CN1599024A - Tin-doped indium oxide film and making process of fine pattern - Google Patents

Tin-doped indium oxide film and making process of fine pattern Download PDF

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CN1599024A
CN1599024A CN 200410026379 CN200410026379A CN1599024A CN 1599024 A CN1599024 A CN 1599024A CN 200410026379 CN200410026379 CN 200410026379 CN 200410026379 A CN200410026379 A CN 200410026379A CN 1599024 A CN1599024 A CN 1599024A
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tin
solution
indium oxide
micropicture
solvent
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CN1299326C (en
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赵高扬
李颖
张卫华
韩晶
陈源清
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Xian University of Technology
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Xian University of Technology
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Abstract

The invention discloses the indium oxide film adulterating with tin and the preparation technique of minute figures. The indium nitrate and the tin tetrachloride are put into the acetylacetone solrent, add the deionized water to it and get the solution A; add the chelating agent of benzoyl acetone into the ethylene glycol monomethyl ether solvent and get the solution B; mix the solution A with the solution B, whisk it, aggradate it and get the indium oxide sol adulterated with light sensitive tin. The high pressure mercury lamp or ultraviolet laser pass through the masking with minute figures, irradiate the indium oxide sol adulterated with light sensitive tin, irradiate it with ultraviolet light in the air environment, get rid of its masking, put it in the absolute ethyl alcohol, dissolve the part that is not irradiated by the ultraviolet light, keep the part irradiated, heat it to get rid of the organic material and get the minute figure of the indium oxide film adulterated with tin. The invention does not need special vacuum, reaction chamber, photoresist and corrosive medium, can produce great areal minute figure and can get the high class minute figures of the ITO film.

Description

The indium oxide film of tin dope and Micropicture preparation technology
Technical field
The present invention relates to photoelectron and microelectronic, particularly the preparation of transparent conductive film and Micropicture preparation method.
Background technology
The indium oxide film of tin dope is commonly called ITO (Indum-tin-oxide) film, is a kind of semiconductive thin film of transparent, conduction, is widely used in the transparency electrode of flat-panel monitor such as liquid crystal, plasma and solar cell.At present, the conventional method for preparing ito thin film has chemical vapour deposition technique, magnetron sputtering method, hot spray process, sol-gel process etc.Yet the ito thin film of using at microelectronic all requires to make specific Micropicture usually.Ito thin film Micropicture preparation at present is to adopt ion etching or traditional photoetching process behind the system film.The common feature of these two all is that system film and Micropicture preparation are separately carried out, and promptly prepares the ito thin film with specific light electrical property earlier, carries out the Micropicture preparation again.The former ion etching method need in vacuum or ionic reaction is indoor carries out, and is subjected to equipment to limit the Micropicture that is difficult to prepare large area film, and apparatus expensive, and inefficiency is seldom used in volume production.And traditional photoetching technique of using in the industry at present is after preparing film, is coated with one deck photoresist on film, by mask exposure, development, carries out chemical corrosion again, removes the Micropicture that residual photoresist obtains ito thin film at last.This method technology is loaded down with trivial details, needs to use the aggressive chemistry medicine in etching process, and environment is had pollution.On the other hand, because ito thin film contains indium, two kinds of elements of tin, when the Micropicture size will show two kinds of different corrosion rates of element than hour (as the thin level of a sub-micro) chemical mordant, make Micropicture lines roughening, be difficult to adapt to the needs of submicron order ito thin film Micropicture technology.
Summary of the invention
The object of the present invention is to provide a kind of indium oxide film and Micropicture preparation technology of tin dope, its technology is simple, and composition is easily transferred, but large tracts of land system film.
Technical scheme of the present invention is achieved in that a kind of indium oxide film of tin dope, at first make the indium oxide colloidal sol of photonasty tin dope, on glass or silicon substrate, prepare indium oxide gel film with the photosensitive tin dope of ultraviolet with conventional dip-coating method or spin-coating method;
The preparation method of the indium oxide colloidal sol of said photonasty tin dope is: with indium nitrate ln (NO 3) 34.5H 2O and butter of tin Sncl 45H 2O is that raw material, BA BzAcH are chelating agent;
Be solvent at first, with indium nitrate ln (NO with acetylacetone,2,4-pentanedione AcAc 3) 34.5H 2O and butter of tin Sncl 45H 2O adds in the acetylacetone,2,4-pentanedione AcAc solvent, adds deionized water then, and making each component mol ratio is ln (NO 3) 34.5H 2O: Sncl 45H 2O: AcAc: H 2O=1: 0.05~0.12: 6~8: 0.1~0.15, use magnetic stirrer 0.5-2 hour down at 18-50 ℃, make solution A;
Be solvent with EGME MOE again, BA BzAcH is that chelating agent adds in the EGME MOE solvent, and its each component mol ratio is BzAcH: MOE=1: 40~50, normal temperature 18-30 ℃ of dissolving down, make solution B;
Solution A, B are mixed, make the ln (NO that derives from A 3) 34.5H 2O is 1: 0.8~1.2 with the BzAcH mol ratio that derives from B, uses magnetic stirrer 1-3 hour down at normal temperature 18-30 ℃, makes solution C;
Solution C through 8-12 hour heavyization, obtains the indium oxide colloidal sol of photonasty tin dope through stirring, under 30-35 ℃.
A kind of indium oxide film that adopts tin dope prepares the method for Micropicture, with high-pressure mercury lamp or Ultra-Violet Laser by having the mask of Micropicture, the indium oxide gel film of irradiation tin dope, ultraviolet lighting is after 10~15 minutes under atmospheric environment, remove mask, in absolute ethyl alcohol, placed then 1~2 minute, not dissolved by the part of illumination, complete the remaining of part through illumination, obtain the Micropicture of the indium oxide gel film of tin dope, further carry out heating in 20-30 minute again, remove organic substance, just obtained transparent at 450-500 ℃, the indium oxide film Micropicture of the tin dope of conduction.
The present invention obtains to have the compound middle transition film of photosensitive organic and inorganic owing to introduce the photonasty chelate in the colloidal sol preparation process, and this middle transition film can change the ito thin film with light transmission and conductivity into by heat treatment.The preparation of Micropicture is a photonasty characteristic of utilizing middle transition film self, by mask exposure, develops in absolute ethyl alcohol, at first obtains the Micropicture of middle transition film, makes it change the ito thin film Micropicture into by heat treatment again.The present invention does not need special vacuum and reative cell, can make the Micropicture of large tracts of land ito thin film.Compare with conventional lithography, need not photoresist and Korrosionsmedium, and can obtain the Micropicture of finer high-quality ito thin film.
Embodiment
Below by embodiment content of the present invention is described in further detail;
Embodiment one:
With indium nitrate ln (NO 3) 34.5H 2O and butter of tin Sncl 45H 2O is that raw material, BA BzAcH are chelating agent;
Be solvent at first, with indium nitrate ln (NO with acetylacetone,2,4-pentanedione AcAc 3) 34.5H 2O and butter of tin Sncl 45H 2O adds in the acetylacetone,2,4-pentanedione AcAc solvent, adds deionized water then, and each component mol ratio is: ln (NO 3) 34.5H 2O: Sncl 45H 2O: AcAc: H 2O=1: 0.05: 6: 0.1, use magnetic stirrer 2 hours down at 25 ℃, make solution A.
Obtain solution B is a solvent with EGME MOE more then, and BA BzAcH is that chelating agent adds in the EGME MOE solvent each component mol ratio BzAcH: MOE=1: 50, in 18 ℃ of dissolvings down of normal temperature, make solution B.With solution A, B is mixed with solution C, in solution C, makes the ln (NO that derives from A 3) 34.5H 2O is 1: 1 with the BzAcH mol ratio that derives from B, uses magnetic stirrer 1 hour down for 18 ℃ at normal temperature, makes solution C.Solution C obtains photonasty ITO colloidal sol through stirring, 35 ℃, 8 hours heavyization.With the photonasty ITO colloidal sol that makes, adopt dip-coating method, be about to silicon substrate and immerse in the solution C, vertically lift and can on glass substrate, make the ITO gel mould.Again Ultra-Violet Laser (high-pressure mercury lamp of 200W) is shone the ITO gel film by mask, ultraviolet lighting removed mask after 15 minutes under atmospheric environment, placed 1 minute in absolute ethyl alcohol, not dissolved by the part of illumination, through complete the remaining of part of illumination.Obtained the Micropicture of ITO gel film.Further carry out heating in 20 minutes, remove organic substance, just obtained ito thin film Micropicture transparent, conduction at 500 ℃.
Embodiment two:
With indium nitrate ln (NO 3) 34.5H 2O and butter of tin Sncl 45H 2O is that raw material, BA BzAcH are chelating agent;
With acetylacetone,2,4-pentanedione AcAc is solvent, with indium nitrate ln (NO 3) 34.5H 2O and butter of tin Sncl 45H 2O adds in the acetylacetone,2,4-pentanedione AcAc solvent, adds deionized water then, and each component ratio is (mol ratio) ln (NO 3) 34.5H 2O: Sncl 45H 2O: AcAc: H 2O=1: 0.1: 8: 0.15, use magnetic stirrer 1 hour down at 18 ℃, make solution A.
Obtain solution B is a solvent with EGME MOE more then, and BA BzAcH is that chelating agent adds in the EGME MOE solvent each component mol ratio BzAcH: MOE=1: 40, under 25 ℃ of normal temperature, make solution B.With solution A, B mixed configuration solution C in solution C, makes the ln (NO that derives from A 3) 34.5H 2O is 1: 0.8 with the BzAcH mol ratio that derives from B, uses magnetic stirrer 2 hours down for 25 ℃ at normal temperature, makes solution C.Solution C obtains photonasty ITO colloidal sol through stirring, 30 ℃, 10 hours heavyization.With the photonasty ITO colloidal sol that makes, adopt spin-coating method on silica-based version, to make the ITO gel mould.Again the high-pressure mercury lamp Ultra-Violet Laser is shone the ITO gel film by mask, ultraviolet lighting is after 10 minutes under atmospheric environment, remove mask, in alcohol solvent, placed 2 minutes then, not dissolved by the part of illumination, through complete the remaining of part of illumination, obtained the Micropicture of ITO gel film, further carry out heating in 30 minutes again, remove organic substance at 450 ℃.Just obtained the Micropicture of ito thin film transparent, conduction.
Embodiment three:
With indium nitrate ln (NO 3) 34.5H 2O and butter of tin Sncl 45H 2O is that raw material, BA BzAcH are chelating agent;
With acetylacetone,2,4-pentanedione AcAc is solvent, with indium nitrate ln (NO 3) 34.5H 2O and butter of tin Sncl 45H 2O adds in the acetylacetone,2,4-pentanedione AcAc solvent, adds deionized water then, and each component mol ratio is ln (NO 3) 34.5H 2O: Sncl 45H 2O: AcAc: H 2O=1: 0.12: 7: 0.8, use magnetic stirrer 1.5 hours down at 30 ℃, make solution A.
Obtain solution B is a solvent with EGME MOE more then, and BA BzAcH is that chelating agent adds in the EGME MOE solvent, and each component mol ratio is BzAcH: MOE=1: 45, at 20 ℃ of following solution of normal temperature, make solution B.Solution A, B are mixed with solution C, in solution C, make the ln (NO that derives from A 3) 34.5H 2O is 1: 1.2 with the BzAcH mol ratio that derives from B, uses magnetic stirrer 3 hours down for 20 ℃ at normal temperature, makes solution C.Solution C obtains photonasty ITO colloidal sol through stirring, heavyization.Adopt dip-coating method to make the ITO gel mould photonasty ITO colloidal sol that makes.Again the high-pressure mercury lamp ultraviolet light is shone the ITO gel film by mask, ultraviolet lighting removed mask after 12 minutes under atmospheric environment, placed 2 minutes in alcohol solvent then.Obtained the Micropicture of ITO gel film.Further carry out heating in 20 minutes again, remove organic substance at 460 ℃.Just obtain the Micropicture of ito thin film.
Embodiment four:
With indium nitrate ln (NO 3) 34.5H 2O and butter of tin Sncl 45H 2O is that raw material, BA BzAcH are chelating agent;
With acetylacetone,2,4-pentanedione AcAc is solvent, with indium nitrate ln (NO 3) 34.5H 2O and butter of tin Sncl 45H 2O adds in the acetylacetone,2,4-pentanedione AcAc solvent, adds deionized water then, each component mol ratio ln (NO 3) 34.5H 2O: Sncl 45H 2O: AcAc: H 2O=1: 0.06: 8: 0.8, use magnetic stirrer 1.2 hours down at 40 ℃, make solution A.Obtain solution B is a solvent with EGME MOE more then, and BA BzAcH is that chelating agent adds in the EGME MOE solvent each component mol ratio BzAcH: MOE=1: 48, in 22 ℃ of dissolvings down of normal temperature, make solution B.Solution A, B are mixed with solution C, in solution C, make the ln (NO that derives from A 3) 34.5H 2O is 1: 0.8 with the BzAcH mol ratio that derives from B, uses magnetic stirrer 1.5 hours down for 22 ℃ at normal temperature, makes solution C.Solution C through 12 hours heavyization, obtains photonasty ITO colloidal sol through stirring, under 32 ℃.Adopt spin-coating method on the glass-based version, to make the ITO gel mould photonasty ITO colloidal sol that obtains.Again the high-pressure mercury lamp Ultra-Violet Laser is shone the ITO gel film by mask, UV-irradiation was removed mask after 12 minutes under atmospheric environment, placed 1.5 minutes in alcohol solvent then, obtained the Micropicture of ITO gel film.Further carry out heating in 25 minutes again, remove organic substance at 470 ℃.Just obtain the Micropicture of ito thin film.
Embodiment five:
With indium nitrate ln (NO 3) 34.5H 2O and butter of tin Sncl 45H 2O is that raw material, BA BzAcH are chelating agent;
With acetylacetone,2,4-pentanedione AcAc is solvent, with indium nitrate ln (NO 3) 34.5H 2O and butter of tin Sncl 45H 2O adds in the acetylacetone,2,4-pentanedione AcAc solvent, adds deionized water then, and each component mol ratio is ln (NO 3) 34.5H 2O: Sncl 45H 2O: AcAc: H 2O=1: 0.11: 8: 0.8, use magnetic stirrer 0.5 hour down at 50 ℃, make solution A.Obtain solution B is a solvent with EGME MOE more then, and BA BzAcH is that chelating agent adds in the EGME MOE solvent each component mol ratio BzAcH: MOE=1: 50, in 30 ℃ of dissolvings down of normal temperature, make solution B.Solution A, B are mixed with solution C, in solution C, make the ln (NO that derives from A 3) 34.5H 2O is 1: 1 with the BzAcH mol ratio that derives from B, uses magnetic stirrer 2.5 hours down for 30 ℃ at normal temperature, makes solution C.Solution C through 8 hours heavyization, obtains photonasty ITO colloidal sol through stirring, under 30 ℃.To obtain photonasty ITO colloidal sol adopts spin-coating method to make the ITO gel mould on silica-based version.Be the He-Cd Ultra-Violet Laser of 325nm again with wavelength: power: 10mW/cm 2, by mask irradiation ITO gel film, shine after 10 minutes, in alcohol solvent, placed 2 minutes.Obtain the Micropicture of ITO gel film.Further 500 ℃ of heating of carrying out 25 minutes, remove organic substance again.Just obtain the Micropicture of ito thin film.

Claims (2)

1, a kind of indium oxide film of tin dope at first, makes the indium oxide colloidal sol of photonasty tin dope, then, prepares the indium oxide gel film with the photosensitive tin dope of ultraviolet with conventional dip-coating method or spin-coating method on glass or silicon substrate; It is characterized in that the preparation method of the indium oxide colloidal sol of said photonasty tin dope is as follows:
With indium nitrate ln (NO 3) 34.5H 2O and butter of tin Sncl 45H 2O is that raw material, BA BzAcH are chelating agent;
Be solvent at first, with indium nitrate ln (NO with acetylacetone,2,4-pentanedione AcAc 3) 34.5H 2O and butter of tin Sncl 45H 2O adds in the acetylacetone,2,4-pentanedione AcAc solvent, adds deionized water then, and making each component mol ratio is indium nitrate ln (NO 3) 34.5H 2O: butter of tin Sncl 45H 2O: acetylacetone,2,4-pentanedione AcAc: water H 2O=1: 0.05~0.12: 6~8: 0.1~0.15, use magnetic stirrer 0.5-2 hour down at 18-50 ℃, make solution A;
Be solvent with EGME MOE again, BA BzAcH is that chelating agent adds in the EGME MOE solvent, and its each component mol ratio is BA BzAcH: EGME MOE=1: 40~50, normal temperature 18-30 ℃ of dissolving down, make solution B;
Solution A, B are mixed, make the indium nitrate ln (NO that derives from solution A 3) 34.5H 2O is 1: 0.8~1.2 with the BA BzAcH mol ratio that derives from solution B, uses magnetic stirrer 1-3 hour down at normal temperature 18-30 ℃, makes solution C;
Solution C through 8-12 hour heavyization, obtains the indium oxide colloidal sol of photonasty tin dope through stirring, under 30-35 ℃.
2, a kind of indium oxide film that adopts tin dope prepares the method for Micropicture, it is characterized in that:
With high-pressure mercury lamp or Ultra-Violet Laser by having the mask of Micropicture, the indium oxide gel film of irradiation tin dope, UV-irradiation is after 10~15 minutes under atmospheric environment, remove mask, in absolute ethyl alcohol, placed then 1~2 minute, not dissolved by the part of UV-irradiation, complete the remaining of part through irradiation, obtain the Micropicture of the indium oxide gel film of tin dope, again further at 450-500 ℃, time is to heat in 20-30 minute, removes organic substance, has just obtained the indium oxide film Micropicture of the tin dope of transparent, conduction.
CNB200410026379XA 2004-07-30 2004-07-30 Tin-doped indium oxide film and making process of fine pattern Expired - Fee Related CN1299326C (en)

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CN101337773B (en) * 2008-08-14 2010-12-08 浙江理工大学 Method for preparing ITO film with high conductivity
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CN101631746B (en) * 2007-03-19 2011-08-24 韩国电子通信研究院 Method of synthesizing ITO electron-beam resist and method of forming ITO pattern using the same
CN105152545A (en) * 2015-06-25 2015-12-16 西安理工大学 Preparation method for nanocrystal-doped tungsten oxide electrochromic film pattern
CN107986637A (en) * 2017-11-23 2018-05-04 西安理工大学 A kind of preparation method of the tin-doped indium oxide nano-crystal film of in-situ crystallization
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US4878993A (en) * 1988-12-22 1989-11-07 North American Philips Corporation Method of etching thin indium tin oxide films
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CN1101352C (en) * 2000-07-15 2003-02-12 昆明理工大学 Process for preparing sol-gel of indium tin oxide film
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CN101631746B (en) * 2007-03-19 2011-08-24 韩国电子通信研究院 Method of synthesizing ITO electron-beam resist and method of forming ITO pattern using the same
CN101174088B (en) * 2007-10-19 2010-08-18 西安理工大学 Polymethyl methacrylate-TiO2 hybrid material preparation and minute pattern production
CN101337773B (en) * 2008-08-14 2010-12-08 浙江理工大学 Method for preparing ITO film with high conductivity
CN102044737A (en) * 2009-10-10 2011-05-04 江国庆 Manufacturing method of film antenna
CN105152545A (en) * 2015-06-25 2015-12-16 西安理工大学 Preparation method for nanocrystal-doped tungsten oxide electrochromic film pattern
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CN107986637A (en) * 2017-11-23 2018-05-04 西安理工大学 A kind of preparation method of the tin-doped indium oxide nano-crystal film of in-situ crystallization
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