CN101156111A - Remover composition for photoresist of semiconductor device - Google Patents
Remover composition for photoresist of semiconductor device Download PDFInfo
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- CN101156111A CN101156111A CNA2006800111313A CN200680011131A CN101156111A CN 101156111 A CN101156111 A CN 101156111A CN A2006800111313 A CNA2006800111313 A CN A2006800111313A CN 200680011131 A CN200680011131 A CN 200680011131A CN 101156111 A CN101156111 A CN 101156111A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
The present invention relates to a photoresist remover composition for a semiconductor device fabrication process. The remover composition comprising an ammonium salt, a water-soluble organic amine and water of the present invention can effectively remove a photoresist film hardened and modified by hard baking, dry etching, wet etching, ashing and/or ion implantation, and a photoresist film modified by a metal byproduct etched from a metal film under the photoresist film, at high or low temperatures, in a short time while minimizing corrosion of metal wiring under the photoresist film.
Description
Technical field
The present invention relates to a kind of being used for, the photoresist remover composition of removal photoresist in the semiconductor devices process for preparing as integrated circuit (IC), large scale integrated circuit (LSI), VLSI (very large scale integrated circuit) (VLSI) etc.
Background technology
Usually, the preparation process of semiconductor devices comprises the formation step of conductive film figure, and wherein the photoresist figure is formed on the conducting film that exists on the semiconductor substrate surface, and removes not conducting film part by photoresist covered by etching.In the cleaning process after conductive film figure forms, should make remover with photoresist, remove the photoresist figure that the figure forming process, is used as mask from conducting film.In nearest semiconductor devices preparation, the etching that is used for the conducting film of conductive film figure formation is mainly undertaken by dry etching, and this makes the removal of photoresist in the cleaning treatment process become difficult.
In the past, use was removed photoresist based on the remover of phenol.But, can not fully remove the photoresist film that passes through dry etching or ion implantation technology based on the photoresist remover of phenol.And, because 100 ℃ of these arts demands or above high temperature and long dip time, so these technologies tend to increase the defective ratio of semiconductor devices.Owing to these reasons, almost can not be used for industrial circle at present based on the photoresist remover of phenol.
Thing has as an alternative proposed to comprise the photoresist remover composition of alkanolamine and diglycol monotertiary alkyl ether recently.Because this photoresist remover composition has less stench and toxicity, and can remove most of photoresist film, so it is widely used.But, owing to this remover composition of discovery is removed the photoresist film that has been exposed to plasma etching gas or ion beam in dry etching or ion implantation technology process unsatisfactorily, therefore need exploitation can effectively remove the new photoresist remover that passes through the photoresist film of dry etching or ion implantation modification.In addition, the photoresist remover that comprises alkanolamine tends to the heavy corrosion aluminium base.
As if the corrosion that betides photoetching process caused by the ionization of the water that causes by alkanolamine when water cleaning after removing photoresist remains in stripper on the substrate.Therefore, if alkanolamine uses with water, do not use the anticorrosive then can not head it off.
Can regard the formation (for example, aluminum chloride) of metal halide as another corrosion mechanism.When contacting water in the cleaning process after photoresist is removed technology, often the metal halide that forms as the plasma etching accessory substance can cause the substrate corrosion.After removing photoresist, the alloy that forms in the process that water cleans (for example, Al-Cu-Si) can be counted as another corrosion mechanism.Usually, local such corrosion of finding is pitch corrosion (pitting).Pitch corrosion is caused by the Galvanic type electrochemical reaction that has between different electronegative two kinds of metals.
And as mentioned above, remover removal with photoresist has been very difficult through the photoresist film of ion implantation technology.Particularly, it is more difficult removing the photoresist film that passes through the high dose ion injection technology that is used to form source/drain region (source/drain region) in the preparation of VLSI (very large scale integrated circuit).The reaction heat that is produced by high dose, high energy ion bundle in the ion implantation technology often makes the photoresist film sclerosis.Simultaneously, the explosion of photoresist often forms the photoresist residue.Typically, during ashing treatment, semiconductor wafer is heated to 200 ℃ or higher temperature.In this process, the solvent that residues in the photoresist has to be evaporated, but owing on the photoresist surface, form cured film, so this is impossible under the situation that high dose ion is injected.
As a result, when carrying out ashing, the pressure in the photoresist film increases, owing to its inner solvent that exists causes the photoresist film skin breakage.Phenomenon is called explosion in this.The surface of breaking is residual as residue, therefore is difficult to remove.In addition, because by the lip-deep cured film of thermosetting photoresist,, thereby cause crosslinked by the oxygen plasma oxidation so alloy or foreign ion can be introduced into photoresist.The oxidation of photoresist causes the pollution that caused by residue and particle, so this is the Another reason that the VLSI (very large scale integrated circuit) productive rate descends.
The flat 9-197681 of Japanese Patent Laid publication number discloses a kind of remover composition that comprises ammonium fluoride to remove effectively at ion injects and the ashing treatment process forms hardened photoresist film.The remover composition of this patent comprises ammonium fluoride, water-miscible organic solvent, water and the anticorrosive of 0.2～8wt%, and its pH value is restricted to 5～8.
But in order to prevent the corrosion of metal film, this remover composition only can be suitable at low temperatures.And, be restricted to pH neutral in the particle that in removing the semiconductor preparing process process, forms.
Summary of the invention
The purpose of this invention is to provide a kind of photoresist remover composition, this photoresist remover composition can be removed the photoresist film that hardens and at short notice by the photoresist film of the metal byproducts institute modification that etches in the above-mentioned technological process in dry etching, ashing and ion implantation process, the corrosion of the metal line below the photoresist film is minimized.
Embodiment
In order to achieve the above object, the invention provides a kind of photoresist remover composition that comprises ammonium salt, water-soluble organic amine and water.
Preferably, described remover composition can further comprise water-miscible organic solvent and anticorrosive.
Provided detailed description of the present invention hereinafter.
The present invention relates to a kind of photoresist remover composition, this photoresist remover composition can be removed effectively at short notice and be used for the photoresist film that the graphical and integrated dry etching of microcircuit, ashing and ion implantation process harden, and, the corrosion of the metal line below the photoresist film is minimized by the photoresist film of the metal byproducts institute modification that in above-mentioned technological process, etches.
In photoresist remover composition of the present invention, ammonium salt penetrates into the photoresist of modification at dissociation in water with ionic species, and removes the dopant ion that penetrates into photoresist in the dry etching process.
Preferably, be used for ammonium salt of the present invention be selected from the group formed by ammonium nitrate, ammonium formate, hartshorn salt, ammonium acetate, ammonium thiocyanate, ammonium sulfate, ammonium sulfide, ammonium oxalate and ATS (Ammonium thiosulphate) one of at least.
Preferably, in remover composition, the remover composition of every 100wt% comprises 0.5～20wt%, more preferably the described ammonium salt of 2.5～10wt%.If the content of described ammonium salt is lower than 0.1wt%, then be difficult to remove fully the modification photoresist.On the contrary, if its content surpasses 20wt%, the possibility that the metal line below photoresist is corroded increases with a little raising of removing efficient.
Preferably, described water-soluble organic amine compound can for be selected from the group formed by monoethanolamine, isopropanolamine, amino ethoxy ethanol, n-methylethanolamine, dimethylethanolamine, diethyl ethanolamine, 2-aminoethylamino ethanol, aminoethylpiperazine, aminopropyl piperazine, hydroxyethyl piperazine, 1-amino-4-methyl piperazine, 2-methyl piperazine, 1-methyl piperazine, 1-benzyl diethylenediamine, 2-phenylpiperazine, 1-amino-ethyl piperidines, 1-amino piperidine and 1-amino methyl piperidines one of at least.
Preferably, the remover composition of every 100wt% comprises the described water-soluble organic amine compound of 7～50wt%.If the content of described water-soluble organic amine compound is lower than 7wt%, then be difficult to remove fully the modification photoresist.On the contrary, if its content surpasses 50wt%, the possibility that the metal line below the photoresist is corroded can increase.
Preferably, be used for the pure water (deionized water) of water for filtering of photoresist remover composition of the present invention, the ultrapure water that more preferably has 18M Ω or bigger resistivity by ion exchange resin.
Preferably, in the photoresist remover composition, comprise 5～80wt%, more preferably the water of 15～55wt%.If the content of water is lower than 5wt%, then the activity of ammonium salt reduces, and therefore make removal by the metal byproducts that forms after the ashing treatment the serious ability drop of the photoresist of modification.On the contrary, if the content of water surpasses 80wt%, the metal line below the photoresist can be corroded, and because the relative content of other component reduces, removes the ability drop of modification photoresist.
Preferably, photoresist remover composition of the present invention further comprises water-miscible organic solvent and anticorrosive.
Preferably, described water-miscible organic solvent is for being selected from least a polar organic solvent of the group of being made up of dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP), dimethyl acetamide (DMAc), dimethyl formamide (DMF) and dimethyl-imidazolinone (DMI).
More specifically, described water-soluble polar organic solvent is preferably has at least 3.0, more preferably the solvent of at least 4.0 dipole moment.Dipole moment is measuring of solvent polarity.The dipole moment of polar organic solvent is big more, and photoresist remover composition of the present invention just has good more removal ability and dissolving power.Preferably, consider the possibility of evaporation, described water soluble polar solvent has 150 ℃ or higher, more preferably 180 ℃ or higher boiling point.
Preferably, the remover composition of every 100wt% comprises the described water soluble polar solvent of 12～60wt%.If the content of described water soluble polar solvent is lower than 12wt%, then dissolve the ability drop of hardened photoresist film.On the contrary, if its content surpasses 60wt%,, remove the modification photoresist film and will become difficult because the relative content of other component descends.
Preferably, use shown in the following general formula 1 have at least one hydroxyl based on the compound of phenol as anticorrosive:
Wherein, R
1, R
2, R
3And R
4Be hydrogen, hydroxyl, C independently of one another
1～C
12Alkyl or alkanol, and A is COOR
5(wherein, R
5Be hydrogen or C
1～C
12Alkyl), carboxyl, aldehyde, acid amides, hydrogen, hydroxyl, C
1～C
12Alkyl or alkanol.
More preferably, in general formula 1, A is COOR
5(wherein, R
5Be hydrogen or C
1～C
12Alkyl).The preferred embodiment based on the compound of phenol with at least one hydroxyl is catechol, pyrocatechol, methyl gallate, gallate, 3,4-dihydroxy-benzoic acid, guaiacol etc.
The polar functional group based in the phenyl ring of the compound of phenol with at least one hydroxyl faintly combines with metal or silicon, thereby prevents between photoresist remover solution and the metal directly electron exchange.Particularly, has larger molecular weight and be more effective than the compound of high polarity and compound with how such functional group.
Except preventing corrosion,, thereby help photoresist in remover solution, to dissolve based on the metal in the compound of phenol and the modification photoresist or halogen chelating formation coordination bond mutually.
Preferably, the remover composition of every 100wt% comprises the compound based on phenol of 0.4～10wt%.If the content based on the compound of phenol is lower than 0.4wt%, it can not fully prevent corrosion in comprising the photoresist remover of water and amine.On the contrary, if its content surpasses 10wt%, serious physisorption meeting causes removing the decline of the ability of modification photoresist.
Photoresist remover composition of the present invention can easily be removed the heat modification photoresist.In other words, photoresist remover composition of the present invention can be used for removing effectively the photoresist film in the semiconductor device fabrication processes process.More preferably, remover composition of the present invention can easily be removed the photoresist film that injects the metal byproducts institute modification that the photoresist film that hardened and the metal film below photoresist film etch by dry etching, ashing or ion at short notice, and the photoresist film by wet etch process.Remover composition of the present invention can make the corrosion of the metal line below the photoresist film minimize, and the side point that aluminium alloy the stood corrosion (side pitting) as Al, Al-Si, Al-Si-Cu etc. is minimized.In addition, when the modification photoresist was dissolved in the described solution fully, remover composition of the present invention can be eliminated the photoresist that residues in the remover solution problem of deposition again on substrate surface.
Therefore, remover composition of the present invention can be used for removing the photoresist that carries out wet method or dry etching institute's modification or sclerosis by the substrate of multiple to comprising (multiple) or single metal line and inoranic membrane.
Hereinafter, the present invention is described in more detail by embodiment.But following examples only are used for understanding of the present invention, and they should not be construed as limitation of the scope of the invention.Unless otherwise indicated, hereinafter given number percent and mixing ratio are all based on weight.
(embodiment 1～12 and Comparative Examples 1～3)
Following table 1 given composition and content prepares the photoresist remover composition.
[table 1]
| The photoresist remover composition | |||||||||
| Ammonium salt | Water | Organic solvent | Amine | Anticorrosive | |||||
| Compound | wt％ | wt％ | Compound | wt％ | Compound | wt％ | Compound | wt％ | |
| Embodiment 1 | NH 4NO 3 | 5 | 50 | DMSO | 30 | MEA | 13 | Pyro | 2 |
| Embodiment 2 | NH 4NO 3 | 1.5 | 50 | DMSO | 30 | MEA | 16.5 | Pyro | 2 |
| Embodiment 3 | NH 4NO 3 | 1.5 | 50 | HEP | 47.5 | Pyro | 2 | ||
| Embodiment 4 | NH 4NO 3 | 1.5 | 50 | DMSO | 30 | nMEA | 16.5 | Pyro | 2 |
| Embodiment 5 | NH 4NO 3 | 5 | 50 | DMSO | 30 | MEA | 13 | MG | 2 |
| Embodiment 6 | CH 3COONH 4 | 1.5 | 50 | DMSO | 30 | MEA | 16.5 | Pyro | 2 |
| The photoresist remover composition | |||||||||
| Ammonium salt | Water | Organic solvent | Amine | Anticorrosive | |||||
| Compound | wt％ | wt％ | Compound | wt％ | Compound | wt％ | Compound | wt％ | |
| Embodiment 7 | (NH 4) 2SO 4 | 1.5 | 50 | DMSO | 30 | MEA | 16.5 | Pyro | 2 |
| Embodiment 8 | (NH 4) 2CO 3 | 1.5 | 50 | DMSO | 30 | MEA | 16.5 | Pyro | 2 |
| Embodiment 9 | (NH 4) 2S | 1.5 | 50 | DMSO | 30 | MEA | 16.5 | Pyro | 2 |
| Embodiment 10 | NH 4SCN | 1.5 | 50 | DMSO | 30 | MEA | 16.5 | Pyro | 2 |
| Embodiment 11 | NH 4NO 3 | 1 | 50 | HEP | 49 | ||||
| Embodiment 12 | CH 3COONH 4 | 1 | 50 | HEP | 49 | ||||
| Comparative Examples 1 | NH 4NO 3 | 5 | 50 | DMSO | 43 | ||||
| Comparative Examples 2 | 20 | DMSO | 55 | MEA | 20 | Catechol | 5 | ||
| Comparative Examples 3 | HDA | 25 | 40 | MEA | 30 | Catechol | 5 | ||
(HEP: hydroxyethyl piperazine, Pyro: pyrocatechol, MG: methyl gallate, MEA: monoethanolamine, nMEA:n-methylethanolamine, HDA: hydramine)
The test example
Performance to the photoresist remover composition for preparing in embodiment and the Comparative Examples is carried out following test.
(1) corrosion of the removal of modification photoresist and metal film
The preparation of sample A
Will be as the aluminium of bottom film or aluminium alloy and the thickness that on 4 inches silicon chip, is deposited into 2000 and 200 as the titanium nitride of top-film respectively.On silicon chip general eurymeric photoresist (DPR-i900, it is U.S. willing that generation is advanced in east) being spin-coated to final film thickness is 1.2 μ m.Subsequently, test mask is placed on the photoresist film.Obtain figure by making sample exposure and using developing solution to develop.Then, sample is descended rigid bakings (hard baking) 100 seconds at 120 ℃.Use CHF3 gas not to be formed on titanium nitride film and the aluminium alloy film that the photoresist figure on the sample is covered with dry etching machine (RIE-80, Plasma Technology) etching.Subsequently, use oxygen gas plasma to remove most of photoresists with asher.
The preparation of sample B
Use PVD equipment, a kind of dielectric film tetraethoxysilane (being called TEOS hereinafter) is deposited into the thickness of 5000 on 4 inches silicon chip.On silicon chip general eurymeric photoresist (DPR-i900, it is U.S. willing that generation is advanced in east) being spin-coated to final film thickness is 1.2 μ m.Subsequently, test mask is placed on the photoresist film.Obtain figure by making sample exposure and using developing solution to develop.Then, sample is descended rigid bakings 100 seconds at 120 ℃.Use CHF
3Gas is not formed on the TEOS film that the photoresist figure on the sample is covered with dry etching machine (RIE-80, Plasma Technology) etching.Subsequently, use oxygen gas plasma to remove most of photoresists with asher.
The removal of＜modification photoresist 〉
Sample A and B were flooded 30 minutes in 40 ℃～70 ℃ photoresist remover composition in temperature range respectively.Subsequently, each sample is taken out from the photoresist remover composition,, and use nitrogen drying with the ultrapure water washing.Estimate the removal efficient of photoresist by the existence of photoetching xanthan polymer on the sidewall surfaces of determining bargraphs and via hole figure with scanning electron microscope (SEM).Show the result in the following table 2.
The corrosion of＜metal film 〉
Sample A was flooded 30 minutes in 40 ℃～70 ℃ photoresist remover composition in temperature range.Subsequently, this sample is taken out from the photoresist remover composition,, and use nitrogen drying with the ultrapure water washing.Corrosion with aluminium or aluminium alloy film on scanning electron microscope (SEM) observation bargraphs and the via hole figure.Show the result in the following table 3.
(2) without the removal of the heat modification photoresist film of ashing treatment
The preparation of sample C
On 4 inches silicon chip general eurymeric photoresist (DPR-i900, it is U.S. willing that generation is advanced in east) being spin-coated to final film thickness is 1.2 μ m.Subsequently, with photoresist film pre-baking 90 seconds on 100 ℃ heating plate.Then, test mask is placed on the photoresist film.Obtain the photoresist figure by sample being exposed to UV light and using developing solution to develop.Then, sample is descended rigid bakings 100 seconds at 120 ℃.Sample is descended rigid bakings 300 seconds at 170 ℃.
＜without the removal of the photoresist film of ashing treatment 〉
Sample C was flooded 5 minutes in 70 ℃ photoresist remover composition.Subsequently, this sample is taken out from the photoresist remover composition,, and use nitrogen drying with the ultrapure water washing.With the naked eye with the existence of microscopic examination photoresist film.Show the result in the following table 4.
[table 2]
The removal ability of photoresist remover composition
| The removal of modification photoresist | ||||||||
| Sample A | Sample B | |||||||
| 40℃ | 50℃ | 60℃ | 70℃ | 40℃ | 50℃ | 60℃ | 70℃ | |
| Embodiment 1 | ○ | ○ | ◎ | ◎ | △ | ○ | ○ | ◎ |
| Embodiment 2 | ○ | ○ | ◎ | ◎ | △ | ○ | ○ | ◎ |
| Embodiment 3 | ○ | ○ | ◎ | ◎ | △ | ○ | ○ | ◎ |
| Embodiment 4 | ○ | ○ | ◎ | ◎ | △ | ○ | ○ | ◎ |
| Embodiment 5 | ○ | ○ | ◎ | ◎ | △ | ○ | ○ | ◎ |
| Embodiment 6 | ○ | ○ | ◎ | ◎ | △ | ○ | ○ | ◎ |
| Embodiment 7 | ○ | ○ | ◎ | ◎ | △ | ○ | ○ | ◎ |
| Embodiment 8 | ○ | ○ | ◎ | ◎ | △ | ○ | ○ | ◎ |
| Embodiment 9 | ○ | ○ | ◎ | ◎ | △ | ○ | ○ | ◎ |
| The removal of modification photoresist | ||||||||
| Sample A | Sample B | |||||||
| Embodiment 10 | ○ | ○ | ◎ | ◎ | △ | ○ | ○ | ◎ |
| Embodiment 11 | ○ | ○ | ○ | ◎ | △ | ○ | ○ | ◎ |
| Embodiment 12 | ○ | ○ | ○ | ◎ | △ | ○ | ○ | ◎ |
| Comparative Examples 1 | × | × | × | △ | × | × | × | △ |
| Comparative Examples 2 | × | × | ◎ | ◎ | × | × | ○ | ◎ |
| Comparative Examples 3 | × | × | ◎ | ◎ | × | × | ○ | ◎ |
(*: removed at all, △: remove zero a little: most of removal, ◎: remove fully)
Just as shown in table 2, photoresist remover composition of the present invention (embodiment 1～12) not only can be at high temperature but also can under low temperature (40 ℃), remove by rigid baking, dry etching effectively, ion injects and ashing is hardened and the photoresist film of modification.
On the contrary, the removal efficient in Comparative Examples 1 is not good, and wherein the photoresist remover composition lacks water-soluble organic amine.But as can be seen, the ability of removing photoresist is not exclusively from water-soluble organic amine in Comparative Examples 2.Shown in Comparative Examples 2, water-miscible organic solvent plays a part less important to the removal efficient of photoresist remover composition, and ammonium salt plays a major role.
As can be seen, when the photoresist remover composition only comprised ammonium salt, the removal ability significantly descended in Comparative Examples 1.In other words, though be that the ammonium salt of ion does not cut much ice to the ability of removing photoresist at dissociation in water, when mixing with water-soluble amine, it has greatly improved this removal ability.This is because water-soluble amine helps ammonium salt to produce free radical.The ammonium and the hydroxyl of high oxidation in removal process, have also been found by the photoresist of hydramine modification.Similarly, when water-soluble organic amine joined in the ammonium salt, it can make ammonium salt produce ammonium and hydroxyl, thereby has obviously improved removal efficient.
[table 3]
| The corrosion of metal film | ||||
| Sample A | ||||
| 40℃ | 50℃ | 60℃ | 70℃ | |
| Embodiment 1 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 2 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 3 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 4 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 5 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 6 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 7 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 8 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 9 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 10 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 11 | ◎ | ◎ | ◎ | ◎ |
| Embodiment 12 | ◎ | ◎ | ◎ | ◎ |
| Comparative Examples 1 | ◎ | △ | × | × |
| Comparative Examples 2 | ◎ | ◎ | △ | △ |
| Comparative Examples 3 | ◎ | ◎ | △ | △ |
(*: corroded fully, △: partial corrosion, ◎: not corrosion at all)
The performance based on the compound of organic phenol with hydroxyl that is used as anticorrosive in photoresist remover composition of the present invention (embodiment 1～12) confirms in table 3.On the contrary, the photoresist remover composition (Comparative Examples 1) that does not comprise corrosion inhibitor demonstrates the heavy corrosion to metal film.And, though the photoresist remover composition of Comparative Examples 2 and 3 comprise have two hydroxyls based on the compound of organic phenol as anticorrosive, they all do not comprise ammonium salt separately or comprise the hydroxyl ammonium.As a result, compare with the photoresist remover composition of the present invention that comprises ammonium salt, water-soluble organic amine and the anticorrosive with two or three hydroxyls, they have relatively poor corrosion resistance.
[table 4]
Removal without the photoresist film of ashing treatment
| Sample C | |
| 70℃ | |
| Embodiment 1 | ◎ |
| Embodiment 2 | ◎ |
| Embodiment 3 | ◎ |
| Embodiment 4 | ◎ |
| Embodiment 5 | ◎ |
| Embodiment 6 | ◎ |
| Embodiment 7 | ◎ |
| Embodiment 8 | ◎ |
| Embodiment 9 | ◎ |
| Embodiment 10 | ◎ |
| Embodiment 11 | ◎ |
| Embodiment 12 | ◎ |
| Comparative Examples 1 | × |
| Comparative Examples 2 | ◎ |
| Comparative Examples 3 | ◎ |
(*: do not removed at all, △: part is removed, ◎: remove fully)
Just as shown in table 4, photoresist remover composition of the present invention (embodiment 1～12) can be removed effectively only through thermally-denatured photoresist, because they comprise water-soluble organic amine and organic solvent and ammonium salt.
On the contrary, the photoresist remover composition that only comprises the Comparative Examples 1 of ammonium salt and organic solvent demonstrates relatively poor removal efficient.Comparative Examples 2 and 3 photoresist remover composition demonstrate suitable removal efficient, because not less and therefore be easier to relatively remove through the photoresist film modification of ashing treatment.But as mentioned above, Comparative Examples 2 and 3 photoresist remover composition demonstrate relatively poor removal efficient to the photoresist film through ashing and the modification of dry etching institute.
Shown in above description, photoresist remover composition of the present invention is used in and removes photoresist in the semiconductor device fabrication processes.Particularly, it can effectively remove the photoresist film that is injected the metal byproducts institute modification that the photoresist film that hardened and the metal film below photoresist film etch by dry etching, ashing and ion at low temperature or in the following short time of high temperature.In addition, the burn into that can make the metal line below the photoresist film particularly side point corrosion minimizes, and can easily remove can not involved ammonium salt the heat modification photoresist removed of conventional remover composition.Therefore, photoresist remover composition of the present invention can substitute the conventional photoresist remover composition that comprises hydramine fully.
Though describe the present invention in detail with reference to preferred embodiment, it will be understood by those skilled in the art that the spirit and scope of the invention that do not depart from as described in the appended claims, can carry out multiple modification and replacement to it.
Claims (9)
1. photoresist remover composition, said composition comprises ammonium salt, water-soluble organic amine and water.
2. photoresist remover composition as claimed in claim 1, wherein, described ammonium salt be selected from the group formed by ammonium nitrate, ammonium formate, hartshorn salt, ammonium acetate, ammonium thiocyanate, ammonium sulfate, ammonium sulfide, ammonium oxalate and ATS (Ammonium thiosulphate) one of at least.
3. photoresist remover composition as claimed in claim 1, wherein, described water-soluble organic amine be selected from the group formed by monoethanolamine, isopropanolamine, amino ethoxy ethanol, n-methylethanolamine, dimethylethanolamine, diethyl ethanolamine, 2-aminoethylamino ethanol, aminoethylpiperazine, aminopropyl piperazine, hydroxyethyl piperazine, 1-amino-4-methyl piperazine, 2-methyl piperazine, 1-methyl piperazine, 1-benzyl diethylenediamine, 2-phenylpiperazine, 1-amino-ethyl piperidines, 1-amino piperidine and 1-amino methyl piperidines one of at least.
4. photoresist remover composition as claimed in claim 1, wherein, the described remover composition of every 100wt% comprises the described water-soluble organic amine of 7～50wt%.
5. photoresist remover composition as claimed in claim 1, wherein, described water is deionized water, and the described remover composition of every 100wt% comprises the described water of 5～80wt%.
6. photoresist remover composition as claimed in claim 1, wherein, the described remover composition of every 100wt% further comprises the water-miscible organic solvent of 12～60wt% and the anticorrosive of 0.4～10wt%.
7. photoresist remover composition as claimed in claim 6, wherein, described water-miscible organic solvent for be selected from the group formed by dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP), dimethyl acetamide (DMAc), dimethyl formamide (DMF) and dimethyl-imidazolinone (DMI) one of at least.
8. photoresist remover composition as claimed in claim 6, wherein, described anticorrosive is for being selected from by catechol, pyrocatechol, methyl gallate, gallate, 3, the group that 4-dihydroxy-benzoic acid and guaiacol are formed one of at least.
9. as any described photoresist remover composition in the claim 1～8, said composition is used to remove the photoresist that carries out wet etching or dry etching modification or sclerosis by to the substrate that comprises multiple or single metal line and inoranic membrane.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2005-0028541 | 2005-04-06 | ||
| KR1020050028541 | 2005-04-06 | ||
| KR1020050028541A KR101164959B1 (en) | 2005-04-06 | 2005-04-06 | Remover composition for photoresist of semiconductor device |
| PCT/KR2006/001241 WO2006107169A1 (en) | 2005-04-06 | 2006-04-04 | Remover composition for photoresist of semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101156111A true CN101156111A (en) | 2008-04-02 |
| CN101156111B CN101156111B (en) | 2011-04-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800111313A Active CN101156111B (en) | 2005-04-06 | 2006-04-04 | Remover composition for photoresist of semiconductor device |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR101164959B1 (en) |
| CN (1) | CN101156111B (en) |
| TW (1) | TWI342471B (en) |
| WO (1) | WO2006107169A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102221791A (en) * | 2011-04-29 | 2011-10-19 | 西安东旺精细化学有限公司 | Photoresist stripper composition |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010091045A2 (en) * | 2009-02-05 | 2010-08-12 | Advanced Technology Materials, Inc. | Non-fluoride containing composition for the removal of polymers and other organic material from a surface |
| BRPI1008034A2 (en) | 2009-02-25 | 2016-03-15 | Avantor Performance Mat Inc | semiconductor silicon disk ion implanted photoresist cleaning compositions |
| CN102617364B (en) * | 2012-03-15 | 2014-04-23 | 南京工业大学 | Hydroxymethyldiamine compound and its preparation method and application |
| KR101686175B1 (en) * | 2013-05-07 | 2016-12-13 | 주식회사 엘지화학 | Stripper composition for removing photoresist and stripping mthod of photoresist using the same |
| KR102023052B1 (en) * | 2014-03-26 | 2019-09-19 | 동우 화인켐 주식회사 | Resist stripper composition |
| KR20250034589A (en) | 2023-09-04 | 2025-03-11 | 주식회사 원익큐엔씨 | Cleaning composition for photo resist componets of parts for photolithography process and cleaning method of parts for photolithography process of semiconductor using the cleaning compostion |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08190205A (en) * | 1995-01-10 | 1996-07-23 | Mitsubishi Gas Chem Co Inc | Photoresist removing agent composition and removing method |
| US6432209B2 (en) * | 1998-03-03 | 2002-08-13 | Silicon Valley Chemlabs | Composition and method for removing resist and etching residues using hydroxylazmmonium carboxylates |
| US6440326B1 (en) | 1998-08-13 | 2002-08-27 | Mitsubishi Gas Chemical Company, Inc. | Photoresist removing composition |
| US6492308B1 (en) * | 1999-11-16 | 2002-12-10 | Esc, Inc. | Post chemical-mechanical planarization (CMP) cleaning composition |
| KR20010113396A (en) * | 2000-06-19 | 2001-12-28 | 주식회사 동진쎄미켐 | Photoresist remover composition comprising ammonium fluoride |
| KR100468714B1 (en) * | 2001-07-03 | 2005-01-29 | 삼성전자주식회사 | Resist removing composition and resist removing method using the same |
| WO2003038529A1 (en) * | 2001-11-02 | 2003-05-08 | Mitsubishi Gas Chemical Company, Inc. | Method for releasing resist |
| DE10331033B4 (en) * | 2002-07-12 | 2010-04-29 | Ekc Technology K.K. R&D Business Park Bldg. D-3F, Kawasaki | A manufacturing method of a semiconductor device and a cleaning composition therefor |
| US20040050406A1 (en) | 2002-07-17 | 2004-03-18 | Akshey Sehgal | Compositions and method for removing photoresist and/or resist residue at pressures ranging from ambient to supercritical |
-
2005
- 2005-04-06 KR KR1020050028541A patent/KR101164959B1/en not_active Expired - Lifetime
-
2006
- 2006-04-04 WO PCT/KR2006/001241 patent/WO2006107169A1/en active Application Filing
- 2006-04-04 CN CN2006800111313A patent/CN101156111B/en active Active
- 2006-04-06 TW TW095112212A patent/TWI342471B/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102221791A (en) * | 2011-04-29 | 2011-10-19 | 西安东旺精细化学有限公司 | Photoresist stripper composition |
| CN102221791B (en) * | 2011-04-29 | 2014-09-03 | 西安东旺精细化学有限公司 | Photoresist stripper composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101164959B1 (en) | 2012-07-12 |
| KR20060106110A (en) | 2006-10-12 |
| CN101156111B (en) | 2011-04-13 |
| WO2006107169A1 (en) | 2006-10-12 |
| TWI342471B (en) | 2011-05-21 |
| TW200700937A (en) | 2007-01-01 |
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