TW591347B - Resist remover composition - Google Patents

Abstract

The present invention relates to a resist remover composition for removing resists during manufacturing process of semiconductor devices such as integrated circuits, large size integrated circuits, very large size integrated circuits. The composition comprises (a) 10 to 40 wt% of a water-soluble organic amine compound, (b) 10 to 60 wt% of water-soluble organic solvents, and (c) 10 to 30 wt% water, (d) 0.1 to 10 wt% of organic phenol compound containing 2 or more hydroxy groups, and it is characterized in that the water-soluble polar organic solvent is 2-hydroxyisobutyric acid methylester (HBM). The composition can easily and quickly remove resist polymer cured by hard baking, dry etching, and/or ion implantation processes and those modified by metallic side-products etched from lower metal film materials during said processes, and it can also minimize the corrosion of lower metal wiring during a resist removal process.

Description

591347 A7 V. Description of the Invention (Field of the Invention The present invention relates to a photoresist composition of R0 t λ λ, which can be used in processes such as integrated circuit (1C), female creation + (please first Read the notes on the back and fill in this page) The original touch of the large-scale integrated circuit (LSI) process and the very large-scale integrated circuit (VLSI) process #j 丄 守 < Remove the photoresistor More specifically, the present invention relates to a photoresist composition which can easily and quickly remove hardened photoresist layers caused by dry etching, ashing, and ion implantation processes. It was introduced in recent years in the lithography process to reduce the size of components and increase the density of integrated circuits; the photoresist removing composition of the present invention can also remove by-products of the underlying metal in the above process at low temperatures. The photoresist layer is hardened, which reduces the over-etching of the underlying metal wires during the photoresist removal process. Background of the Invention: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Generally speaking, during the manufacturing process of semiconductor components, the lithography process is Repeat Dozens of times, the lithography process is to form a conductive layer pattern on the semiconductor substrate by etching and removing the conductive layer not covered by the photoresist pattern on the semiconductor substrate. After the patterning process of the conductive layer is completed, Photoresist remover to strip the photoresist pattern originally used as a photomask. However, in the ultra-large integrated circuit manufacturing process, a dry etching process is often used to form a conductive layer pattern, which makes it more and more difficult in the subsequent stripping process. Remove the photoresist. Unlike the wet etching using the liquid composition formed by the acid mixture, in the dry etching process, the etching process is performed in the gas phase. The solid phase reaction is the etching of plasma gas and a Thin material such as conductive layer Page 3 This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) 591347

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Because the dry etching process is easier to control and 1 A A W π has become the mainstream of the current etching process. However, the dry etching process will cause a complex chemical reaction between the ions and radicals in the plasma gas on the surface of the photoresist film to cause the photoresist to harden rapidly, making it difficult to remove the photoresist. Examples of dry etching include reactive ion etching (RIE), which makes it more difficult to repeatedly and practically remove these hardened photoresist layers with conventional photoresist removers. Another process that makes the photoresist layer difficult to remove is the ion implantation process. This process is to diffuse atoms such as phosphorus, arsenic, boron, and so on, to make a certain area of the wafer conductive during the semiconductor process. In this process, the ion system is implanted only into the area of the silicon wafer surface that is not covered by the photoresist pattern. At the same time, the area of the photoresist pattern surface as a photomask is also interposed between the surface and the accelerated ion beam. Modified by chemical reactions. Therefore, after the ion implantation process, these modified photoresist layers become difficult to remove with conventional photoresist removers. Once the photoresist layer modified by the above-mentioned dry etching process or ion implantation process cannot be removed by the conventional photoresist remover, even after the removal, the photoresist layer required for removing the photoresist is 100t or higher. The temperature and the long immersion time 'cause the yield of the semiconductor wafer to decrease, so this photoresist stripping process cannot be performed stably. So ‘manufacturers have rarely used phenol photoresist. At the same time, a recently developed M-resistor combination containing alkanolamine and diethylene glycol monoalkyl ether was developed, which can effectively remove most of the photoresist film, and has little taste and toxicity. Become the most widely used on page 4 of this paper standard Turnover Standard (CNS) A4 specification — x297 IIII I- I I- il · 1111111 ^ * — — — — — — — — # 14--i ( Please read the notes on the back before filling this page) 591347 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (Photoresist composition. However, it is known that the photoresist removal composition cannot sufficiently remove Photoresist layer exposed to plasma etching gas or ion beam during the etching process or ion implantation process. Therefore, there is an urgent need to develop a novel process for removing the photoresist layer modified by dry etching and ion implantation processes. Photoresist composition. As mentioned above, it is difficult to remove the photoresist layer that has been improved by the ion implantation process with a photoresist remover. In particular, it is difficult to implant an ion implantation process using a high radiation dose in an ultra-large volume. Source / Drain Formation in Circuit Process Improved photoresist layer removal in the polar region. During the ion implantation process, the surface of the photoresist layer is hardened by the heat of reaction between the high-energy ion beam and the high radiation dose. In addition, popping of resist ), Resulting in photoresist residues. Generally, semiconductor wafers that have been subjected to ashing are heated to a temperature of 200 C or higher. At this time, the solvent still remaining in the photoresist should be completely evaporated. However, the hardened layer produced by the photoresist surface after being irradiated with a high radiation dose cannot be completely evaporated. Therefore, as the ashing process proceeds, the pressure inside the photoresist layer will rise, resulting in the photoresist layer Cracked due to the residual solvent inside, this is called "popping." After the surface of the hardened layer is cracked, residues appear and are difficult to remove. In addition, the photoresist surface hardened layer is caused by heat, impurities, or impurities. Debris replaces the structure in the photoresist molecule, resulting in a cross-linking reaction, and the reaction area will be oxidized by the plasma. Therefore, this oxidized photoresist will become residue and contaminated particles, which reduces the super-large size. The yield rate of the body circuit. It has been proposed that all kinds of photoresist hardened layers that can effectively remove the above-mentioned page 5 11 JL I ιιΐ -------- ^ 0 — — — — — — — — + 111¾ Γ Please read the notes on the back before filling in this page} 591347 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () Dry or wet etching process, one of which is the two-stage gray disclosed in the literature Method, in which the second ashing is performed after the normal ashing procedure is performed (Fujimura, Spring Preliminary Collection of Japaness Spring Application Physical Society Announcement, IP-13, p5 74, 1989). However, these processes also have problems. In addition to the complicated processes, large-scale equipment is required and the yield is low. In addition, a photoresist composition containing an organic amine compound and various organic solvents has also been proposed for use in a conventional wet photoresist stripping process. Specifically, a photoresist composition containing monoethanolamine (MEA) as an organic amine compound has been widely used. For example, a photoresist composition comprising two components comprises &) organic compounds such as monoethanolamine (? ^ Eight), 2- (2-aminoethoxy) ethanol (eight ££), and the like Amine compounds, and b) such as N, N, -dimethylacetamide (DMAc), N, N'-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl Polar solvents (DMS0), carbon acetate, methoxyacetoxypropane (U.S. Patent No. 4,617,251), and the like; a polar photoresist composition comprising two compositions a) such as monoethanolamine (ME A), monopropanolamine, methylaminoethanol, and the like, and b) such as N-methylacetamide (Mac), n, n, dimethylacetamide (DMAc), Ν, Ν-dimethylformamide (DMF), smaller than diethylacetamide, N, N-diethylpropanamide, 叱 ... dimethylpropanamide, n, n • dimethyl Butylamine, N-methylethylpropylamine (US Patent No. 4,770,713), etc .; amidamine solvents; a photoresist composition comprising two compositions comprising a) such as Organic amine compounds such as monoethanolamine (MEA), etc. 6 pages I--IJ L- I IΙΊ --- — — — — — ^ --— — — — ——— I— ^ (Please read the notes on the back before filling this page) 591347 Economy A7 printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau V. Description of the Invention (Younger 4-124668), a photoresist composition containing a) l, 3-dimethyl-2-imidazolone (DMI), b) Dimethylarsine (DMS〇), and c) organic amine compounds such as monoethanolamine (Japanese Laid-Open Patent Publication No. 4_35〇66〇); a photoresist removing composition system comprising a) monoethanolamine, b) two Dimethylarsin (DMSO), and c) catechol (Japanese Laid-open Patent Publication No. 5_28i753); These photoresist removing compositions exhibit quite excellent properties in terms of safety, handling, and removal of photoresist. However, the recent popular semiconductor device manufacturing process is to heat several substrates, including silicon wafers, at a high temperature of about 11 (rc to 14 (rc), so the photoresist is often baked at high temperatures. However, The above photoresist remover is an example and is used to remove the photoresist formed by baking at high temperature. It has been suggested that a photoresist remover containing water and / or hydroxylamine is used as a composition for removing hard bake photoresist. For example , A photoresist composition containing fluorene hydroxylamine, b) alkanolamine, and C) water (Japanese Patent Laid-Open Publication No. 4_289866); a photoresist composition containing a) hydroxylamine, b) Alkanolamine, magic water, and d) anti-corrosive agent (Japanese Laid-open Patent Publication No. 6-266199), a photoresist composition comprising a) such as GBL (Y-butyrolactone), Nn_ Polar solvents (DMF), N, N, -Dimethylacetamide (DMAe), N-methylpyrrolidone (NMP) and other polar solvents, b) Amino alcohols such as methylaminoethanol, etc. , And c) water (Japanese Patent Publication No. ^ 6961 8);-a photoresist composition containing amino alcohols such as monoethanolamine (MEA) and the like Compound, b) water, and c) butanediol (Japanese Kaiping Publication No. 8-1 23043); a photoresist composition system comprising 1) k-alcohol amine, oxoamine, b) two Glycol mono-ether, c) Eight alcohol sugars, page 8 The inversion of private paper is applicable to China National Standard (CNS) A4 specifications (210 X 297 public meals _ one-installed -------- Order --------- I ^ ----- (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 591347 A7 -___ B7___ V. Description of Invention () d) quaternary ammonium hydroxide, and e) water (Japanese Laid-Open Patent Publication No. 8 262746); a photoresist composition system comprising a) monoethanolamine (mea) or / and 2- (2-amino Ethoxy) Alkanolamine compounds such as ethanol (AEE), b) hydroxylamine, c) diethylene glycol monoalkyl ether, d) sugar (sorbitol), and 6) water (Japanese Patent Laid-Open Publication No. No. 9-1 52721);-a photoresist composition comprising a) a hydroxylamine, b) water, c) an amine compound having an acid dissociation value (pKa) between 7.5 and 13, d) a water-soluble organic solvent , And e) Anti-corrosive agent (Japanese Laid-open Patent Publication No. 9-9691 1) and so on. However, it is known that the photoresist composition described above has the ability to remove the photoresist layer hardened by metal by-products due to dry etching, ashing, ion implantation process, and inscription of the lower metal layer in the process. It is not good, and its anti-corrosion ability of the lower metal wires in the photoresist removal process is not good. Therefore, it is urgent to develop a photoresist removing composition that can solve these problems. SUMMARY OF THE INVENTION One of the objectives of the present invention is to provide a photoresist removing composition which can easily and quickly remove the process caused by dry etching, ashing, ion implantation, and the process of etching the underlying metal layer during the process. Improved and hardened photoresist layer by metal by-products can minimize the corrosion of the underlying metal layer (especially copper wiring). In order to achieve this objective, the present invention provides a photoresist composition comprising at least a) 10-40% by weight of a water-soluble organic amine compound 'b) a polar organic solvent of 10-60% by weight, c) i0300% by weight Page 9 • III IV ϋ ϋ 1 · 1 ϋ ϋ ϋ ϋ ϋ II ^ 1 ϋ I ^ 1 · (Please read the notes on the back before filling this page) 591347 A7 B7 V. Invention Description () [Formula 2]

[Formula 3]

I ϋ ϋ —4 ϋ I 1L il · I ϋ II ϋ ϋ One δ * · III ϋ ϋ II a ^ i ϋ I (Please read the notes on the back before filling this page) Page 11 of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 591347 A7 B7 V. Description of the invention () [Formula 4]

(〇H) m3 (Please read the precautions on the back before filling this page) -------- Order ---- [Formula 5] Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

第 12 页 # This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 591347 A7 ______B7___ V. Description of the invention () In formulas 1 to 5, Ri , Can be the same or different, is a Cl 4 alkyl group or 〇ν4 alkoxy; r2, can be the same or different, is a hydrogen, (^ _4 alkynyl or Ch alkoxyl group, and 3 and R4 ' Can be the same or different, is a C _ 4 alkyl or Cw alkoxy; k is an integer between 1 and 3; called to m7 is an integer between 1 and 3; and ~ to, is a between An integer to 3. Preferably, 1 is a CV4 alkyl group, and r2 to r4 are Ci 4 alkyl groups; k and mi to m7 are 1; and η to n4 are 0 or 1. The photoresist removing agent of the present invention The composition can easily remove the deteriorated and hardened photoresist due to dry etching, ashing, and ion implantation processes in a short time, and remove by-products caused by etching the underlying metal at low temperature Photoresist polymer that deteriorates and hardens. Furthermore, the photoresist removing composition of the present invention has a lower metal connection during photoresist removal. The advantage of minimizing the corrosion situation, especially the bulging of the sidewall during the photoresist removal process, and the phenomenon of the photoresist dissolved in the photoresist to be deposited on the surface of the substrate to the minimum In addition, in the subsequent rinsing step, the rinsing can be carried out only with water, without using an organic solvent such as isopropyl alcohol or dimethylarsine. Brief description of the pass type: With the following detailed description and drawings The present invention can be fully understood. T. Figure 1 shows sample b-1 6 through a dry etching process and an ashing process that removes most of the resistance. The above dry etching process forms one and one lower metal wiring patterns and can As the hole of the electrical connection (1); Figure 2 shows the scanning type of electrical photoresist removal capability test,% D_micromirror photo page 13

This paper size applies to China National Standard (CNS) A4 specifications (210 X -------- L ---- -------- Order ----------- 1 (Please read first (Notes on the back then fill out this page) 591347

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, which is the result obtained by removing the photoresist composition at 5 (rc) in Example i 〇; and Figure 3 shows the photoresist removal ability test Scanning electron microscope photograph 'It is the result obtained by performing the photoresist removal of the photoresist removing composition of Comparative Example 7 at 50 ° C. Example: In the following detailed description,' only described and shown The best embodiment of the present invention. Therefore, the various possible improvements of the present invention should be regarded as still within the scope of the present invention. Therefore, the following description is only for the purpose of illustrating the invention, and the invention is not limited to this. In the photoresist removing composition of the invention, the water-soluble organic amine of a) is preferably an amino alcohol. For example, it is preferably selected from 2-amino- 丨 -ethanol, ^ amino-2-propanol, 2.amino_propanol, 3.amino-propanol, 2-amino-1 · butanol Among 4-amino-1-butanol and mixtures thereof, and considering its delustering resistance and cost from the viewpoint of industrial cost, it is preferable to select 2-amino-1-ethanol. The content of the water-soluble organic amine compound is preferably between 10 and 40% by weight, and more preferably between 20 and 30% by weight. Specifically, if the content of the organic amine compound is less than 10% by weight, it will be difficult to remove the photoresist polymer after the dry etching process and ashing treatment; and if the content exceeds 40% by weight, the underlying metal The wiring layer material will be excessively eroded. The water-soluble organic solvent of the photoresist removing composition (b) of the present invention is preferably the Chinese paper standard (CNS) A4 size (210 X 297 meals) on page 14 of this paper '' ------ 1 ί .-- install -------- order --------- stupid-(Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 591347 5 2. Description of the invention () 2-Hydroxyisobutyl methyl ester (HBM). In addition, it may further include a water-soluble polar organic solvent selected from dimethyl sulfoxide (DMSO), N · methylpyrrolidone (NMP), dimethylacetamide (DMAc), and dimethylformamide ( Dmf), dimethylimidazolone (DMI), fatty carboxylic acid esters, and mixtures thereof. The fatty carboxylic acid ester in the water-soluble polar organic solvent is preferably selected from the following groups, including β-methoxyisobutyric acid methyl ester (HBM), isoamyl 2-hydroxypropionate, and 2- # xylpropyl Butyl acid ester, ethyl 3-ethoxypropionate (εερ), methyl 3-methoxypropionate (MMP), ethyl 2-hydroxypropionate and mixtures thereof. Specifically, the water-soluble polar organic solvent preferably has a dipole moment of 3.0 · 3.0 or more, and more preferably has a dipole moment of 4.0 or 4.0 · 0 or more. A dipole moment represents the polarity of a solvent, the higher the value, the greater the polarity. The water-soluble polar organic solvent in Table 1 has a dipole moment of 3.0 or more, and the solvent having a dipole moment of 4.0 or more includes DMSO, NMP, DMI, and the like. b) The higher the dipole moment of the solvent, the better its ability to remove and dissolve the photoresist. As the water-soluble polar organic solvent of b), methyl 2-hydroxyisobutyrate (HBM) is preferred because it can be easily mixed with the water-soluble organic amine compound of a). The research results show that when the amino alcohol reacts with 2-hydroxyisobutyric acid methyl ester (hBm) to produce amines, the ability to strip the photoresist becomes different due to the reducing power of the residual amine. When fatty carboxylic acid esters react with amino alcohols to form amines, these amines have a higher reducing power than polar organic solvents such as DMSO, NMP, DMAc, DMF, and DMI and therefore have better stripping resistance. Ability. In particular, 'by-products such as ethanol due to HBM have the least by-products, so compared to other fatty carboxylic acid esters, it has the most page 15 --------- L Ί ^ ---- ---- ^ --------- (Please read the notes on the back before filling this page) 591347

V. Description of the invention (The ability of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs to print and remove photoresistance. In addition, (b) the water-soluble polar organic Rupan 3 yards / mixture preferably has a 150t: 150 ° C The above boiling point is preferably 180V ten n WC or 180 t: above. The water-soluble polar organic solvents / mixtures of Table 1 that meet this condition, because they have a high affinity for water, can exhibit the most transformation Gold, has a stable photoresist removal ability. In addition, it also has another advantage, that is, the photoresist deposited on the substrate can be deposited on the substrate with water instead of organic solvents after the photoresist removal process. The composition is rinsed clean. In addition, even if there is a small amount of polar organic solvent remaining, it does not seriously affect the semiconductor element because of its low corrosiveness to the conductive metal layer. Table 1 DMSO NMP dmi DMF DMA c Dipole moment 4.3 4.09 4.05 3.86 3.79 Boiling point 189 202 225 153 166 (° c) (b) The content of the water-soluble polar organic solvent is preferably between 106% by weight, more preferably between 25-50% by weight , Preferably between 25-45% by weight The research results confirm that as the dipole moment of the water-soluble organic solvent increases, the ability of the solvent to dissolve the photoresist on the photoresist composition also increases, and it has an excellent effect on the photoresist that has passed the aforementioned process but has not been modified. Solubility. If the content of this water-soluble polar organic solvent is less than 20% by weight, the solubility of the photoresist treated by a dry etching process such as etching or ion implantation process will be greatly reduced. Considering its composition with other components The water-soluble polarity on page 16 of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 male f) LL .-- Aw-M -------- Order-- -rtt first read the notes on the back before filling this page} # 591347 V. Description of the invention (The upper limit of the content of organic lotion is set to 50% by weight. Water in the photoresist removing composition (C) of the present invention, It is better to be ion-exchanged (please read the precautions on the back before filling in this page). Resin-purified water is better. Deionized water with resistance value of about 8MΩ. Less; Between -30% by weight, more preferably between 15-25% by weight If the water content is less than 10%, its ability to remove photoresist will be greatly reduced due to metal by-products generated after dry etching and ashing treatment. However, if the water content exceeds 30%, there is a reason to remove it. The fear of excessive corrosion of the underlying metal wiring during the photoresist process will reduce the amount of (a) water-soluble organic amine compounds and (b) water-soluble polar organic solvents, leading to reduced photoresistance. The research results confirm that the water ambiguity is preferably between 10-30% by weight. The organic phenol compound containing 2 or more hydroxyl groups in the photoresist removing composition (d) of the present invention is preferably selected from the group of compounds having the following formulae (5) to (5). [Formula 1] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Page 17 The paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 591347 A7 B7

:Oh

Fine iwriw · Ga, _ c

(〇H) m3 p.18 (mm, (β ^ \) η2 --------- 1 -1Ί Equipment -------- Order --------- si ( Please read the notes on the back before filling out this page) This paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 591347 Α7 Β7 V. Description of the invention () [Formula 4]. (H0) ni ( R])

j n3 (Ri) (〇H) ------ K ---- l · --install -------- order ----------- V (please read first (Notes on the back, please fill in this page) [Formula 5] Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

Page 19 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 591347 Printed by the Intellectual Property Bureau Employee Consumer Cooperatives of the Ministry of Economic Affairs A7 B7 V. Description of the invention () where 'Ri' can be the same or similar Di is a Cu-based or CV4 pit-based, R2 'can be the same or different, and is mono-, Cw, or C! · 4 alkoxy; R3 and R4 can be the same or different and are Cw alkyl or CV4 alkoxy; k is an integer ranging from 1 to 3; ^^ to m7 is an integer ranging from 1 to 3; and ~ to ^ is / an integer ranging from 0 to 3. More preferably, K is a Cw alkyl group, and r2 to r4 are a CV4 alkyl group; k and m7 are 1; and n4 is 0 or 1. Many studies have shown that compared to compounds containing less than two light groups (such as resorcinol, hydroquinone, and salicylaldehyde), it is known to contain 2 or more hydroxyl groups The organic phenol compound can significantly improve the photoresist removal ability. Examples of organic phenol compounds containing 2 or more hydroxyl groups include the following: such as 2,4'-methylenebisphenol, bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol AP, bis Phenol M, bisphenol P, 1,1'-bis (4-hydroxyphenyl) cyclopentane, 9,9, -bis (4-hydroxyphenyl) fluorine, 1,1, bis (5-methyl- Bisphenol compounds such as 2-hydroxyphenyl) methane, 3,5-dimethyl-4-hydroxybenzylphenol, 4,4'-hydroxyphenylbenzophenone, etc .; such as 1,1,1-tri (4 -Hydroxyphenyl) methane, ι, ι, ι_tris (4-hydroxyphenyl) ethane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl ) Methane, ι, ΐ-bis (3,5-methyl-4-hydroxyphenyl) -l- (2-hydroxyphenyl) methane, 2,6 · bis (5-methyl-2-hydroxybenzyl) Radical) -4 -methylphenol, 2,6-bis (3-methyl-4-hydroxybenzyl) -4 -methylphenol, 2,6-bis (3,5-dimethyl-4- Hydroxybenzyl) _ 4-methylbenzidine, triphenylene-TC and other triphenyl compounds; such as i, i, 2,2_ tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1 , 1,3,3_tetrakis (4-hydroxyphenyl) propene :): charge, 1,1,5 , 5-tetrakis (4- # to phenylphenyl) pentyl pits, α, α, α ', α'-tetrakis (4-quinylbenzene) page 20 This paper applies Chinese National Standard (CNS) A4 specifications ( 210 X 297 mm) IL I- L Ί --------Order ----— II-- (Please read the precautions on the back before filling this page) Preparation 591347 V. Description of the invention () yl) -3-xylene, α, α, α ', α, tetra (4-hydroxyphenyl) _4 xylene, α, α, α', α'-tetra (3_ Tetraphenol compounds such as hydroxy_4 · hydroxyphenyl) _3_xylene, ααα ,, α, _tetrakis (3-methyl-4-hydroxyphenyl) · 4-xylene, etc .; such as 2,3,4 -Trihydroxyphenyl ketone, 2,4,4, trihydroxyphenyl ketone, 2,3,4,4, tetrahydroxyphenyl ketone, 2,2,, 3,3,4_pentahydroxybenzene Hydroxyphenyl benzophenone compounds such as acetophenone, 2,2 ', 3,3', 4,4, and hexahydroxyphenyl benzophenone, 1- [1-methylhydroxyphenyl) ethylbenzene, bis_ (4-Hydroxyphenyl) ethyl] benzene, 2,6-bis (2, -hydroxy-5, -methylphenylethyl) _4-methyl-1-hydroxybenzene, and the like. d) < Organic phenol compounds containing 2 or more hydroxyl groups for the removal of hardened photoresist polymers due to dry etching, ashing, and ion implantation processes, and removal of etched underlying metals The photoresist polymer that is deteriorated and hardened by the by-products is very important; it can effectively absorb and bring the hydroxide ions generated by the reaction of water-soluble organic amine compounds with the hydrogen ions of water to the photoresist The contact surface between the layer and the semiconductor substrate. In addition, d) contains 2 or more organic benzene-based compounds which can prevent the lower metal layer from being corroded by hydroxide ions generated from the photoresist. In the photoresist composition of the present invention, the content of the organic phenol compound containing 2 or more hydroxyl groups in d) is preferably between 0 and 10% by weight, and more preferably between 0.5 and 5% by weight. between. If this compound; "The amount is less than 0.1% by weight, its ability to wipe out the photoresist layer at low temperature: It is severely damaged and reduced due to the gold ions produced by the dry etching and ion implantation processes, and at the same time, It will also severely rot and cause corrosion to the underlying metal. If the amount of winter exceeds 10% by weight, the operation of the dehumidifier composition will be turned into a fresh home (CNS) ) A4 secret X 297H " r I —cl I ---- I — i — — — — — — — — I IV II (Please read the precautions on the back before filling out this page) 591347 Employees of Intellectual Property Bureau of the Ministry of Economic Affairs Consumption A7 printed by the cooperative V. Description of the invention () It will rise and make the photoresist removal process uneconomical. Although the organic phenol compound containing 2 or more hydroxyl groups alone can help the photoresist removal combination of the present invention The anti-corrosive effect of materials, but it can not completely solve the pitting phenomenon, that is, the partial corrosion phenomenon of the upper surface of the underlying metal connection. The research results show that the triazole compound and 2 or more hydroxyl groups Organic phenol Compound mixing can suppress this bulging phenomenon. In particular, it is known to add one or two constituent triazole compounds (including at least benzotriazole (BT) and dibenzotriazole (ττ)) to 2 or more I groups. Among the organic benzene g compounds, it has an additive protective effect on preventing the corrosion phenomenon on the surface of the underlying metal layer or on the side wall thereof. The photoresist removing composition of the present invention may further include benzotriazine (By), Benzodiazole (ττ), carboxylated benzotriazole (CBT), and mixtures thereof. The triazole compound of the two systems preferably contains at least benzotriazole (Bτ) and dibenzotriazole (TT). The content of the compound in the photoresist removing composition of the present invention is preferably between 0.5-5% by weight. If the content is less than 05%, its effect of preventing partial corrosion will not be obvious, and if the content is not significant, Above 5%, the viscosity of the photoresist removing composition will increase, causing inconvenience in use. The photoresist removing composition of the present invention preferably contains a silicone-type surfactant of the following formula 6. Page 22 297 mm ) R ----- Awi ^ -------- ^ ---------— (Please read the note on the back first Please fill in this page again) 591347 A7 B7 V. Description of the invention () [Formula 6] ch3 ch3 (t ^ C ^ -SiO ^ Si (CH3) 3CH3 CH2CH2CH2O -z Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs where x is An integer from 0 to 10; y is an integer from 0 to 10; m is an integer from 0 to 10; η is an integer from 0 to 10; E0 represents an ethyleneoxy group; P0 represents A propyleneoxy group; and Z represents a prime atom or an alkyl group. The surfactant may be selected from compounds having sufficient solubility in water-soluble organic amine compounds, water-soluble polar organic solvents, and water. Studies have shown that it is known that the silicone surfactant represented by Formula 6 is a better choice for reducing surface tension and preventing photoresist redeposition. In addition, although the fluorine-based surfactants widely used in traditional photoresist compositions need only a small amount to show excellent surface activation effects, they cannot be used in the photoresist composition of the present invention because when When it is dissolved in water, impurities or impurities are generated, so its solubility in the composition of the present invention is low. However, the silicone surfactant represented by Formula 6 has a relatively high solubility in water, water-soluble organic amine compounds, and water-soluble polar organic solvents, and also exhibits excellent surface activation effects, which can be achieved without causing the above. In the case of the problem, the desired surface activation effect is achieved. At the same time, also on page 23 of this paper rule " ^ use • Jiasu --------- install -------- order --------- f (please read the back first Please pay attention to this page before filling in this page) ^ 1347 A7 B7 V. Description of the invention (excellent effect on preventing photoresist redeposition, different from traditional polyethylene glycol surfactants. Photoresist redeposition phenomenon is already The solid composition of the photoresist dissolved in the photoresist composition is deposited again on the surface of the substrate to become an irremovable residue. When a semiconductor substrate is used in a photoresist composition that has been used for a long time, Deposition is the main reason for poor photoresist removal. Surfactants can reduce the surface tension between the contact surface of the underlying metal such as aluminum, doped silicon, copper, titanium, and tungsten and the photoresist composition So that the photoresist removing composition can penetrate between the photoresist patterns of the conductive layer formed on the lower metal surface. Although the function of the surfactant is not obvious for the large lithographic pattern, only the volume of the lithographic pattern It is quite important that it is relatively small, and this directly affects the yield of semiconductor devices. The content of the surfactant is preferably between 0.001 and 1% by weight. If the content of the surfactant is less than 0.001%, it will not be able to remove the metal oxide on the side wall of the lithographic pattern and cannot achieve sufficient Surfactant activation effect. If the surfactant content is higher than 1%, it will reduce its effect of preventing redeposition of photoresist. Therefore, the content of the photoresist removing composition of the present invention is preferably between 0.001 and 1. % By weight. A method of using the photoresist composition of the present invention to remove the photoresist used as a photomask in the aforementioned photoetching process will be described in detail below. The photoresist composition of the present invention is removed from the surface of a substrate. A photoresist method includes contacting a substrate with a photoresist layer on its surface with the photoresist removing composition of the present invention in a conventional manner. The contact method may be by soaking the substrate on page 24 r ---- l · ^-^ -------- ^ --------- (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Consumer Cooperatives ^ 91347 ---------- Pull 、 Explanation of the invention () In the photoresist combination, the photoresist composition can be sprayed on the surface of the substrate in 7 φ S, medium or 疋. Other methods can also be used. In addition, the traditional photoresist composition is only Only when it is heated to a temperature of 80 ° C or above 80 ° C, will it exhibit sufficient photoresistance. However, the photoresist composition of the present invention can be seen at a relatively low temperature of 50 ° C to 50 ° C. The photoresist removal ability can be demonstrated below. Therefore, the photoresist composition of the present invention can reduce the photoresist dose and energy consumption rate which are volatilized (ie, consumed) during the photoresist removal process, and can also reduce Operator health problems due to volatilization of organic solvents. The present < photoresist removing composition can be applied to a photoresist of positive photoresist, negative photoresist, or both positive and negative use. For example, it can be applied to a positive photoresist composition comprising a novolac resin and a naphtoquinonediazide compound < a positive photoresist composition including a photoacid generator that generates an acid upon exposure to light, The solubility of the compound in the alkaline solution will increase after the compound is decomposed by the acid and alkali soluble resin; a positive photoresist composition containing a photoacid generator that generates an acid after being irradiated with light and an alkali soluble resin, wherein the alkali The solubility of the functional groups contained in the soluble resin after being decomposed by the acid will increase the solubility in the alkaline solution; and a photoacid generator containing a light < photoacid generator, a crosslinking agent, and an alkali soluble resin Negative photoresist; a positive photoresist composition comprising a benzoic acid varnish resin and a naphtoquinonediazide compound is particularly effective. The present invention will be described by the following examples, but the scope of the present invention is not limited to these examples. In addition, unless otherwise specified, the paper size on page 25 of this article applies to the Chinese National Standard (CNS) A4 (210 X 297 mm). Read the notes on the back and fill in this page) # Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau, 1347 Α7 '^ s ^ —----_ Β7 ____ 5. Description of the invention () The percentages and mixture ratios refer to weight ratio. In the examples and comparative examples of the present invention, the ability of the photoresist removing composition was evaluated in the following manner.

(1) Photoresist removal test 1 Prepare sample A on a 5-inch silicon wafer on which an aluminum layer has been deposited, and spin-coat a layer of a commonly used positive photoresist composition (IS40 1 produced by Mitsubishi) to make the final film thickness approximately It was 1.6 μm. After that, the silicon wafer was pre-baked for 90 seconds on a hot plate at a temperature of 100 ° (:). A mask having a predetermined pattern was placed on the photoresist layer, and after exposure, tetramethylammonium hydroxide ( TM ΑΗ) (DPD-100S produced by Dongjin Chemical Co., Ltd.) was developed at 21 ° C for 60 seconds. After that, the wafers with this photoresist pattern were respectively at a temperature of 140 ° C, 16 ° C (180 ° C and 180 ° C). Bake on a hot plate for 300 seconds and call them A-14, A-16, and A-18.

Prepare sample B. Use the photoresist pattern on sample A as a photomask, CF4 / 〇2 gas as the etching gas, and dry etching equipment (Applied Material's product model: P / 500). The patterned aluminum layer forms a metal wiring pattern. At this time, the process conditions are controlled so that the organic metal layer is not formed during the dry etching process. After that, only a part of the upper layer of the photoresist layer was prepared by ashing with h / N2 gas as the reactive gas in the ashing equipment (produced by Dongkyung Chemical Company, model: tCA-2400). Page 26 This paper applies Chinese national standards (CNS) ) A4 size (210 X 297 male ---- I.J --- install -------- order --------- (Please read the precautions on the back before filling this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 591347 5. The description of the invention (removed in the process. The samples thus produced are called 丨 4, b_ 丨 6, and B -1 8. The etching conditions for dry etching are as follows: [Dry etching conditions] Etching gas: CF4 / 02 mixed gas gas flow rate: 200 seem Pressure: 20 m torr RF source: 400 W Magnetic field: 140 Gauss Temperature: 20 ° C Etching time: 300 seconds [Ashing conditions] Reaction gas: 02 / N2 mixed gas = 950/50 seem Pressure: 5 mtorr Microwave power supply: 1 kw Wafer temperature: 200 ° C Ashing time: 120 seconds / wafer

Preparation of sample C: As + was doped on the front end of sample A by ion implantation, the irradiating agent 'was 1 × 10 16 ions / cm 2, and the acceleration energy was 80 KeV. Set the ion implantation angle to 0. So that the introduced ions are perpendicular to the side of the substrate. Move the sample to the downstream microwave ashing equipment (Dongkyung Chemical Co., Ltd. Model TCA-2400). Only part of the upper layer of the photoresist layer uses 〇2 / n2 gas as the reactive gas in the ashing process of the ashing equipment Was removed. Page 27 I ---- r I I L l · *---- 丨!丨 Order-! —! !! 4,! — (Please read the notes on the back before filling out this page) 591347 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention () The samples so produced are called C_14, C-16, and C_18. [Ashing conditions]

Reactive gas: o2 / n2 mixed gas = 95〇 / 5 () sccm Pressure: 5 mtorr Microwave power: 1 kw Wafer temperature: 200 ° C Ashing time: 120 seconds / wafer photoresist removal measurement, sample A, B, and C were immersed in 25 respectively. 〇 and 5〇c in the photoresist gas removing composition 3 > minutes. After that, remove the sample, rinse with 纟 Me, ^ dry with nitrogen, and evaluate its ability to remove photoresist according to the following criteria: An electron microscope was used to determine whether the photoresist polymer remaining on the hole side # was completely removed, and the results are shown in Tables 3 and 4. 〇〇: Residual photoresist remaining on the surface of the hole photoresist and the line photoresist has been removed. Completely removed. △ • Represents that more than 80% of the photoresist on the surface of the photoresist and the photoresist on the surface of the line photoresist have been removed. Only a small amount of residue has not been removed. The photoresist residue on the surface of the photoresist and the photoresist was not removed. (2) Preparation of sample D-19 for metal wire corrosion test. A 5 inch silicon wafer with a 10,000A aluminum layer was deposited on the surface by spin coating. Positive photoresist composition (I — i. — —-^ -------- — — — — — — 1 ^ .-- f by Mitsubishi Corporation Please read the precautions on the back before filling This page} Page 28

591347 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention () IS401), so that the final film thickness is about 6μηι. After that, the silicon wafer was pre-baked for 90 seconds at a temperature of 10 ° C on a hot plate. A mask having a predetermined pattern was placed on the photoresist layer, and 2.38% tetramethyl hydrogen was exposed after exposure. Ammonium oxide (TMAH) (DPD-100S produced by Dongjin Chemical Co., Ltd.) was developed at 21 ° C for 60 seconds. After that, the photoresist patterned wafer was hardened and baked on a hot plate at a temperature of 12 ° C for 300 seconds. The photoresist pattern thus formed was used as a photomask, CF4 / 02 gas was used as an etching gas, and dry etching equipment (Applied Material's product model: P / 500) was used to etch the bottom of the aluminum not covered by the photoresist pattern. Layer to form a metal wiring pattern. At this time, the process conditions are controlled so that the organometallic layer is not formed in the dry etching process. After that, only a part of the upper layer of the photoresist layer uses 02 gas as a reactive gas in the ashing equipment ( Dongkyung Chemical Co., Ltd., model: TCA-24〇) was removed in the ashing process. The samples thus produced were called 丨 2. Metal wire corrosion test immersed sample D-12 in 50. (: go to 10 minutes, 2 hours, and 24 hours in the photoresist composition. After that, the sample was taken out, rinsed with pure water, and then dried with nitrogen, and the degree of corrosion was evaluated according to the following criteria: The scanning electron microscope was used to determine whether the metal layer under the hole was over-etched. The results are shown in Table 5. 〇 · Represents no corrosion on the surface or side of the inscribed line. △: Corrosion on the surface or side of some aluminum lines. Page 29 ^ ^ -------- ^ ------- -^ C Please read the notes on the back before filling this page) 591347 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (X · It means that the entire aluminum wire has severe corrosion on the surface or side (3) Metal ion burst test (metai i〇I1 eruption test) 20 samples of D-12 were immersed in 2 kg of the photoresist composition, and the temperature was maintained at 5 (rc. After 12 hours, 24 hours, respectively). And 48 hours to sample the photoresist composition.

ETV (Electf. Thermal Vaporizer, ICP-MS instrument) (Inductively Coupled Plasma-Mass Spectroscopy, PERKIN-ELMER company, model: ELAN 6000) measured from the sample D-12 lower layer wiring pattern burst out The amount of aluminum ions is shown in ppb and is shown in Table 6. (4) Photoresist redeposition test 20 kg of the photoresist removing composition of Example 7 and Comparative Example 3 were subjected to the photoremoving resistance test, and the treated samples B _ 丨 4 and c -1 4 were processed at the same time. The number was increased from 1 to 100, 2000, 300, and 400, respectively, and the temperature was maintained at 50 ° C. During the test, the amount of photoresist deposited on the substrate was detected. When the number of treatments were 1, 100, 200, 30 () and 400, respectively, the substrate was sampled, washed with pure water, and then dried with nitrogen. After that, the number of micro photoresist residues deposited on the surface of the substrate again was measured with a surface detector (product of Japan Kasei Kogyo Co., Ltd., model: w IS-8 50). The results are shown in Table 7. Page 30 'Packing -------- Order ---------. (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 591347 A7 ____B7___ V. Description of the invention () Photoresist removing compositions of Examples 1 to 11 and Comparative Examples 1 to 7 Examples 1 to 11 and Comparative Examples 1 to 7, respectively, by mixing a) to d in Table 2 below ) Ingredients. The above (1) photoresist removal test, (2) metal wire corrosion test, (3) metal ion burst test, and (4) photoresist redeposition test are performed in the obtained photoresist composition, The results are shown in Tables 3-7 below. [Table 2] Classification of composition of photoresist composition Composition of photoresist composition (w / °) a) organic amine compound b) organic solvent c) water d) organic phenol compound (containing 2 or more Hydroxyl group) e) Hydroxylamine type Dosing form Dosing form Dosing Example 1 MIPA 15 NMP 45 32.0 Formula 7 8-Example 2 MIPA 17 DMF 50 29.5 Formula 8 3.5-Example 3 MIPA 25 HBM 49.5 23.0 Catechol 2.5-Example 4 MEA 21 NMP 47 30.0 Formula 9 2-Example 5 MEA 35 DMI 30 30.3 Formula 10 5-Example 6 MEA 30 NMP 50 18.0 Formula 11 2-Example 7 MEA 40 GGG 30 25.0 Catechol 5 -Example 8 MEA 40 HBM 30 26.0 Formula 12 4-Example 9 MEA 30 HBM 47 21.0 Catechol 2-Example 10 MEA 30 HBM + NMP 30+ 10 28.0 Catechol 2 Example 11 MEA 32 HBM + NMP 31+ 11 24.0 Catechol 2-Comparative Example 1 MEA 10 MFDG 22 48 20 Comparative Example 2 MEA 15 EC 30 30 _ 25 Comparative Example 3 MEA 3 DMAc 97 _ Comparative Example 4 AEE 70 MF 20 8 mC 2 Comparative Implementation Example 5 MEA 60 BC 35 5 Comparative Example 6 MEA 60 BC 30 10 " Comparative Example 7 ME A 40 EC 30 26 SA 4 MIPA: Monoisopropanolamine MEA: Monoethanolamine AEE: Aminoethoxyethanol Page 31 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) '- ----- install -------- order --------- X .--- * (Please read the precautions on the back before filling this page) 591347 A7 B7 V. Description of the invention () HBM: methyl 2-hydroxyisobutyrate DMF: dimethylformamide NMP: N-methylpyrrolidone DMI: dimethylimidazolone DMAc: dimethylacetamide MFDG: dipropylene glycol monoethyl ether EC: Diethylene glycol ether BC: Diethylene glycol butyl ether MF · Methylformamide PEG: Polyethylene glycol mC: Resorcinol SA: Printed by the Employees' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

0H page 32 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ----- 1 ----: l · · --installation -------- order- -------- + --- T (Please read the notes on the back before filling out this page) 591347 A7 B7 V. Description of the invention ([Formula 8]

[Formula 9]

0H

0H

0H i:!; I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

®. :: 11 ----- \ ----- L'—install -------- order --------- l · --L. (Please read the Note: Please fill in this page again.) Page 33 The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 591347 A7 _B7 V. Description of the invention () [Formula 10] Employees ’Intellectual Property Bureau, Ministry of Economic Affairs Printed by a cooperative

Page 34 (Please read the notes on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 591347 A7 B7 V. Description of the invention () [Form 12]

0H

0H H3C —C—CH3

0H (Please read the precautions on the back before filling in this page) Loading -------- Order ---- #

Jr. Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, page 35 This paper applies the Chinese National Standard (CNS) A4 (210 X 297 mm) 591347 A7B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs () [Table 3] Ability of removing photoresist composition at 25 ° C

Photoresist removal temperature 25 ° C Sample (hard baking temperature) A-14 A-16 A-18 B-14 B-16 B-18 C-14 C-16 C-18 Example 1 〇Δ 〇〇Δ Example 2 〇 △ △ 〇 〇〇〇〇 △ Example 3 00000 〇 〇 〇 Example 4 〇 △ △ △ 〇 〇 △ Example 5 〇 〇 〇 △ Δ Δ〇〇 Example 6 000000 Δ Δ Δ Δ Example 7 0000 Δ 〇 Δ 〇 〇 Example 8000 〇 〇 〇 Example 9 0000 〇 〇 〇 〇 〇 00 〇 Example 10 100,000 0000 Example 11 100,000 0000 Comparative Example 1 Δ XX Δ XX Δ XX Comparative Example 2 〇 Δ X 〇 Δ Δ 〇 Δ X Comparative implementation Example 3 △ XXXXXXXX Comparative Example 4 △ XXXXX Δ XX Comparative Example 5 〇Δ XXXXXXX Comparative Example 6 〇Δ X 〇XX Δ XX Comparative Example 7 XX Δ XX Δ Δ X Page 36 ^ ----- ,-Install -------- order ---- (Please read the notes on the back before filling this page) # This Zhang scale applicable Chinese National Standard (CNS) A4 size (210 X 297 mm) 591347 A7 B7 Ministry of Economy wisdom property office employees consumer cooperatives PRINTED

The paper standard bribery standard (CNS) A4 specification ⑵0 X V. Description of the invention () [Table 4] 50 C ability of photoresist composition to remove photoresist

Referring to Tables 3 and 4 ', it can be seen that the photoresist removing composition (Examples 1 to 11) of the present invention can effectively remove hard bake, dry etching process, ion implantation even at low temperature (25t, 50 °). The photoresist layer after curing and / or ashing treatment. Although the photoresist composition of the comparative example is relatively, it can effectively remove the dry etching process, ion implantation and / or even at low temperature. Or ashing photoresist layer (samples A · 14, A_16, A · 18), but with hard supply on page 37 of 297 mm) ^ 1 ϋ e ^ i ϋ ϋ 1 ϋ ϋ 1 I n II. 1 1 $, e I na— ϋ ϋ I ϋ i ^ > Jr (please read the precautions on the back before filling this page) 591347 A7 V. Description of the invention () The increase in baking temperature, and its ability to remove photoresistance With the decline, and

The ability of photoresist layers (HB-14 to C-18) caused by dry etching process, ion implantation and / or ashing process also decreases. 'W Examining Tables 3 and 4 in detail, it can be found that the photoresist removing composition of Comparative Example 3, which does not include the organic benzene test compound and water containing 2 or more light groups, removes the hardened photoresist layer or Modified hardened photoresist layer = worst performance. In addition, the composition of Comparative Example 4 which contained water and a relatively excessive amount of a water-soluble organic amine compound had a poor ability to remove a hardened photoresist layer or a modified hardened photoresist layer. It can be seen that the composition of the comparative example that does not include an organic phenol compound containing 2 or more hydroxyl groups, or the composition of the comparative example that includes an organic phenol compound containing 1 hydroxyl group, which removes hardening light The ability of the resist layer or the modified hardened photoresist layer is not good. From Tables 3 and 4, it can be confirmed that the most influential component for removing the hardened photoresist layer or the modified hardened photoresist layer is an organic phenol compound containing 2 or more hydroxyl groups. The results of Examples 3, 8 and 9 of organic polar solvents, and Examples 10 and 11 containing ΗBM + NMρ were confirmed, and they exhibited superior photoresistance than compositions containing other organic solvents. P.38 The paper size timely standard (CNS) A4 specification ⑵Q χ 297 male. — ^ -------- ^ --------- (Please read the precautions on the back before (Fill in this page) 1. · Bucket / V. Description of the invention ([Table 5] Metal Wire Corrosion Test Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-Photoresist Remover 亘----------实施 实施 实施 实施 实施Example 1 zzzz © 2 H3 ~ · 3 4 ~~~ 5 ~~ ^ 6 ~~ ~~ 7 IZZΓ 9 — 10 11 than ¥ real ~ " i Example ~~ 2 ~ 3 ~~ 4 ~~ ZZZ — 6 ~~ 7 t = fc = 3 24 hours-mutual 5 Δ XA ~ x ~ x ~ Y ~ χ v—Μ -------- Order ---- (Please read the notes on the back before filling This page) Refer to Table 5 'It is known that the anti-corrosive effect contained in the W remover of the present invention contains ... two substances (Example 1 · Phenol compounds hardly corrode the underlying gold', check the pattern, Until more than 2 hours after immersion; and 3, 8 and 9 using HBM as the organic polar solvent, and 10 and η using HBM + NMP as the organic polar solvent, the soaking time is 2 hours or The metal connection pattern of the spoiled layer will not be left for more than 2 hours. However, In Comparative Example 丨 _7, the corrosion phenomenon began to occur after soaking for only 10 minutes, and the underlying metal wiring pattern was severely corroded after 2 hours. Therefore, if the comparative implementation is used, page 39 of this paper applies to China National Standard (CNS) A4 Specification (210 X 297 mm) # 591347

7 7 A B Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention () The composition may be used to perform the photoresist removal process. The possible concern is that it will cut the metal wiring pattern of the semiconductor components, resulting in a decrease in yield. The delustering agent composition of the present invention can effectively reduce this problem. After examining Table 5 in more detail, it can be seen that the compositions of Comparative Examples 3, 5, and 7 excluding organic phenol compounds containing 2 or more hydroxyl groups will seriously corrode the upper surface of the underlying metal wiring pattern and Side, so that the width of the pattern is seriously affected. In addition, the amount of water contained in the comparative example 1 which has an anticorrosive effect is relatively high, and the underlying metal wiring pattern is severely corroded. [Table 6] Metal ion (expressed in ppb) burst test de-resist temperature 50 ° C immersion time 0 hours 12 hours 24 hours 48 hours Example 1 1 3 19 35 2 1 3 17 36 3 1 2 13 29 4 2 3 19 37 5 1 4 21 41 6 1 3 16 32 7 2 3 15 34 8 1 5 14 31 9 1 1 15 30 10 1 3 13 30 11 1 2 12 29 Comparative Example 1 1 35 69 145 2 1 19 42 210 3 2 24 39 109 4 1 25 45 167 5 1 42 63 231 6 2 28 45 114 7 2 31 48 121 page 40 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) .- -Install -------- Order --------- · (Please read the precautions on the back before filling this page) 591347 A7 V. Description of the invention (refer to Table 6, we can see that the present invention ^ The pre-resistor composition (Example 1-U) hardly releases aluminum ions, and it shows that it hardly corrodes the underlying metal wiring pattern after 12 hours of dark exposure for a hour. Contrast 1 Comparative Example 1 -7 The palpitant Example 1-7 The amount of ions released in Example 1-7 is about 10 times the average release amount of the example after 2 hours, which is not as serious as that of the comparative example. Connect These results are due to the corrosiveness of Example 1 and 1 and / or Wu, where Example 1 to 1 1 contains anti-corrosive corrosion effect < d) contains 2 or more Organic phenol compound with a hydroxyl group, and therefore the comparative example does not contain this component. 0 Refer to Table 7 'for the number of processed photoresistive particles 100 i 10 " and the number of photoresistive residual particles in Comparative Example 3. Approximately 10 times that of Example 10. As described above, the photoresist removing composition of the present invention can easily remove the photoresist polymer that has been deteriorated and hardened due to dry etching, ashing, and ion implantation processes in a short time °, and the underlying metal due to etching Degraded, hardened photoresist that is changed by industry by-products. Furthermore, the photoresist removing composition of the present invention has the advantages of reducing the underlying metal connection, especially the bulging corrosion of the side wall to a minimum, and preventing the photoresist from being removed again # P. 41 This paper ruler is applicable China National Standard (CNS) A4 specification (210 X 297) 591347 A7 B7 5. Description of the invention () Advantages of depositing on the surface of the substrate; and in the subsequent washing step, it can be washed with water only. There is no need to rinse with organic solvents such as isopropyl alcohol or dimethyl sulfoxide. Although the present invention has been described with specific embodiments, those skilled in the art will understand that other improvements can be substituted for the present invention without departing from the scope of the present invention, and these improvements are also included in the scope of the present invention. ---- l · --- install -------- order --------- ^ 9 (Please read the precautions on the back before filling out this page) Staff Consumption of Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative page 42 This paper is sized for China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

§1591347 Printed and patented by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs • A photoresist composition that contains at least a) 10-40% by weight of a water-soluble organic amine compound; b) 10-60% by weight Percent water-soluble polar organic solvent, which contains at least 2-hydroxyisobutyrate methyl alcohol (HBM); c) 10-30% by weight of water; and d) 0.1-10% by weight containing 2 or Organic phenolic compounds with multiple hydroxyl groups. 2. The photoresist removing composition according to item 1 of the scope of the patent application, wherein the water-soluble organic amine compound is an amino alcohol compound. 3. The photoresist removing composition according to item 2 of the scope of the patent application, wherein the amino alcohol compound is selected from the group consisting of 2-amino-1-ethanol, 1-amino-2-propanol, and 2-amino-1- Propanol, 3-amino-1-propanol, 2-amino-1-butanol, 4-aminobutanol, and mixtures thereof. 4. The photoresist removing composition according to item 1 of the scope of the patent application, wherein the water-soluble polar organic solvent of b) further comprises a solvent selected from the following groups, including: dimethyl sulfoxide (DMSO), N- Methylpyridinone (NMP), N, N'-dimethylacetamide (DMAc), N, N'-dimethylformamide (DMF), dimethylimidazoledione (DMI), Fatty carboxylic acid esters and mixtures thereof. 5 · The photoresist removing composition described in item 4 of the scope of the patent application, wherein the fatty carboxylic acid ester is selected from the following groups, including ... CNS) A4 specification (210 X 297 mm): «Μ IIJ ^ ------- Im — (Please read the notes on the back before filling in this page) 591347 A8 B8. C8 D8 6. Apply for a patent Range of methyl isobutyrate (MBM), isoamyl 2-hydroxypropionate, butyl 2-hydroxypropionate, ethyl 3-ethoxypropionate (EEP), ethyl 3-methoxypropionate (MMP) , Ethyl 2-hydroxypropionate, butyl 2-hydroxypropionate and mixtures thereof 0 .. IIMIIJ1— ---- 1III ^-— — — — 111 — IJ (please read the notes on the back before filling in (This page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, 44W This paper size applies to China's National Standard (CNS) A4 specification (210 X 297 mm)