CN102925879A - Method for depositing tin dioxide film by sol technology - Google Patents
Method for depositing tin dioxide film by sol technology Download PDFInfo
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- CN102925879A CN102925879A CN2012104605911A CN201210460591A CN102925879A CN 102925879 A CN102925879 A CN 102925879A CN 2012104605911 A CN2012104605911 A CN 2012104605911A CN 201210460591 A CN201210460591 A CN 201210460591A CN 102925879 A CN102925879 A CN 102925879A
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- tin
- thin film
- colloidal sol
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- tin dioxide
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Abstract
The invention provides a method for depositing a tin dioxide film by a sol technology, which belongs to the field of ceramic materials. The method comprises the steps that a tin compound, a dopant body compound, a compound with complexing ability and the like are dissolved in water; a pH value of a system is adjusted to ensure that the system is subjected to solation to obtain stable sol; a deposition body material is immerged in the sol to ensure that the tin dioxide sol is deposited on the surface of a substrate; and the substrate is subjected to high-temperature atmosphere treatment to obtain the tin dioxide film of which the resistivity can be adjusted within a certain range according to specified requirements.
Description
Technical field
The invention provides a kind of method of collosol craft deposition tin dioxide thin film, belong to field of inorganic nonmetallic material.
Background technology
The inorganic non-metallic thin-film material has widespread use in a plurality of fields, as coating metal material surface as erosion shield; Be deposited on the surface of metal, plastics, timber etc. as wear-resistant coating; Be deposited on resin lens or glass surface as optical coating; Be deposited on metal, ceramic surface as slip coating; Wherein tin dioxide thin film since tin dioxide material have the physical property characteristics such as acidproof, alkaline-resisting, high temperature resistant, anti-mechanical shock and in optical coating, corrosion-resistant finishes, be widely used.And tindioxide is broadband semiconductor, can realize that by mixing tin dioxide material resistivity is from thousands of Ω cm to 10
-5Controllable variations between the Ω cm, the tin dioxide material of low-resistivity can as conductive powder body add to rise in the insulating material conduction or anti-static electrification, can be as ceramic electrode as glass furnace or electrode for electrolgtic aluminium, can be used as the viewing window that transparent conductive film plays the effect of reflected infrared and is used for the equipment such as glass transparent insulating or High Temperature Furnaces Heating Apparatus, can be as the transparency electrode of liquid-crystal display, can be used as electromagnetic wave shield film, can be used for heating unit as sheet resistance.
Chinese patent 88108194.9,92106609.0,93104258.5,96117069.7,200810039112.2, CN201010296911.5,201010605576.2 etc. have proposed the mode that salts solution with tin and dopant ion carries out the high-temperature spray film forming and have prepared the tindioxide resistance film.There are a plurality of shortcomings in this employing pressurized air as the mode of atomizing power, such as common compressed-air actuated pressure below 8 kilograms, the size droplet diameter that obtains with this pressure is about 100 microns, large droplet solution like this sprays to the insulating body surface can make the uniformity of film of acquisition poor, drop is difficult to form rapidly at short notice the tin dioxide thin film phase, thereby so that film fails to be completed into, finally in use sheet resistance is unstable, and impact is as the heating properties of heating unit.In addition, the component of failing to transform fully in use also can be corroded heating electrical appliance, reduction of service life.Heat electric energy when the atmospheric carrier air of large pressure has also consumed deposit film greatly.The unstable of nebulizer gas pressure also can affect the unstable, inhomogeneous of solution spraying amount, thereby so that the sheet resistance that obtains is unstable.
Chinese patent 88106876.4,97197266.4,99105710.4,01807010.8, US Patent No. 5698262, USW8097302B2 proposes to adopt chemical Vapor deposition process to prepare tin dioxide thin film, high, the steady performance of the uniformity of film that this technique has acquisition, but exist simultaneously raw material availability low, basically only have about 5-10%.Ingredient requirement can gasify to obtain stable phase feed under lower temperature, the alternative that this has just dwindled raw material has greatly also increased raw materials cost.
The method that Chinese patent 02139432.6 has proposed the material ullrasonic spraying prepares the tindioxide resistance film.The size droplet diameter that the atomizing type of this technique obtains is reduced to about 3 microns, the drop that the specific pressure spraying obtains is much smaller, this has improved the properties of film, but homogeneity and the chemical vapor deposition method of film still have larger difference, and the extremely strong corrodibility of raw material so that the production unit life-span shorter.Atomizing droplet is easy to aggegation and becomes large drop in being transported to the nozzle process, reduced the effect of ultrasonic atomizatio acquisition small particle size drop.The noise of ultrasonic generation is also so that production environment is more abominable.
Adopting magnetron sputtering technique also is the basic skills of preparation film, also extensively utilized with metallic tin target or stannic oxide target deposition tin dioxide thin film, although obtaining film performance, this technique is better than the tin dioxide thin film that chemical method obtains, but this arts demand high-vacuum apparatus and target utilising efficiency are low, and target particularly the cost of manufacture of ceramic target is high, these have limited its range of application greatly all so that the cost of this technique is higher than chemical method far away.
For above deficiency, this patent proposes by preparing first tindioxide precursor colloidal sol, deposits above-mentioned colloidal sol at the body material face by dip coating afterwards, the last formation that realizes tin dioxide thin film in high-temperature atmosphere.
Summary of the invention
The method that the purpose of this invention is to provide a kind of collosol craft deposition tin dioxide thin film.Specific implementation method forms stable colloidal sol for tin compound, adulterate body compound, the compound with coordination ability and acid or alkali are added to the water, the add-on of adulterate body compound is limited with the tindioxide phase that does not change final film, simultaneously to change the tin dioxide thin film properties as purpose.All do not contain the halide-ions that under the high temperature metal is had strong corrosion in above-mentioned each compound.Body material is immersed in the above-mentioned colloidal sol, thereby deposit the tindioxide precursor at material surface, with this body material that deposits precursor colloidal sol place high-temperature atmosphere furnace in oxidizing atmosphere or reducing atmosphere in 400-900 ℃, can be within the specific limits by the tin dioxide thin film of specifying requirements adjustment thereby obtain resistivity.
Concrete preparation condition and processing step are:
A. the preparation condition of tindioxide precursor colloidal sol: with tin compound such as mercaptan ethyl tin, tribenzyltin, normal-butyl tin, butyl oxygen tin, stannous oxalate, tin acetate, methyl tin, ethanol tin, nitric acid tin, oxysuccinic acid tin, methyl alcohol tin, sorbyl alcohol tin, adulterate body compound such as metallic compound and boron, compounds of phosphorus, and the compound with coordination ability, being added to the water with acid or alkali forms stable tindioxide precursor colloidal sol, and the pH value of colloidal sol is between 5-9.
B. film precursor mode of deposition: body material is immersed in the above-mentioned colloidal sol, thereby deposits the tindioxide precursor at material surface.
C. tin dioxide thin film formation condition: the body material that will deposit precursor colloidal sol place high-temperature atmosphere furnace in oxidizing atmosphere or reducing atmosphere in 400-900 ℃, can be within the specific limits by the tin dioxide thin film of specifying requirements adjustment thereby obtain resistivity.
Embodiment:
Embodiment 1
With mercaptan ethyl tin, iron nitrate (wherein iron is 2:100 with the ratio of the amount of substance of tin), ethylenediamine tetraacetic acid (EDTA), (wherein ethylenediamine tetraacetic acid (EDTA) is 3:1 with the ratio of the amount summation of tin, iron substance) is dissolved in the water, add the pH to 9 of ammoniacal liquor regulation system, form stable tindioxide precursor colloidal sol.Microcrystalline glass is immersed in this colloidal sol, and takes out, place high-temperature atmosphere furnace, pass into oxygen, furnace temperature is set as 700 ℃, is incubated naturally cooling after 3 hours, take out this microcrystalline glass, surface deposition has tin dioxide thin film, and the resistivity of film is 1200 Ω cm.
Embodiment 2
With tin acetate, chromium sulphate (wherein chromium is 1:100 with the ratio of the amount of substance of tin), quadrol (wherein quadrol is 1:1 with the ratio of tin, chromium amount of substance summation) are dissolved in the water, add the pH to 7 of ammoniacal liquor regulation system, form stable tindioxide precursor colloidal sol.Common glass sheet is immersed in this colloidal sol, and takes out, place high-temperature atmosphere furnace, pass into oxygen, furnace temperature is set as 600 ℃, is incubated naturally cooling after 1 hour, takes out this sheet glass, and surface deposition has tin dioxide thin film, and the resistivity of film is 70 Ω cm.
Embodiment 3
Nitric acid tin, ethylene glycol niobium (wherein niobium is 6:100 with the ratio of the amount of substance of tin), tartrate (its unresolvable tartaric acid is 2:1 with the ratio of tin, niobium amount of substance summation) are dissolved in the water, add the pH to 6 of sulfuric acid regulation system, form stable tindioxide precursor colloidal sol.Alumina ceramic plate is immersed in this colloidal sol, and takes out, place high-temperature atmosphere furnace, pass into oxygen, furnace temperature is set as 900 ℃, is incubated naturally cooling after 2 hours, take out this alumina ceramic plate, surface deposition has tin dioxide thin film, and the resistivity of film is 0.00068 Ω cm.
Claims (7)
1. the method for a collosol craft deposition tin dioxide thin film is characterized in that: comprise that the preparation of colloidal sol, colloidal sol transform formation in the deposition of matrix surface and the high-temperature atmosphere of tin dioxide thin film.
2. a kind of collosol craft as claimed in claim 1 deposits the method for tin dioxide thin film, and it is characterized in that: the employed tin compound of the preparation of described colloidal sol is that mercaptan ethyl tin, tribenzyltin, normal-butyl tin, butyl oxygen tin, stannous oxalate, tin acetate, methyl tin, ethanol tin, nitric acid tin, oxysuccinic acid tin, methyl alcohol tin, sorbyl alcohol tin etc. do not contain the tin compound that under the high temperature metal is had the strong corrosion halide-ions.
3. a kind of collosol craft as claimed in claim 2 deposits the method for tin dioxide thin film, it is characterized in that: the employed adulterate body compound of the preparation of described colloidal sol is mainly metallic compound and boron, compounds of phosphorus, and these compounds do not contain the halide-ions that under the high temperature metal is had heavy corrosion.
4. a kind of collosol craft as claimed in claim 1 deposits the method for tin dioxide thin film, it is characterized in that: the preparation of described colloidal sol is employed to have the compound of coordination ability for not containing the compound that at high temperature metal is had the halide-ions of heavy corrosion.
5. a kind of collosol craft as claimed in claim 1 deposits the method for tin dioxide thin film, it is characterized in that: the process for preparation of described colloidal sol is formation solution that tin compound, adulterate body compound, ligand compound are added to the water, and adds the pH value of not halogen-containing acid or alkali adjustment system between 5-9 simultaneously in solution.
6. a kind of collosol craft as claimed in claim 1 deposits the method for tin dioxide thin film, it is characterized in that: the deposition method of described film is for immersing body material in the colloidal sol that obtains, again body material is shifted out colloidal sol, colloidal sol namely deposits at substrate material surface like this.
7. a kind of collosol craft as claimed in claim 1 deposits the method for tin dioxide thin film, it is characterized in that: the high-temperature atmosphere of described tin dioxide thin film transforms and forms is to have the body material of colloidal sol to place high-temperature atmosphere furnace to heat-treat surface deposition, atmosphere can be oxidizing atmosphere or reducing atmosphere, thermal treatment temp is 400-900 ℃, can be within the specific limits by the tin dioxide thin film of specifying requirement to adjust thereby obtain resistivity.
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| CN2012104605911A CN102925879A (en) | 2012-11-16 | 2012-11-16 | Method for depositing tin dioxide film by sol technology |
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| CN2012104605911A CN102925879A (en) | 2012-11-16 | 2012-11-16 | Method for depositing tin dioxide film by sol technology |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104972710A (en) * | 2014-04-10 | 2015-10-14 | 苏州驭奇材料科技有限公司 | Electromagnetic wave absorption apparatus and preparation method thereof |
| CN105992410A (en) * | 2015-02-11 | 2016-10-05 | 佛山市顺德区美的电热电器制造有限公司 | Electrothermal film layer manufacturing method, electrothermal film layer, electric heating disc and cooking utensil |
| CN108085721A (en) * | 2017-12-18 | 2018-05-29 | 广西正润新材料科技有限公司 | A kind of method and system of aluminium foil surface sol-gal process in-situ deposition tin nucleus |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1367494A (en) * | 2001-07-14 | 2002-09-04 | 潍坊润泰智能电气有限公司 | Tin-antimony oxide conducting film and its production method |
| CN101219860A (en) * | 2007-12-25 | 2008-07-16 | 天津大学 | Method for producing nano-tin dioxide based conductive film with stannous oxalate neutral complexometry |
-
2012
- 2012-11-16 CN CN2012104605911A patent/CN102925879A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1367494A (en) * | 2001-07-14 | 2002-09-04 | 潍坊润泰智能电气有限公司 | Tin-antimony oxide conducting film and its production method |
| CN101219860A (en) * | 2007-12-25 | 2008-07-16 | 天津大学 | Method for producing nano-tin dioxide based conductive film with stannous oxalate neutral complexometry |
Non-Patent Citations (1)
| Title |
|---|
| 王灵伟: "SnO2透明导电薄膜的溶胶—凝胶制备与性能研究", 《天津大学硕士学位论文》, 15 December 2011 (2011-12-15), pages 16 - 19 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104972710A (en) * | 2014-04-10 | 2015-10-14 | 苏州驭奇材料科技有限公司 | Electromagnetic wave absorption apparatus and preparation method thereof |
| CN104972710B (en) * | 2014-04-10 | 2017-08-25 | 苏州驭奇材料科技有限公司 | A kind of electro-magnetic wave absorption device and preparation method thereof |
| CN105992410A (en) * | 2015-02-11 | 2016-10-05 | 佛山市顺德区美的电热电器制造有限公司 | Electrothermal film layer manufacturing method, electrothermal film layer, electric heating disc and cooking utensil |
| CN105992410B (en) * | 2015-02-11 | 2019-09-27 | 佛山市顺德区美的电热电器制造有限公司 | Manufacturing method, electric membranous layer, electric heating plate and the cooking apparatus of electric membranous layer |
| CN108085721A (en) * | 2017-12-18 | 2018-05-29 | 广西正润新材料科技有限公司 | A kind of method and system of aluminium foil surface sol-gal process in-situ deposition tin nucleus |
| CN108085721B (en) * | 2017-12-18 | 2019-09-17 | 广西正润新材料科技有限公司 | A kind of method and system of aluminium foil surface sol-gal process in-situ deposition tin nucleus |
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Application publication date: 20130213 |