO and the solar battery efficiency of BZO, document shows when BZO does Window layer that the efficiency value of battery is higher.But existing B:ZnO film generally all is to adopt vacuum method to make (as magnetron sputtering method), and the environmental requirement of its operation is higher, generally needs complex apparatus, operation to be difficult for, and this kind equipment all abroad monopolized, and is expensive; And the ratio of boron-doping amount and zinc oxide can not be accurately controlled in the vacuum method preparation, makes the product effect be difficult to control; Moreover vacuum method has only about 30% for utilization ratio of raw materials, has caused a large amount of wastage of material.As seen, it is higher and be difficult to control quality product that vacuum method prepares boron-doping zinc-oxide film cost.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art, two kinds of preparation methods that can accurately control the boron-doping zinc-oxide film of boron-doping amount and easy to operate and control are provided.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of preparation method of boron-doping zinc-oxide film wherein may further comprise the steps:
Add stablizer in the organic solution of Xiang Xinyuan, add the boron source after being warming up to 25-80 ℃, ageing is handled then, obtains gel;
Described gel is filmed and drying treatment, obtain precursor thin-film;
Described precursor thin-film is heat-treated, and cooling obtains the boron-doping zinc-oxide film.
The preparation method of another kind of boron-doping zinc-oxide film may further comprise the steps:
Zinc source, stablizer and boron source are dissolved in the organic solvent, and preparating mixture solution refluxes described mixture solution evaporation, obtains gel; Wherein, the mol ratio of boron atom and zinc atom is 0.2～1.0:100 in the described gel;
Described gel is filmed and drying treatment, obtain precursor thin-film;
Described precursor thin-film is heat-treated, and cooling obtains the boron-doping zinc-oxide film.
The preparation method of above-mentioned two kinds of boron-doping zinc-oxide films, do not need to use special equipment, do not need special environmental requirement yet, as vacuum tightness etc., but place the organic solvent complexing to form gel in zinc source, boron source, through the zinc-oxide film of follow-up filming, drying and thermal treatment etc. namely obtain boron-doping.Prepare the boron-doping zinc-oxide film than existing vacuum method, simple, the control easily of whole process of preparation, the utilization ratio of raw materials height, more than 90%, and above-mentioned raw materials range of choice used in the present invention extensively, draw materials easy, cheap.Moreover, the composition of the boron-doping zinc-oxide film of making by above-mentioned two kinds of preparation methods of the present invention is zinc oxide and boron oxide, boron oxide and zinc oxide exist with the form of sosoloid, the present invention can control the amount of the raw material of adding in the preparation by a series of calculation formula, thereby accurately control the content of boron oxide and zinc oxide in the film, guaranteed the film quality of making and reduced the waste of raw material that this is that vacuum method institute is inaccessible.
As seen, than existing vacuum preparation method, the present invention has reduced production cost, and makes whole process of preparation be easy to control, has guaranteed quality product.
The Figure of description explanation
Fig. 1 is the transmitance design sketch of embodiment 1 provided by the invention;
Fig. 2 is the transmitance design sketch of embodiment 2 provided by the invention;
Fig. 3 is the transmitance design sketch of embodiment 3 provided by the invention;
Fig. 4 is the transmitance design sketch of embodiment 4 provided by the invention.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
The embodiment of the invention provides the preparation method of two kinds of boron-doping zinc-oxide films, and a kind of preparation method of boron-doping zinc-oxide film wherein may further comprise the steps:
S01: the zinc source is dissolved in the organic solvent fully, forms first solution;
S02: in described first solution, add stablizer, form second solution;
S03: described second solution is warming up to 25-80 ℃;
S04: add the boron source in described second solution after intensification, wherein, the boron atom is 0.2～1.0:100 with the quantity of zinc atom than (or mol ratio);
S05: all raw material stirring in the solution that step S04 handles are even, and ageing obtains gel after handling;
S06: described gel is filmed and drying treatment, obtain precursor thin-film;
S07: described precursor thin-film is heat-treated, and then cooling obtains the boron-doping zinc-oxide film.
Particularly, among the above-mentioned steps S01, a kind of in described organic solvent preferred alcohol, methyl alcohol, Virahol and the ethylene glycol monomethyl ether, these organic solvents can be realized effect preferably, and molecular weight is all smaller, be easy to follow-up disaggregating treatment, being beneficial to and finally obtaining composition only is the boron-doping zinc-oxide film of boron oxide and zinc oxide.Described zinc source can be Zinc diacetate dihydrate, Glacial acetic acid zinc, zinc acetylacetonate etc., and preferred Zinc diacetate dihydrate and Glacial acetic acid zinc because the two molecular weight is less, are easy to decompose.In addition, Glacial acetic acid zinc is not because contain crystal water, can not introduce moisture in subsequent thin film preparation and be beneficial to reason such as film drying and can become better selection.
Among the above-mentioned steps S02, the purpose that adds stablizer is: one, complete solving zinc source under the help of organic solvent; Two, between stablizer, zinc source and the organic solvent complex reaction takes place, the complex compound of formation can be combined with the boron source better.Described stablizer is preferably monoethanolamine, because its molecular weight ratio is less, be easy to follow-up disaggregating treatment, being beneficial to and finally obtaining composition only is the boron-doping zinc-oxide film of boron oxide and zinc oxide, certainly, if do not pursue the effect same that plays as this monoethanolamine, stablizer of the present invention can also be selected other known stablizer of this area for use.For the addition of stablizer, according to determining with the required molar weight of the complex reaction in zinc source, unsuitable too much or not enough.Because if adding is excessive, then the stablizer of follow-up remnants is too much, can strengthen follow-up decomposition reaction; If add deficiency, can cause reaction not exclusively, influence the rate of utilization in zinc source, also strengthened the decomposition difficulty simultaneously.Therefore, stablizer is monoethanolamine, when the zinc source is Zinc diacetate dihydrate, and monoethanolamine is preferably 1:1 with the molar weight ratio of Zinc diacetate dihydrate.
Among the above-mentioned steps S03, the complex reaction for accelerating to take place between organic solvent, stablizer and the zinc source can be warming up to 25-80 ℃.Also can not realize complex reaction when not heating certainly, just speed of response is very slow, and the reaction times that needs is very long.Certainly because general production environment is room temperature, it is told the truth does not have about 25 degrees centigrade when heating yet.For mixing, in temperature-rise period, stir simultaneously, and after temperature rises to set(ting)value, continue to stir 0.5-2h again.
Among the above-mentioned steps S04, a kind of in described boron source preferred boric acid, trimethyl borate, trimethyl-boron and the borine.They can satisfy the boron-doping zinc-oxide film to the requirement in boron source, and molecular weight is all smaller, is easy to follow-up disaggregating treatment, and it is remaining to reduce impurity, and finally obtaining composition only is the boron-doping zinc-oxide film of boron oxide and zinc oxide.Wherein, the boron atom is 0.2～1.0:100 with the quantity of zinc atom than (or mol ratio), like this, the mol ratio of boron oxide and zinc oxide is 0.2～1.0:100 in the boron-doping zinc-oxide film of making, make film have excellent photoelectric properties, when the quantity of boron atom and zinc atom was 0.6～0.8:100 than (or mol ratio), the performance of film was better.
Addition for above-mentioned organic solvent, boron source and zinc source calculates by following formula: the concentration of colloidal sol=(amount in the amount in zinc source+boron source)/organic solvent, for guaranteeing the quality of boron-doping zinc-oxide film, the concentration of colloidal sol is as the criterion with 0.4-1.2mol/L.Organic solvent is analytical pure, and the purity height can be set the amount of organic solvent earlier, draws separately molar weight according to the relation of the zinc atom quantity between zinc source and the boron source and boron atomic quantity then, thereby obtains the amount of the required adding of each raw material.The zinc source here is preferably the zinc source, and it is easy to complexing and decomposition in the film preparation process.
Among the above-mentioned steps S05, generally need to stir about 1h to stir to reach, then still aging 24h.
Among the above-mentioned steps S06, preferably, described filming may further comprise the steps with drying treatment:
Employing glass is substrate, and substrate is used scrubbing powder, deionized water, hydrochloric acid, deionized water, acetone, washed with de-ionized water successively, and purges dry for standby with high pure nitrogen.If substrate is not cleaned, then can have influence on the quality of filming, as the homogeneity of film, planeness etc., and can in film, introduce impurity;
The employing dip-coating method is filmed, and pull rate is 1-8cm/min, and preferred 4cm/min can obtain the uniformity coefficient good film like this;
With wet film at 100-120 ℃ of dry 10-15min, again with film at 240-260 ℃ of thermal pretreatment 10-15min;
Repeat aforesaid operations, obtain described precursor thin-film.
In preheating treatment procedure, can or divide and take off organic solvent and stablizer evaporation.Through such filming and drying treatment, can obtain the good precursor thin-film of transparency height, uniformity coefficient and planeness, guaranteed the quality that it is good.
Among the above-mentioned steps S07, preferably, described precursor thin-film heat-treated be: described precursor thin-film is placed under 400-600 ℃ the temperature and handle 1-3h, heat-treating atmosphere is air, room temperature is put in cooling then, simple to operation like this, other remaining ingredients in the precursor thin-film are decomposed fully, only stay zinc oxide and the boron oxide composition of determining ratio.And this heat-treating apparatus can be tube type resistance furnace, can also be other devices certainly.
The preparation method of another kind of boron-doping zinc-oxide film may further comprise the steps:
S08: zinc source, stablizer and boron source are dissolved in the organic solvent together, form mixing solutions; Wherein, the same a kind of preparation method, the boron atom is 0.2～1.0:100 with the quantity ratio of zinc atom; Preferred boron atom is 0.6～0.8:100 with the quantity ratio of zinc atom.
S09: described mixing solutions evaporation is refluxed, obtain transparent homogeneous gel;
S10: described gel is filmed and drying treatment, obtain precursor thin-film;
S11: described precursor thin-film is heat-treated, then be cooled to room temperature, obtain the boron-doping zinc-oxide film.
Particularly, the same a kind of preparation method, among the above-mentioned steps S08, a kind of in described organic solvent preferred alcohol, methyl alcohol, Virahol and the ethylene glycol monomethyl ether, a kind of in described boron source preferred boric acid, trimethyl borate, trimethyl-boron and the borine.Described stablizer is preferably monoethanolamine, and the preferred version of the addition of described stablizer and reason thereof be a kind of preparation method as above.
Among the above-mentioned steps S09, adopt the evaporation reflux type, purpose is in the complex reaction that guarantees between stablizer, boron source, zinc source and the organic solvent, and the backflow that makes boiling point be lower than the material of setting temperature of reaction is used.When selecting above-mentioned preferred organic solvent, boron source and stablizer for use simultaneously, can namely obtain transparent homogeneous gel with described mixing solutions at 60-85 ℃ of evaporation backflow 2-5h.
Above-mentioned steps S10 and S11, identical with last a kind of preparation method's step S06 and S07, preferred version is not given unnecessary details at this too.
Than existing vacuum method, two kinds of preparation methods of the present invention do not need to use special equipment, do not need special environmental requirement yet, as vacuum tightness etc., but place the organic solvent complexing to form gel in zinc source, boron source, through the zinc-oxide film of follow-up filming, drying and thermal treatment etc. namely obtain boron-doping.Simple, the control easily of whole process of preparation, the utilization ratio of raw materials height, more than 90%, and above-mentioned raw materials range of choice used in the present invention extensively, draw materials easy, cheap.Moreover the present invention controls the amount of the raw material of adding in the preparation by a series of calculation formula, thereby has accurately controlled the content of boron oxide and zinc oxide in the film, has guaranteed the film quality of making.Particularly, the transmitance of the boron-doping zinc-oxide film of being made by the present invention is 85%-95%, and resistivity is 1 * 10
-3～9 * 10
-3Ω cm.
Now with the example that is prepared as of concrete boron-doping zinc-oxide film, the present invention is further elaborated.
Embodiment 1
(1) Zinc diacetate dihydrate is dissolved in the certain amount of solvent, solvent is methyl alcohol, dissolving back fully adds the stablizer monoethanolamine, the molar weight of stablizer and the molar weight of Zinc diacetate dihydrate are 1:1, are warming up to 60 ℃ and stir 2h, add boric acid then, the doping of boron is that 0.2at%(is than zinc atom), the concentration of colloidal sol is 0.4mol/L, continues to stir 1h, and still aging 24h obtains gel.
(2) film and drying: at glass substrate preparation B:ZnO film.Adopting common soda-lime glass is substrate, substrate is used scrubbing powder-deionized water-hydrochloric acid-deionized water-acetone-washed with de-ionized water successively, and purge with high pure nitrogen.The employing dip-coating method is filmed, and pull rate is 1cm/min.With wet film at 100 ℃ of dry 10min, again with film at 240 ℃ of thermal pretreatment 10min, repeat aforesaid operations for several times, obtain precursor thin-film.
(3) thermal treatment: precursor thin-film is placed tube type resistance furnace, and annealing atmosphere is air, handles 1h for 600 ℃, cools to room temperature with the furnace, obtains the B:ZnO film.
Adopting the resistivity of four point probe tester and Hall effect instrument testing film is 6.7 * 10-3 Ω cm, adopts the transmitance of ultraviolet-visible pectrophotometer testing film, can reach 85%, referring to Fig. 1.
Embodiment 2
(1) Glacial acetic acid zinc is dissolved in the certain amount of solvent, solvent is Virahol, dissolving back fully adds the stablizer monoethanolamine, the molar weight of the molar weight of stablizer and Glacial acetic acid zinc is 1:1, is warming up to 80 ℃ and stirs 0.5h, adds trimethyl-boron then, the doping of boron is that 1.0at%(is than zinc atom), the concentration of colloidal sol is 1.2mol/L, continues to stir 1h, and still aging 24h obtains gel.
(2) film and drying: preparation B:ZnO film on the glass substrate.Adopting common soda-lime glass is substrate, substrate is used scrubbing powder-deionized water-hydrochloric acid-deionized water-acetone-washed with de-ionized water successively, and purge with high pure nitrogen.The employing dip-coating method is filmed, and pull rate is 1cm/min.With wet film at 100 ℃ of dry 10min, again with film at 240 ℃ of thermal pretreatment 10min, repeat aforesaid operations for several times, obtain precursor thin-film.
(3) thermal treatment: precursor thin-film is placed tube type resistance furnace, and annealing atmosphere is air, 400 ℃ of processing 3h, cools to room temperature with the furnace, obtains the B:ZnO film.
Adopting the resistivity of four point probe tester and Hall effect instrument testing film is 1.2 * 10-3 Ω cm, and the transmitance of employing ultraviolet-visible pectrophotometer testing film can be up to 92%, referring to Fig. 2.
Embodiment 3
With Zinc diacetate dihydrate, borine, monoethanolamine are dissolved in the ethanol, at 85 ℃ of evaporation backflow 2h, obtain transparent homogeneous gel.The doping of boron is that 0.6at%(is than zinc atom), the concentration of colloidal sol is 1.2mol/L.Secondly, adopting common soda-lime glass is substrate, and substrate is used scrubbing powder-deionized water-hydrochloric acid-deionized water-acetone-washed with de-ionized water successively, and purges dry for standby with high pure nitrogen.Adopt crystal pulling method to film then, pull rate is 1cm/min.With wet film at 100 ℃ of dry 10min, again with film at 240 ℃ of thermal pretreatment 10min, repeat aforesaid operations for several times, obtain precursor thin-film.At last, with precursor thin-film in air, 550 ℃ handle 1h, cool to room temperature with the furnace, obtain the B:ZnO film.
Adopting the resistivity of four point probe tester and Hall effect instrument testing film is 7.8 * 10-3 Ω cm, adopts the transmitance of ultraviolet-visible pectrophotometer testing film, can be up to 94%, referring to Fig. 3.
Embodiment 4
With Zinc diacetate dihydrate, trimethyl-boron, monoethanolamine are dissolved in the solvent ethylene glycol methyl ether, at 60 ℃ of evaporation backflow 5h, obtain transparent homogeneous gel.The doping of boron is that 0.8at%(is than zinc atom), the concentration of colloidal sol is 0.7mol/L.Secondly, adopting common soda-lime glass is substrate, and substrate is used scrubbing powder-deionized water-hydrochloric acid-deionized water-acetone-washed with de-ionized water successively, and purges dry for standby with high pure nitrogen.Adopt crystal pulling method to film then, pull rate is 4cm/min.With wet film at 100 ℃ of dry 10min, again with film at 240 ℃ of thermal pretreatment 10min, repeat aforesaid operations for several times, obtain precursor thin-film.At last, with precursor thin-film in air, 600 ℃ handle 1h, cool to room temperature with the furnace, obtain the B:ZnO film.
Adopting the resistivity of four point probe tester and Hall effect instrument testing film is 5.0 * 10-3 Ω cm, adopts the transmitance of ultraviolet-visible pectrophotometer testing film, can be up to 95%, referring to Fig. 4.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. the preparation method of boron-doping zinc-oxide film may further comprise the steps:
Add stablizer in the organic solution of Xiang Xinyuan, add the boron source after being warming up to 25-80 ℃, ageing is handled then, obtains gel; Or
Zinc source, stablizer and boron source are dissolved in the organic solvent, and preparating mixture solution refluxes described mixture solution evaporation, obtains gel; Wherein, the mol ratio of boron atom and zinc atom is 0.2～1.0:100 in the described gel;
Described gel is filmed and drying treatment, obtain precursor thin-film;
Described precursor thin-film is heat-treated, and cooling obtains the boron-doping zinc-oxide film.
2. the preparation method of boron-doping zinc-oxide film as claimed in claim 1 is characterized in that, described zinc source is Zinc diacetate dihydrate or Glacial acetic acid zinc.
3. the preparation method of boron-doping zinc-oxide film as claimed in claim 1 or 2 is characterized in that, described organic solvent is selected from a kind of in ethanol, methyl alcohol, Virahol and the ethylene glycol monomethyl ether.
4. the preparation method of boron-doping zinc-oxide film as claimed in claim 1 or 2 is characterized in that, described boron source is selected from a kind of in boric acid, trimethyl borate, trimethyl-boron and the borine.
5. the preparation method of boron-doping zinc-oxide film as claimed in claim 1 or 2 is characterized in that, described stablizer is monoethanolamine.
6. the preparation method of boron-doping zinc-oxide film as claimed in claim 1 is characterized in that, the mol ratio of boron atom and zinc atom is 0.6～0.8:100.
7. the preparation method of boron-doping zinc-oxide film as claimed in claim 1 is characterized in that, described filming may further comprise the steps with drying treatment:
The employing dip-coating method is filmed, and pull rate is 1-8cm/min;
With wet film at 100-120 ℃ of dry 10-15min, again with film at 240-260 ℃ of thermal pretreatment 10-15min;
Repeat aforesaid operations, obtain described precursor thin-film.
8. the preparation method of boron-doping zinc-oxide film as claimed in claim 1 is characterized in that, it is to place 400-600 ℃ to handle 1-3h described precursor thin-film that described precursor thin-film is heat-treated, and heat-treating atmosphere is air.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105779976A (en) * | 2016-05-10 | 2016-07-20 | 中国环境科学研究院 | Boron oxide film-plating method for combustion reactor under condition of laboratory |
| CN116809347A (en) * | 2023-04-28 | 2023-09-29 | 厦门理工学院 | Preparation method of boron-magnesium co-doped zinc oxide film |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293741A (en) * | 2008-06-17 | 2008-10-29 | 浙江大学 | Method for preparing silver/zinc oxide compound film |
| CN101560059A (en) * | 2009-05-27 | 2009-10-21 | 中南大学 | Aluminum-doped zinc oxide film coating and nano-rod array material as well as preparation method thereof |
| CN101671119A (en) * | 2009-09-27 | 2010-03-17 | 上海大学 | Method for preparing Li-doped P-type zinc oxide film |
| CN102251236A (en) * | 2011-07-08 | 2011-11-23 | 华南理工大学 | Yttrium-aluminum co-doped zinc oxide film and preparation method thereof |
| CN102312192A (en) * | 2010-06-30 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | Seed crystal layer-assisting surface texturing zinc oxide transparent conductive film and preparation method thereof |
-
2013
- 2013-06-08 CN CN201310227559.3A patent/CN103343335B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293741A (en) * | 2008-06-17 | 2008-10-29 | 浙江大学 | Method for preparing silver/zinc oxide compound film |
| CN101560059A (en) * | 2009-05-27 | 2009-10-21 | 中南大学 | Aluminum-doped zinc oxide film coating and nano-rod array material as well as preparation method thereof |
| CN101671119A (en) * | 2009-09-27 | 2010-03-17 | 上海大学 | Method for preparing Li-doped P-type zinc oxide film |
| CN102312192A (en) * | 2010-06-30 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | Seed crystal layer-assisting surface texturing zinc oxide transparent conductive film and preparation method thereof |
| CN102251236A (en) * | 2011-07-08 | 2011-11-23 | 华南理工大学 | Yttrium-aluminum co-doped zinc oxide film and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105779976A (en) * | 2016-05-10 | 2016-07-20 | 中国环境科学研究院 | Boron oxide film-plating method for combustion reactor under condition of laboratory |
| CN105779976B (en) * | 2016-05-10 | 2018-03-16 | 中国环境科学研究院 | The boron oxide film plating process of combustion reactor under laboratory condition |
| CN116809347A (en) * | 2023-04-28 | 2023-09-29 | 厦门理工学院 | Preparation method of boron-magnesium co-doped zinc oxide film |
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