CN1868948B - Preparation method of indium tin oxide precusor size and ITO thin film - Google Patents
Preparation method of indium tin oxide precusor size and ITO thin film Download PDFInfo
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- CN1868948B CN1868948B CN2005100722507A CN200510072250A CN1868948B CN 1868948 B CN1868948 B CN 1868948B CN 2005100722507 A CN2005100722507 A CN 2005100722507A CN 200510072250 A CN200510072250 A CN 200510072250A CN 1868948 B CN1868948 B CN 1868948B
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- indium
- tin oxide
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Abstract
A process for preparing the precursor slurry of indium tin oxide (ITO) includes such steps as dissolving In and Sn in strong acid respectively or dissolving the soluble In salt and Sn salt in water respectively, mixing, stirring while adding precipitant to obtain InSn deposit, washing with deionized water, adding disperser and precipitant to obtain the colloid deposit of indium tin hydroxide (or carbonate), and adding alcohol and additive to obtain the target slurry. An ITO film is prepared through coating said slurry on the glass plate and calcining.
Description
Technical field
The present invention relates to can be used as the indium tin oxide precursor slurry of the transparency and electroconductibility and the technology of preparing of indium and tin oxide film.
Background technology
Indium tin oxide (indium-tin-oxide abbreviates ITO as) or tin-doped indium oxide (tin-dopedindium oxide) are a kind of transparent electrode materials.Ito thin film has good electrical conductivity and to the characteristic of visible transparent, in addition wear-resisting, the antiacid alkali of its rete, corrosion-resistant and be convenient to characteristics such as etching.Be widely used industrial, play an important role in high-tech sector, main application is useful on the plane and shows that causing colour TV as liquid-crystal display (LCD), electricity shows (ECD), transmitter, electrochromism (EC) smart windows, solar cell, demist window and antistatic coating and heating glass or the like.
The preparation method of existing electrically conducting transparent ITO film is more, mainly adopts magnetron sputtering method (CN2516564Y), electron-beam vapor deposition method (CN1434879A), spray pyrolysis (CN1395138A), evaporation of metal method (CN87107654A), sol-gel method (CN1280960A) etc.Industrial main employing magnetron sputtering method, the vacuum tightness that this method is had relatively high expectations, very harsh to the requirement of ITO target, and target utilization is lower than 50%, the cost height.It is raw material that process for preparing sol-gel (CN1280960A) mainly adopts indium alkoxide and tin alkoxide, but the preparation process of indium tin alkoxide is more complicated assorted, and preparation cost is higher.
Summary of the invention
In order to solve the above problems, the object of the present invention is to provide a kind of with metal or its inorganic salts be feedstock production indium tin oxide precursor slurry and with slurry by applying the transparent and conductivity of the directly preparation technology of preparing of ito thin film preferably.
The main technology of preparing scheme of indium tin oxide precursor slurry of the present invention is, with indium, tin metal or indium, tin metal soluble salt is feedstock production or preparation mixing solutions, add dispersion agent, fully under agitation condition, drip precipitation agent behind the dissolving mixing, obtain indium tin hydroxide or carbonate colloidal precipitation thing, ageing for some time.With the foreign ion in clean indium tin hydroxide of deionized water or the carbonate colloid, use soaked in absolute ethyl alcohol indium tin hydroxide or carbonate colloid more then, add dehydrated alcohol, ethylene glycol (HOCH
2CH
2OH) or Virahol (C
3H
7One of OH), add multiple additives (acetate (CH at last
3COOH), thanomin, polyethylene glycol type, tween series and polyvinylpyrrolidone (PVP)), obtain indium tin oxide precursor slurry.
The technology of preparing scheme of indium and tin oxide film is: blank glass sheet or surface are coated with skim SiO
2The sheet glass of film cleans up; Sheet glass immerses in the above-mentioned ITO precursor slurry of the present invention, evenly lifts with 4～60cm/min speed then; Perhaps apply film forming with the 500-9000r/min speed of rotation with spin-coating method.This process is repeated again in dry back after heat-treating under 300 ℃～900 ℃, obtain certain thickness ito thin film.
Technique effect
Effect of the present invention: indium tin oxide precursor slurry of the present invention leaves standstill not precipitation appearance in 20 days, and the viscosity of slurry is 1.2～50.0 * 10
-3Pas, the content of indium tin is 1%～20% in the slurry, the particle diameter in the slurry is 2～20nm.Is 40nm～500nm by paint-on technique with the thickness of the ito thin film of this pulp preparation, is that the transmissivity at 550nm place is more than 85% at the visible region wavelength, and the film resistance per square is 40-400 Ω/.The film surface is evenly smooth.
Description of drawings:
Fig. 1 is preparation technology's schema of ITO slurry of the present invention and ito thin film.
Fig. 2 is the transmission electron microscope picture of ITO precursor slurry of the present invention
Fig. 3 is the optical property figure of ito thin film of the present invention.A curve representation film thickness among Fig. 3 is the transmittance curve of 300nm; B curve representation film thickness is the transmittance curve of 100nm.
Embodiment
Concrete implementing process of the present invention such as Fig. 1: with indium, tin metal or indium, tin soluble metal salt is feedstock production or preparation mixing solutions: be indium metal and metallic tin to be dissolved in purity respectively mix more than or equal to back in the pure concentrated nitric acid of top grade, concentrated hydrochloric acid, the vitriol oil any two kinds or the three kinds of mixed aqueous solution more than or equal to the pure concentrated nitric acid of top grade, concentrated hydrochloric acid, concentrated sulfuric acid aqueous solution or purity, wherein indium metal, tin purity are greater than 99.99%, and the add-on of indium metal, tin is according to Indium sesquioxide and stannic oxide mass percent In after converting in the mixing solutions
2O
3: SnO
2Add at=90: 10; Or purity is dissolved into respectively in the deionized water of resistance greater than 10M Ω .CM more than or equal to top grade pure indium salt and pink salt, thorough mixing, used indium salt and pink salt be In (NO normally
3)
3, In
2(SO
4)
3, InCl
3, Sn (NO
3)
4, Sn (SO
4)
2, SnCl
4Deng, the add-on of indium salt and pink salt is according to Indium sesquioxide and stannic oxide mass percent In after converting in the mixing solutions
2O
3: SnO
2Add at=90: 10.Add dispersion agent (polyoxyethylene glycol or tween), fully under agitation condition, drip precipitation agent (yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, volatile salt, bicarbonate of ammonia, ammoniacal liquor, sodium hydroxide, potassium hydroxide, hydrated barta, lithium hydroxide or urea etc.) behind the dissolving mixing, obtain indium tin hydroxide or carbonate colloidal precipitation thing, ageing for some time.With the foreign ion in clean indium tin hydroxide of deionized water or the carbonate colloid, use soaked in absolute ethyl alcohol indium tin hydroxide or carbonate colloid more then, add solvent (dehydrated alcohol (C
2H
5OH), ethylene glycol (HOCH
2CH
2OH) or Virahol (C
3H
7OH)), add additive (acetate (CH at last
3COOH), thanomin, polyethylene glycol type, tween series and polyvinylpyrrolidone (PVP)), obtain indium tin oxide precursor slurry.The transmission electron microscope picture of precursor slurry such as Fig. 2.Blank glass sheet and surface are coated with skim SiO
2The sheet glass of film cleans up; Sheet glass immerses in the ITO precursor slurry, evenly lifts with 4～60cm/min speed then; Perhaps apply film forming with the 500-9000r/min speed of rotation with spin-coating method.This process is repeated again in dry back after heat-treating under 300 ℃～900 ℃, prepare certain thickness ito thin film.The optical property of ito thin film such as Fig. 3.
Embodiment 1
Take by weighing in the 1.435 gram indium metal adding concentrated nitric acids and dissolve, take by weighing 0.451 gram SnCl
45H
2O is dissolved in the deionized water, two kinds of solution is mixed obtaining the solution that concentration of metal ions is 0.1～2.0mol/L then, adds 0.5%～20% PEG, and after the dissolving, under agitation dropping ammonia is until being alkalescence, ageing for some time fully; Then with deionized water washing sediment to there not being other foreign ion, centrifugation, indium tin hydroxide after washing with soaked in absolute ethyl alcohol again 3 times adds dehydrated alcohol and a spot of acetate, thanomin, tween and PVP stirring and makes indium tin oxide precursor slurry.
Embodiment 2
Take by weighing in the 2.296 gram indium metal adding concentrated nitric acids and dissolve, take by weighing 0.718 gram SnCl
45H
2O is dissolved in the deionized water, two kinds of solution is mixed obtaining In then
3+Concentration is the solution of 0.1～2.0mol/L, adds 0.5%～20% tween, after the dissolving, under agitation drips sal volatile to alkalescence, ageing for some time fully; Then with deionized water washing sediment to there not being other foreign ion, centrifugation, indium tin hydroxide after washing with soaked in absolute ethyl alcohol again 3 times adds Virahol and a spot of acetate, PEG, thanomin and PVP stirring and makes indium tin oxide precursor slurry.
Embodiment 3
Take by weighing in the 2.296 gram indium metal adding concentrated nitric acids and dissolve, taking by weighing 0.243 gram metallic tin is dissolved in the hydrochloric acid, then two kinds of solution are mixed and obtain the solution that concentration of metal ions is 0.1～2.0mol/L, the PEG of adding 0.5%～20%, fully after the dissolving, under agitation drip urea soln to being alkalescence, ageing for some time; Then with deionized water washing sediment to there not being other foreign ion, centrifugation, indium tin hydroxide after washing with soaked in absolute ethyl alcohol again 3 times adds dehydrated alcohol and a spot of acetate, PEG, thanomin, tween and PVP stirring and makes indium tin oxide precursor slurry.
Embodiment 4
Take by weighing in the 5.741 gram indiums adding concentrated nitric acids and the mixed aqueous solution of the vitriol oil and dissolve, take by weighing 1.755 gram SnCl
45H
2O is dissolved in the deionized water, two kinds of solution is mixed obtaining the solution that concentration of metal ions is 0.1～2.0mol/L then, adds 0.5%～20% PEG, after the dissolving, under agitation drips yellow soda ash until being alkalescence, ageing for some time fully; Then with deionized water washing sediment to there not being other foreign ion, centrifugation, indium tin hydroxide after washing with soaked in absolute ethyl alcohol again three times adds ethylene glycol and a spot of acetate, thanomin, tween and PVP stirring and makes indium tin oxide precursor slurry.
Embodiment 5
Take by weighing in the 11.482 gram indium metal adding hydrochloric acid and dissolve, take by weighing in the aqueous solution after 1.215 gram metallic tins are dissolved in nitric acid and mixed in hydrochloric acid, then two kinds of solution are mixed and obtain the solution that concentration of metal ions is 0.1～2.0mol/L, the PEG of adding 0.5%～20%, fully after the dissolving, under agitation drip bicarbonate of ammonia to being alkalescence, ageing for some time; Then with deionized water washing sediment to there not being other foreign ion, centrifugation, indium tin hydroxide after washing with soaked in absolute ethyl alcohol again three times adds dehydrated alcohol and a spot of acetate, thanomin, tween and PVP stirring and makes indium tin oxide precursor slurry.
Embodiment 6
The blank glass sheet is cleaned up, leave standstill more than the 60s in the slurry of sheet glass immersion embodiment 1 preparation then, evenly lift with 4cm/min speed then, this process is repeated again in dry back after heat-treating under 300 ℃, 600 ℃ of following anneal, obtain the ito thin film sample at last.The performance index of this film are:
Thickness: 40～300nm
Film resistance per square: 60～400 Ω/
Transmitance (550nm): 〉=90%
Embodiment 7
The surface is coated with skim SiO
2The sheet glass of film cleans up, leave standstill more than the 60s in the slurry of sheet glass immersion embodiment 2 preparations then, evenly lift with 40cm/min speed then, this process is repeated again in dry back after heat-treating under 500 ℃, 600 ℃ of following anneal, obtain the ito thin film sample at last.The performance index of this film are:
Thickness: 60～300nm
Film resistance per square: 40～400 Ω/
Transmitance (550nm): 〉=85%
Embodiment 8
The surface is coated with skim SiO
2The sheet glass of film cleans up, leave standstill more than the 60s in the slurry of sheet glass immersion embodiment 3 preparations then, evenly lift with 18cm/min speed then, this process is repeated again in dry back after heat-treating under 400 ℃, 550 ℃ of following anneal, obtain the ito thin film sample at last.The performance index of this film are:
Thickness: 40～500nm
Film resistance per square: 40～300 Ω/
Transmitance (550nm): 〉=87%
Embodiment 9
The surface is coated with skim SiO
2The sheet glass of film cleans up, sheet glass is placed on the spin coater then, slurry with embodiment 4 preparations drips on the sheet glass, then with 6000r/min speed spin-coating film, this process is repeated again in dry back after heat-treating under 500 ℃, 600 ℃ of following anneal, obtain the ito thin film sample at last.The performance index of this film are:
Thickness: 40～500nm
Film resistance per square: 50～400 Ω/
Transmitance (550nm): 〉=88%
Embodiment 10
The surface is coated with skim SiO
2The sheet glass of film cleans up, and sheet glass is placed on the spin coater then, and the slurry of embodiment 5 preparations drips on the sheet glass, then with 8000r/min speed spin-coating film, this process is repeated again in dry back after heat-treating under 400 ℃, 600 ℃ of following anneal, obtain the ito thin film sample at last.
The performance index of this film are:
Thickness: 30～500nm
Film resistance per square: 40～400 Ω/
Transmitance (550nm): 〉=90%
Claims (10)
1. the preparation method of an indium tin oxide precursor slurry, it is characterized in that: with indium, tin metal or indium, tin metal salt is the preparation of raw material mixing solutions, add dispersion agent and precipitation agent in the mixing solutions, obtaining indium tin hydroxide or carbonate colloid, is that solvent adding additive obtains indium tin oxide precursor slurry with anhydrous monobasic lower alcohol then.
2. the preparation method of indium tin oxide precursor slurry as claimed in claim 1, it is characterized in that: described mixing solutions is that indium metal and metallic tin are dissolved in mixing then in the acid solution respectively fully, wherein the purity of indium, tin metal is greater than 99.99%, acid solution be purity more than or equal to the pure concentrated nitric acid of top grade, concentrated hydrochloric acid, concentrated sulfuric acid aqueous solution or purity more than or equal to the pure concentrated nitric acid of top grade, concentrated hydrochloric acid, the vitriol oil any two kinds or three kinds of mixed aqueous solution.
3. the preparation method of indium tin oxide precursor slurry as claimed in claim 1, it is characterized in that: the dispersion agent that adds in the described mixing solutions is tween series and polyethylene glycol type, precipitation agent be purity more than or equal to the pure yellow soda ash of top grade, sodium bicarbonate, salt of wormwood, saleratus, volatile salt, bicarbonate of ammonia, ammoniacal liquor, sodium hydroxide, potassium hydroxide, hydrated barta, lithium hydroxide or urea, under condition of stirring, add.
4. the preparation method of indium tin oxide precursor slurry as claimed in claim 1, it is characterized in that: described indium tin hydroxide or carbonate colloid are with deionized water wash repeatedly, then repeatedly, add described solvent and described additive again with soaked in absolute ethyl alcohol.
5. the preparation method of indium tin oxide precursor slurry as claimed in claim 1 is characterized in that: described solvent is dehydrated alcohol or Virahol, and described additive is acetate, thanomin, tween series, polyethylene glycol type and polyvinylpyrrolidone.
6. the preparation method of indium tin oxide precursor slurry as claimed in claim 1 is characterized in that: the viscosity of described indium tin oxide precursor slurry is 1.2～50.0 * 10
-3Pas, the quality percentage composition of indium and tin is 1%～20% in the slurry, the particle diameter in the slurry is 2～20nm.
7. the indium tin oxide precursor slurry with claim 1 preparation applies the preparation method who prepares ito thin film, it is characterized in that: after sheet glass is cleaned up, apply thin film with dip-coating method or spin-coating method at sheet glass, obtain ito thin film after drying, the thermal treatment then.
8. paint-on technique as claimed in claim 7 prepares the preparation method of ito thin film, it is characterized in that: the pull rate of described dip-coating method is 4～60cm/min, and the speed of rotation of described spin-coating method is 500～9000r/min.
9. the paint-on technique described in claim 7 prepares the preparation method of ito thin film, it is characterized in that: described thermal treatment temp is 300 ℃～900 ℃, and heat-up rate is 1～20 ℃/min.
10. the paint-on technique described in claim 7 prepares the preparation method of ito thin film, it is characterized in that: the thickness of described ito thin film is 30nm～500nm, at the visible region wavelength is that the transmissivity at 550nm place is more than 85%, and the film resistance per square is 40-400 Ω/, and the film surface is evenly smooth.
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| CN2005100722507A CN1868948B (en) | 2005-05-27 | 2005-05-27 | Preparation method of indium tin oxide precusor size and ITO thin film |
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| CN1868948B true CN1868948B (en) | 2010-12-01 |
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| CN102339905B (en) * | 2011-10-24 | 2013-03-20 | 通用光伏能源(烟台)有限公司 | Method for manufacturing transparent conductive oxide film glass by using LPCVD (low pressure chemical vapor deposition) technology and taking inorganic salt as precursor |
| CN102646759B (en) * | 2012-05-04 | 2015-05-27 | 深圳市科聚新材料有限公司 | Preparing method for transparent conductive oxide film |
| CN105776882B (en) * | 2014-12-15 | 2018-07-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of preparation method of ito thin film |
| CN105174742B (en) * | 2015-08-31 | 2018-02-16 | 东北电力大学 | A kind of preparation method of electro-conductive glass |
| CN108178511A (en) * | 2017-12-06 | 2018-06-19 | 吕莉 | A kind of preparation method of high coloring stable type electrochomeric glass |
| CN112457025B (en) * | 2020-12-11 | 2022-08-30 | 广西晶联光电材料有限责任公司 | Preparation method of nano ITO powder with large specific surface area |
Citations (1)
| 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 |
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2005
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Patent Citations (1)
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 张维佳,王天民等.纳米ITO粉末及高密度ITO靶制备共用的研究现状.稀有金属材料和工程33 5.2004,33(5),第450页第1栏第2行至第32行. |
| 张维佳,王天民等.纳米ITO粉末及高密度ITO靶制备共用的研究现状.稀有金属材料和工程33 5.2004,33(5),第450页第1栏第2行至第32行. * |
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