CN1570772A - Anticorrosive developing composition - Google Patents
Anticorrosive developing composition Download PDFInfo
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- CN1570772A CN1570772A CN 03147049 CN03147049A CN1570772A CN 1570772 A CN1570772 A CN 1570772A CN 03147049 CN03147049 CN 03147049 CN 03147049 A CN03147049 A CN 03147049A CN 1570772 A CN1570772 A CN 1570772A
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- corrosion protection
- developer composition
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- tmah
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Abstract
The anti-corrosive developing compound in this invention comprises organic solution with one to ten weight percent organic alkali, one to ten weight percent of glycosyl compound and one to ten weight percent of polyatomic alcohol. The anti-corrosive developing compound excels in anti-metal corrosion and developing property and is applied in the production of semiconductor component and LCD component.
Description
Background of invention
1, invention field
The present invention relates to a kind of corrosion protection developer composition of novelty, be particularly related to a kind of corrosion protection developer composition of producing semiconductor element and liquid crystal display device that is applicable to, reason is the performance that this corrosion protection developer composition has the corrosion of good prevention metal substrate, good prevention forms on substrate not of the same race metal laminated in the performance of metal erosion and good developing performance.
2, prior art
By convention, semiconductor element and liquid crystal display device are produced by lithography usually, and this method is used resist before being included in etching processing or DIFFUSION TREATMENT, optionally to protect the substrate below the resist; This resist has photosensitization to acting on on-chip dynamic rays as ultraviolet ray, far ultraviolet, laser, X-ray and electron beam; The oven dry resist is to form resist layer; Selectively resist layer is exposed to dynamic rays; With the resist layer after the exposure is developed to form the resist pattern picture on substrate.
In lithography, use a kind of alkaline aqueous solution to prevent the electrical property deterioration of semiconductor element and liquid crystal display device usually, the principal ingredient that this alkaline aqueous solution contains is the organic base of free metal ion.
The developer solution that known developing performance improves to some extent is to prepare by adjuvant being added in the aqueous solution that principal ingredient is the top organic base of carrying, for example, the aqueous developer solution (Japanese Unexamined Patent Publication No 64-19344) that contains the polyvalent alcohol of the tetramethylammonium hydroxide of 0.2-3.5% weight and 0.2-10% weight.
In the production of semiconductor element and liquid crystal display device, as substrate for silicon wafer or have the metal level that is used to form telegraph circuit such as the glass plate of aluminium lamination.Offscreen method makes on-chip metal level form image.Yet known developer solution is easy to the corroding metal layer.In the recent period, the substrate as thin film transistor (TFT) (TFT) display device that people paid close attention to generally comprises glass plate, transparency conducting layer on the glass plate such as indium oxide layer and indium oxide-Xi layer (ITO layer), and the vapor deposition layer of the aluminium on the conductive layer.By using general developer solution, make the aluminium lamination of this substrate form lithographic image, this substrate has the not lamination of metal of the same race, and in this process, aluminium lamination or other metals that contact this aluminium lamination usually are corroded easily.Therefore, press for the trend that reduces the developer solution corrosion.
In order to address this problem, Japanese Unexamined Patent Publication No 8-160634 proposes: in the Resist development liquid of organic base as principal ingredient, add the polyvalent alcohol of 20-50% weight.Yet,, unsatisfactory aspect developing performance although the developer solution that proposes in this application is to have reduced to corrosion of metal.That is to say that compare the developer solution of the tetramethylammonium hydroxide that contains 2.38% weight of widespread use in the art, the developer solution in this application has increased minimum exposure, has exposed deficiency aspect developing performance.
Summary of the invention
Consider various situations above in this area, the purpose of this invention is to provide a kind of corrosion protection developer composition of producing semiconductor element and liquid crystal display device that is applicable to, reason is that said composition has the performance that good prevention metal substrate is corroded and has good developing performance.
The present inventor in line with development a kind of prevent metal substrate be corroded aspect the purpose of well behaved corrosion protection developer composition, through a large amount of research, found that the corrosion protection developer composition for preparing all is being excellent aspect prevention corrosion and the developing performance by add the sugar compounds and the polyvalent alcohol of certain content in containing the developer solution that principal ingredient is an organic base.The present invention finishes on the basis of this discovery.
Detailed Description Of The Invention
The organic base that uses in the composition of the present invention can be primary amine, secondary amine or the tertiary amine that has straight chain, side chain or ring texture.The example comprises Diaminoalkane, as 1, and the 3-diaminopropanes; Arylamine, as 4,4 '-diamino-diphenylamine; Alkyl amine, as N, N '-diamido dialkylamine has 3-5 and becomes ring carbon atom and 1 or 2 heterocyclic amine that becomes ring hetero atom, and this heteroatoms is selected from nitrogen-atoms, oxygen atom and sulphur atom, as pyrroles, pyrrolidine, pyrrolidone, pyridine, morpholine, pyrazine, piperidines, oxazole and thiazole.In addition, lower alkyl quaternary ammonium salt also can be used as organic base.The example comprises tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydroxide tetrapropylammonium, hydroxide trimethyl (2-hydroxyethyl) ammonium, hydroxide triethyl (2-hydroxyethyl) ammonium, hydroxide tripropyl (2-hydroxyethyl) ammonium and hydroxide trimethyl (1-hydroxypropyl) ammonium.In above-mentioned organic base, preferred lower alkyl quaternary ammonium salt, preferred especially tetramethylammonium hydroxide.These organic salts can use separately or two or more is used in combination.
The concentration of organic base can be carried out suitable selection with the type of the resist that will use according to its type, normally the 1-10% weight of Resist development composition, preferably 2-8% weight.If be less than 1% weight, the development capability of resist is undesirable.If surpass 10% weight, the loss of resist increases unfriendly in the territory, non-exposed area, causes forming accurate corrosion protection image.
Employed polyvalent alcohol is the alcohol that contains two or more carbon atoms in the corrosion protection developer composition of the present invention, can comprise ethylene glycol, 1,2-propylene glycol, 1, ammediol, glycerine, 1,2-butylene glycol, 1,3 butylene glycol, 1,4-butylene glycol, 1,2,4-butantriol, 1,2,3-butantriol, erythrite, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2,3-penta triol, 1,2,4-penta triol, 1,2,5-penta triol, 1,3,4-penta 3 pure and mild 1,3,5-penta triol, preferred especially 1,2-propylene glycol.These polyvalent alcohols can use separately or two or more is used in combination.
The concentration of polyvalent alcohol is the 1-10% weight of corrosion protection developer composition.If be less than 1% weight, do not reach sufficient corrosion protection result.If surpass 10% weight, the loss of resist increases unfriendly in the territory, non-exposed area, causes forming accurate corrosion protection image.
Employed sugar compounds is sugar or sugar alcohol in the corrosion protection developer composition of the present invention.Sugar can comprise the monose that contains 3-6 carbon atom, as glyceraldehyde, threose, erythrose, arabinose, wood sugar, ribose, ribulose, xylulose, glucose, mannose, galactose, Tagatose, allose, altrose, gulose, idose, talose, sorbose, psicose and fructose.The example of sugar alcohol comprises threitol, antierythrite, arabite, ribitol, xylitol, iditol, galactitol, glucitol (D-sorbite), volemitol, crocodile plough sugar alcohol and octane alcohol (octitol).In above-mentioned sugar compounds, preferably have ribose, wood sugar, arabinose, D-sorbite and the xylitol of high corrosion inhibition ability.
The concentration of sugar compounds is the 1-10% weight of corrosion protection developer composition of the present invention.If be less than 1% weight, can not get suppressing fully the effect of corrosion.If surpass 10% weight, the dissolution velocity of resist reduces.
As long as purpose of the present invention is not destroyed, corrosion protection developer composition of the present invention can also comprise the normally used adjuvant of general corrosion protection developer composition, as surfactant, lubricant, wetting agent, stabilizing agent and dissolution aids.
Suppress effect because Resist development composition of the present invention has fabulous corrosion, use it to make and be deposited on on-chip metallic film and accurately form image, and do not corrode metallic film.The metallic film that has prevented corrosion effectively can comprise aluminium and aluminium alloy, as Al-zn-mg-cu alloy, aluminium-silicon alloys, aluminum-neodymium alloys and aluminum-zirconium alloy.Metal laminated substrate not of the same race is corroded corrosion protection developer composition of the present invention equally also is effective to preventing to contain.For example, contain in transparency conducting layer such as indium oxide layer and the vapor deposition layer substrate that contains the aluminium on the ITO layer of indium-tin-oxide and can effectively handle, and do not cause the corrosion of aluminium lamination and ITO layer.
The resist that can develop with corrosion protection developer composition of the present invention can be two types of negativity and positivities, and as long as this resist can develop by known alkaline aqueous solution, resist of the present invention is not defined as a certain particular type.
Because corrosion protection developer composition of the present invention has the fabulous corrosive effect that prevents, so it is applied to metal level, and to carry out that resist develops be effective, simultaneously do not cause corrosion of metal, and to have metal laminated substrate not of the same race for processing also be effective.Therefore, this corrosion protection developer composition is specially adapted to need the production that the production of the semiconductor element of accurate telegraph circuit and liquid crystal display device and use have the TFT display device of metal laminated substrate not of the same race.
With reference to the following examples, the present invention is further detailed explanation, but this should not be construed as and is used to limit the scope of the invention.
Embodiment 1-3 and Comparative Examples 1-9
In the time of 23 ℃, will comprise glass plate, on the glass plate on the ITO layer of 1000 and the ITO layer substrate of the aluminium lamination of 3000 be immersed in each listed composition of table 1 60 seconds, water rinses substrate then, dries up with nitrogen again.Observe the surface of aluminium-ITO lamination under optical microscope, assess its Corrosion Protection according to grade A and grade B, grade A represents not observe etch pit on the surface; Grade B represents to observe etch pit on the surface.Be displayed in Table 1 viewed result.
Table 1
Organic base sugar compounds polyvalent alcohol Corrosion Protection
(% weight) (% weight) (% weight)
Embodiment
1 TMAH xylitol 1,2-propylene glycol A
3.0 6 6
2 TMAH D-sorbites 1,2-propylene glycol A
3.0 6 6
3 TMAH xylitol 1,3 butylene glycol A
3.0 6 6
Comparative Examples
1 TMAH - - B
2.38
2 TMAH - - B
3.0
3 TMAH xylitol-A
3.0 6
4 TMAH D-sorbite-A
3.0 6
5 TMAH-1,2-propylene glycol B
3.0 6
6 TMAH-1,3 butylene glycol B
3.0 6
7 TMAH-glycerine A
3.5 20
8 TMAH-ethylene glycol A
4.0 30
9 TMAH-1,2-propylene glycol A
3.5 40
TMAH: tetramethylammonium hydroxide
Embodiment 4-6 and Comparative Examples 10-18
Positive corrosion-resisting agent is coated on 6 inches the silicon wafer, and on hot plate, cured 3 minutes in 120 ℃, to form the thick resist layer of about 17000 of one deck.The wafer that has a resist layer is through after the exposure of varying strength, is immersed in each listed composition of table 2 60 seconds in 23 ℃, and water rinses wafer then, dries up with nitrogen again.By using n﹠amp; The n﹠amp that k company limited produces; K analyzer 1280 is measured the thickness of resist layers before and after exposure, makes the loss of resist in minimum irradiation amount that resist develops and the territory, non-exposed area with mensuration.Show measurement result in the table 2.
Table 2
Organic base sugar compounds polyvalent alcohol
Developing performance
(% weight) (% weight) (% weight) minimum irradiation amount non-exposed area
(mJ) territory loss
Embodiment
4 TMAH xylitols 1,2-propylene glycol 15 210
3.0 6 6
5 TMAH D-sorbites 1,2-propylene glycol 16 195
3.0 6 6
6 TMAH xylitol 1,3 butylene glycols 15 210
3.0 6 6
Comparative Examples
10 TMAH - - 15 200
2.38
11 TMAH - - 10 210
3.0
12 TMAH xylitols-45 5
3.0 6
13 TMAH D-sorbites-55 5
3.0 6
14 TMAH-1,2-propylene glycol 8 400
3.0 6
15 TMAH-1,3 butylene glycol 8 390
3.0 6
16 TMAH-glycerine 30 10
3.5 20
17 TMAH-ethylene glycol 25 20
4.0 30
18 TMAH-1,2-propylene glycol＞100-100*
3.5 40
TMAH: tetramethylammonium hydroxide
* in Comparative Examples 18, resist swelling in development treatment causes the increase of resist layer thickness in the territory, non-exposed area.Therefore, loss is represented with negative value.
Though the corrosion protection developer composition of embodiment 1-6 is suitable at the developer solution (Comparative Examples 1-10) with those widespread uses in semiconductor element and liquid crystal display device are produced aspect the developing performance, shown the corrosive power that prevents that has improved.The composition of Comparative Examples 3-4 and 7-9 does not corrode aluminium and the ITO in aluminium/ITO lamination, proves as Comparative Examples 12-13 and 16-18, and it needs the very long time shutter unfriendly.
As mentioned above, organic base, sugar compounds and polyvalent alcohol are in conjunction with a kind of corrosion protection developer composition of producing semiconductor element and liquid crystal display device that is applicable to is provided, reason is the performance that this corrosion protection developer composition has the corrosion of good prevention metal substrate, good prevention forms on substrate not of the same race metal laminated in the performance of metal erosion and good developing performance.
Claims (7)
1, a kind of corrosion protection developer composition, said composition comprises the organic base that contains 1-10% weight, the aqueous solution of the polyvalent alcohol of the sugar compounds of 1-10% weight and 1-10% weight.
2, corrosion protection developer composition as claimed in claim 1, wherein organic base is the tetramethylphosphonihydroxide hydroxide mirror
3, corrosion protection developer composition as claimed in claim 1 or 2, wherein sugar compounds is at least a sugar that is selected from ribose, wood sugar and arabinose.
4, corrosion protection developer composition as claimed in claim 1 or 2, wherein sugar compounds is at least a compound that is selected from the sugar alcohol that contains 4 or 4 above carbon atoms.
5, corrosion protection developer composition as claimed in claim 4, the sugar alcohol that wherein contains 4 or 4 above carbon atoms is D-sorbite or xylitol.
6, as the described corrosion protection developer composition of arbitrary claim among the claim 1-5, wherein polyvalent alcohol is at least a compound that is selected from ethylene glycol, propylene glycol, butylene glycol and butantriol.
7, as the described corrosion protection developer composition of arbitrary claim among the claim 1-5, wherein polyvalent alcohol is 1, the 2-propylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN03147049A CN100580561C (en) | 2003-07-16 | 2003-07-16 | Anticorrosive developing composition |
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|---|---|---|---|
| CN03147049A CN100580561C (en) | 2003-07-16 | 2003-07-16 | Anticorrosive developing composition |
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| CN1570772A true CN1570772A (en) | 2005-01-26 |
| CN100580561C CN100580561C (en) | 2010-01-13 |
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| CN03147049A Expired - Fee Related CN100580561C (en) | 2003-07-16 | 2003-07-16 | Anticorrosive developing composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102466986A (en) * | 2010-11-09 | 2012-05-23 | 苏州瑞红电子化学品有限公司 | Anticorrosion alkaline developing composition |
| CN106292207A (en) * | 2015-06-10 | 2017-01-04 | 安集微电子科技(上海)有限公司 | A kind of photoresistance residual washing liquid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3302120B2 (en) * | 1993-07-08 | 2002-07-15 | 関東化学株式会社 | Stripper for resist |
| DE4419166A1 (en) * | 1994-06-01 | 1995-12-07 | Hoechst Ag | Developer for photoresist layers |
| JP3968177B2 (en) * | 1998-09-29 | 2007-08-29 | Ａｚエレクトロニックマテリアルズ株式会社 | Fine resist pattern forming method |
| CN1126006C (en) * | 1999-12-30 | 2003-10-29 | 奇美实业股份有限公司 | Composition of developing liquid |
-
2003
- 2003-07-16 CN CN03147049A patent/CN100580561C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102466986A (en) * | 2010-11-09 | 2012-05-23 | 苏州瑞红电子化学品有限公司 | Anticorrosion alkaline developing composition |
| CN106292207A (en) * | 2015-06-10 | 2017-01-04 | 安集微电子科技(上海)有限公司 | A kind of photoresistance residual washing liquid |
| CN106292207B (en) * | 2015-06-10 | 2021-06-25 | 安集微电子科技（上海）股份有限公司 | Photoresist residue cleaning solution |
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| Publication number | Publication date |
|---|---|
| CN100580561C (en) | 2010-01-13 |
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