TW201204828A - Photoresist stripper composition - Google Patents

Abstract

A photoresist stripper composition comprising 0.5 to 5 % by weight of alkyl ammonium hydroxide; 60 to 90 % by weight of aprotic polar solvent; 0.1 to 3 % by weight of aromatic polyhydric alcohol; 0.1 to 5 % by weight of linear polyhydric alcohol; and 5 to 30 % by weight of water has an excellent capacity for stripping a positive and a negative photoresists, and dose not corrode a metal wiring under the photoresist.

Description

201204828 VI. Description of the Invention: [Technical Field] The present invention relates to a method for manufacturing a semiconductor, a device, or a device for removing a photoresist. The photoresist stripper composition. C Previous J Background Art / Take, a 峪 峪 导体 导体 conductor, LED or LCD device is produced through a series of micro-shirt methods. The lithography method comprises the steps of: forming a genus layer or an insulating layer on the substrate; exposing the photoresist to the layer of gold > 1 layer; The mask is selectively exposed to form a desired light. In this method, the pattern of the metal layer or the insulating layer is after the core material is removed, and the photoresist pattern is removed by a lift-off method. ▲Heat::According agent: According to the solubility and the change of the developer during exposure, the photoresist becomes a photoresist which is soluble in the developer. Exposure of the ray of light _ becomes soluble in the developer, can be: 岐 岐 岐 f f f 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 剥离 难以 难以 难以 难以 难以 难以 难以 难以 难以 难以 难以 难以 难以The ease and yield is better - is two =: the result of the gas-solid reaction between the formation of 1_ (4) 电 plasma gas and the material layer such as conductive layer 201204828, plasma gas ions and free radicals and light The resist reaction' thus hardens and denatures the photoresist. Furthermore, ion implantation in a method of fabricating a semiconductor, LED or LCD device is a method of causing a blending atom such as P, As, B, etc. to enter a desired region of a germanium wafer to produce a conductivity, thus The type of photoresist is denatured by chemical reaction with the plasma. At the same time, a negative photoresist is used for the throwing method. The exposed portion of the negative photoresist is rendered insoluble by cross-linking, therefore, it cannot be completely removed using a general solvent' and the cleaning method needs to be carried out under severe conditions, such as a south temperature of more than 1 〇〇c. And long dipping time. Various aqueous strippers have been proposed to remove a hardened and denatured photoresist during dry etching or ion implantation. For example, a composition comprising a hydroxylamine, a hospital amine, and a water stripper has been reported (Japanese Patent Publication No. 1992-289866); comprising a hydroxylamine, an alkanolamine, water, and a rot # inhibitor One of the release agent compositions (Japanese Patent Publication No. 1994_266119); containing a polar solvent (such as butyrolactone, dimethylformamide, dimethylacetamide, hydrazine-methylpyrrolidone, etc.), an amine a base alcohol (such as 2-methylaminoethanol) and a water-release agent composition (Japanese Patent Publication No. 1995 69618); comprising an alcohol amine (such as monoethanolamine/aminoethoxyethanol), a hydroxyl group a stripping agent composition of an amine, a diethylene glycol monoalkyl ether, a saccharide (sorbitol) and water (Japanese Patent Publication No. 1997-152721); and comprising a hydroxylamine, water, having a pKa of 7.5~ An amine of 13, an organic solvent which is soluble in water, and a release agent composition which is one of corrosion inhibitors (Japanese Patent Publication No. 997_969丨i). However, such compositions do not have sufficient ability to strip negative photoresists, even if they are useful for stripping crosslinked or denatured positive photoresists. 4 201204828 Acid strippers or alkaline strippers have traditionally been used to remove negative light. The inclusion of an alkylbenzene sulfonate, a phenol compound, a gasification solvent, and a flavonoid-degradable-representative read release agent, but the ability of the negative-type light is not sufficient. Further, a peeling agent containing a water-soluble organic amine and an organic solvent not only has a poor ability to peel off a negative photoresist, but also has a metal corrosion. In order to solve this problem, a composition containing ruthenium, a polar organic solvent, an alkali compound, and water is proposed in Korean Patent No. 718527. As a result, although this compound has a good ability to peel off a negative photoresist, the corrosion of the metal wiring under the photoresist is not sufficient. Recently, as methods for fabricating semiconductor, LED or LCD devices have become more sophisticated and complex, such methods use positive and negative photoresists. Therefore, without a common stripper for positive and negative photoresists, individual strippers and processing equipment would be required, resulting in increased manufacturing costs and time. Therefore, there is a need for a stripper composition which is capable of efficiently removing positive and negative photoresists without causing corrosion of the metal wiring under the layers. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a release agent composition which has excellent ability to peel off a positive photoresist and a negative photoresist without corroding a light. One of the metal wiring under the barrier layer. According to one aspect of the invention, there is provided a photoresist stripper composition comprising 0.5 to 5% by weight of one alkylammonium hydroxide; 60 to 90% by weight of an aprotic polar solvent; 〇·1 to 3% by weight One of aromatic polyhydric alcohols; 〇1 201204828 to 5% by weight of one linear polyhydric alcohol; and 5 to 30% by weight of water. The photoresist stripper composition according to the present invention has excellent peeling ability to harden and denature a positive-type photoresist by a dry etching or ion implantation method and a negative photoresist for a throwing method And it does not corrode one of the metal wirings under a photoresist layer in the stripping method and the ultrapure water rinsing method. C Embodiment 3 The alkyl ammonium hydroxide used in the composition of the present invention, which is exemplified in the best mode of the present invention, comprises tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and a mixture of such. Due to the cross-linking therein, the positive photoresist which is hardened and denatured by a dry etch, touch or ion implantation method, and the negative photoresist which is crosslinked during an exposure method are not soluble in one Solvent. Therefore, it is preferred to change the content of the crosslinked photoresist to the soluble C-alkylammonium hydroxide by using a base component for cutting the crosslinked base component in an amount of preferably 0.5 to 5% by weight. If the content of the alkylammonium hydroxide is less than 0.5% by weight, the efficiency of removing the photoresist becomes lower because it is difficult to cut the denatured and crosslinked polymer chain; and if it exceeds 5% by weight, the aproticity The relative content of the polar solvent is reduced, thereby reducing the solubility of the photoresist and increasing the corrosion of the underlying metal film. The aprotic polar solvent of the composition of the present invention may be N,N-dimercaptodecylamine, hydrazine, fluorenyl-dimercaptoacetamide, hydrazine, Ν'-diethylacetamide, dimercapto Sulfone, hydrazine-methylformamide, hydrazine, hydrazine-dihydrazinyl decylamine, hydrazine-hydrazinopyrrolidone, 7-butyrolactone, propylene carbonate, 1,3-dimethyl-2-imidazolidine Ketone, and a mixture of 6 201204828. The aprotic polar solvent may be present in an amount of from 60 to 9% by weight. If the content of the aprotic polar solvent is less than the amount of the teacher, 'the solubility of the sister is less; and if it exceeds 90% by weight, the relative content of the water is reduced, thereby reducing the activity of the alkylammonium hydroxide and reducing the peeling or denaturation or The ability of Lianzhi plastic and negative photoresist. The water content in the composition is preferably in the range of from 5 to 3 % by weight. If the water content is less than 5% by weight, the degree of dissociation of the base hydrogen hydroxide becomes lower, resulting in the ability to reduce the stripping of the denatured or crosslinked positive and bismuth type resist. 1 water contains more than 30% by weight, burning The base of the hydrogen hydroxide in the live eight ah is thus caused by the right; the underlying metal film is insufficient to suppress the surname. The aromatic polyhydric alcohol and the main component of the composition of the present invention, the polyhydric alcohol acts as a corrosion inhibitor. The content of the aromatic polyhydric alcohol may be 0% by weight of the content of less than CU% by weight. The metal of the bottom layer is two::::: Manufactured: r The content of the linear polyhydric alcohol may be less than the content of the 01 to 5 heavy alcohol. 〇]% by weight, for the metal of the bottom layer: the dihydroxyl group has a reduced ability; and if it exceeds 5% by weight, the residual, etch inhibiting method causes defects. The rot recipe itself is in its silk group. If the amount of the radical group is less than 3, the adsorption resistance becomes lower, and the 201204828 red oxime light light inhibitor preferably has at least a base vine group. If the base group or the base group is burned, the base group or the so-called "Yuan Erli" is reduced in 1', which may cause insufficient corrosion inhibition ability. Examples of the pentane-based alcohol include gallic acid, gallic acid, etc., gallic acid propyl vinegar, gallic acid butyl vinegar, and the likes thereof, and examples of linear polyhydric alcohols are propylene sorbitol, mannitol , xylitol, and the like of the present invention, because of the synergistic effect obtained by using an aromatic polyhydric alcohol in combination: =, the alcohol of the present invention. For (10), reading money is superior to the inhibitory effect. For example, the test compound 'increased:' and the test compound was added to the -_agent composition to erode the inhibitor. Under the condition of πρ, the aromatic polyhydric alcohol and #腐腐余 inhibiting ability. Eosin exhibits a better surface: t-suppression is achieved by adsorbing a sulphide to the metal. During the adsorption, the performance of the four sub-layer preparations which are inhibited from being attached to the metal surface depends on the strength of the metal surface and the adhesion capacity and the molecular layer density, and the performance of the P-capacity in the adsorption knife and the molecular growth It becomes higher as the density increases. The aromatic polyhydric alcohol alcohol inhibitor forms a one-turn structure of a benzene ring, and at the same time dissociates the hydrogen atom from the group via the base group. Therefore, the ruthenium is adsorbed to the metal. The linear polyhydric alcohol residue inhibitor does not form a resonance structure, even if the hydrogen atom in the base ruthenium is dissociated, since 8 201204828 lib 5 ρ» alcohol ~: = Γ metal. Therefore, the linearity of the area and the attached area have an adsorption to "鸩 :: which has a low adsorption force. Because of the advantages of the two parts in the stripping agent, the metal surface (surface migration) tends to be larger, and the adsorption of the light inhibitor is increased to the inhibition increase, resulting in a higher brain inhibition = force on the surface of the brain -, ==:=:, (10) The structural preparations can be strongly adsorbed to the metal due to the corrosive inhibition of the aromatic polyhydric alcohol due to the 7-shaped eight-vibration and the structure. The temple has a low-density, metal surface due to the wrapable structure. Sword layer. Linear poly-methanol, but not strong in its flexible chain structure, has a high-density molecular layer, attached to the metal: (d) on a metal surface, because this structure can not be strongly absorbed to achieve excellent corrosion (10) System, - metal surface county W money suppression coffee (four) strongly adsorbed to the aromatic polyhydric alcohol t, the density of the genus layer needs to be higher. Because aromatic more _ can not be used by the combination of linear polyhydroxy - preferred rot The metal layer provides the ability to be a dianthic photoresist. Conversely, the corrosion is suppressed and only: When the alcohol is used alone, the ability to strip the photoresist cannot be obtained when it is excellent. Make it alone. The stagnation of the chain inhibitor to obtain the relative content of the polar solvent, "the ability of the human rice to inhibit rice, the ability to dissolve the photoresist, or the use of the composition to reduce the solubility of the stripper composition with low solubility" Inhibitor in composition 201204828 The composition of the present invention may further contain a diol and a triazole according to a desired purpose, as long as the effect of the present invention is not degraded. Suitable diols include, without limitation, gans Alcohol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, dipropylene glycol decyl ether, hexanediol, polyethylene glycol having a weight average molecular weight ranging from 100 to 400, and the like The triazole includes, without limitation, benzotriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole, dihydroxypropylbenzotriazole, etc. As described above, according to the present The photoresist stripper composition of the invention has excellent ability to harden and denature one of the positive photoresists and one of the negative photoresists used in the throwing method by dry etching or ion implantation, and Peeling method and an ultra-pure water rinsing method will not corrode One of the metal wirings under a photoresist layer. In particular, due to the synergistic effect produced by the aromatic polyhydric alcohol corrosion inhibitor and the linear polyhydric alcohol corrosion inhibitor, an excellent corrosion inhibition effect can be only a small amount. The corrosion inhibitor is obtained without reducing the ability to strip the photoresist. EXAMPLES Hereinafter, the following examples are intended to further illustrate the invention without limiting its scope. Examples 1 to 9 and Comparative Example 1 to 21 The compositions of Examples 1 to 9 and Comparative Examples 1 to 21 were prepared by mixing the components shown in Table 1. The mixing was carried out at room temperature for 1 hour or longer to fully dissolve solid corrosion. The inhibitor was then filtered through a Teflon filter. Experimental Example 10 201204828 The compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 21 were evaluated for the ability to separate and inhibit the mash resistance as follows: (1) Preparing a positive photoresist sample - a positive photoresist (THMR-iP 33, TOK) is applied to a tantalum nitride coated silicon wafer, and thereafter formed by exposure and development methods a photoresist pattern. The pattern is dry etched Move to the tantalum nitride layer under the photoresist to obtain a positive photoresist sample. (2) Prepare a negative photoresist sample TOK) coated on a Shishi Xishi-negative photoresist (PMER N-HC600, On the circle, thereafter, by exposure, development and baking methods - the photoresist pattern aluminum and titanium are sequentially spread on the germanium wafer to obtain a thrown negative resist pattern test example 1 · peeling ability evaluation test composition The material was maintained at 60t:, and the positive resistive and negative resist samples were immersed in the bath for 20 minutes, rinsed with deionized water for 3 sec seconds, and then dried with nitrogen to dry the residual photoresist in the sample. Optical magnification: X200) and one FE-SEM (magnification: xl〇〇〇, drink ~x50, 〇〇〇). Test sample 2. Corrosion inhibition ability evaluation test composition was maintained at 6 (TC, and If the negative cut is like this, the sample of the shell 1 is blocked for 90 minutes. The formed sample was rinsed with deionized water for 3 hours and then dried for 10 seconds. The surface of the dried sample and the loading surface are attached to an FE-SEM (magnification: xl〇, 〇〇〇~x5〇()(), inspection. Yushibu, . The 20-minute ratio is more severe than the general peeling condition, and the difference in the hybridity is found in the formula 5. 1 Μ Condition for 11 201204828 Evaluation of corrosion inhibition ability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 0 < XXX < X ◎ ◎ 〇 〇 ◎ 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ < 〇 composition (% by weight) 10.0 10.0 15.0 15.0 20.0 20.0 15.0 20.0 20.0 12.0 17.0 22.0 10.0 15.0 15.0 1_120 13.0 20.0 13.0 | 10.0 15.0 15.0 15.0 : Corrosion inhibitor linear polyhydric alcohol ρ d »0 d 1〇〇 C5 d Ο d 1 1 1 ρ 对 · q ρ — 1 1 1 〇〇ό 〇〇6 〇〇6 1 1 glycerin sorbitol xylitol glycerol xylitol glycerol glycerol sorbitol Alcohol xylitol 1 1 1 glycerol sorbitol xylitol • 1 • glycerol sorbose Alcohol xylitol 1 1 ! Aromatic polyhydric alcohol 〇ρ q ρ ρ qqqq 〇CO 〇〇1 1 < 〇〇〇1 1 1 〇〇i gallic acid i gallic acid gallic acid i gallic acid ate gallate gallate Ester|Methyl gallate 1 Propyl gallate 1 Propyl gallate propyl gallate 1 Gallic acid Gallate gallate Gallic acid 1 1 1 Gallic acid gallic acid methyl gallate propyl ester 1 1 1 Pyro- gallic acid Catechol aprotic polar solvent 86.0 86.5 I 81.5 II 81.5 I 1 76.5 II 76.5 I 1 81.5 1 I 76.5 II 76.5 I 83.0 78.0 I 73.0 I 84.0 79.0 79.0 80.0 79.0 I 72.0 II 77.0 II 80.0 II 75.0 II 77.0 1 75.0 DMSO NMP DMSO 1 NMP DMSO DMSO 1 1 DMSO DMSO _ DMSO DMSO NMP DMSO _ DMSO DMSO ΝΜΡ 1 DMSO NMP alkyl ammonium hydroxide 〇 (N 〇ci 〇CN 〇 <N ο <Ν 〇〇〇〇 (N 〇 (N 〇<N 〇<N 〇(N 〇CN 〇CN 〇CN 〇Η 〇CN 〇CN 〇(N 〇CN ΤΜΑΗ TMAH _ 1 TMAH TEAH ΤΕΛΗ TEAH TEAH 1 1 1 TMAH _ 1 TEAH TEAH _ _ _ 1 1 1 Embodiment 1 Embodiment 2 Embodiment 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 1 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 | Comparative Example 9 I Comparison Example 10 Comparative Example 11 Comparative Example 12 | Comparative Example 13 I Comparative Example 14 12 201204828 << XX ◎ ◎ 〇PI Invitation Φ I 1 1 <Hi s ^ ^ ^ ^ ^ B ^ ^ 芝 ◎ 〇 < X ◎ ◎ ◎ ◎ XXX ◎ ◎ ◎ ◎ <<<3 15.0 in 卜 1 ο CN pp ο CN 〇ο <Ν 1 glycerol xylitol sorbitol 1 xylitol sorbitol xylose醇^里采采$ ^ ^ ^ 1 ¢-f ®0<3 X ο \ό Ο <Ν ο Ο (Ν p 寸· q — q salicylic acid pyrophoric acid salicylic acid gallic acid catechin Salicylic acid 75.0 79.0 78.0 80.0 78.0 I 76.0 I 76.0 DMSO ΝΜΡ DMSO DMSO 1 DMSO i | 1 S ^ ^ ^ ^ &- Τη ¢- ^ B 0 ;l J ^ ^ 5 S Oh fiiSi ο (Ν ο ο ( ο ο CN 〇 (N 〇 <NO (N 1 1 ΤΕΑΗ ΤΕΑΗ TMAH II Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 Comparative Example 21 13 201204828 As can be seen from the first table, The invention exhibits an excellent ability to release positive and negative photoresist of Example 1-9, and no corrosion of Al / Ti, the lower metal film. However, Comparative Examples 1 to 21 which are outside the scope of the present invention exhibited low peeling ability and increased corrosion. Although the present invention has been described with respect to the specific embodiments thereof, it is to be understood that various modifications and changes can be made within the scope of the invention as defined by the appended claims. [Simple description of the figure 3 (none) [Description of main component symbols] (none) 14

Claims (1)

201204828 VII. Patent application scope: 1. A photoresist stripper composition comprising: 0.5 to 5% by weight of alkylammonium hydroxide; 60 to 90% by weight of aprotic polar solvent; 0.1 to 3% by weight of aromatic a polyhydric alcohol; 0.1 to 5% by weight of a linear polyhydric alcohol; and 5 to 30% by weight of water. 2. The photoresist stripper composition of claim 1, wherein the aromatic polyhydric alcohol comprises at least one carboxyl group or alkyl ester group, and at least three hydroxyl groups. 3. The photoresist stripper composition of claim 1, wherein the aromatic polyhydric alcohol is selected from the group consisting of gallic acid, decyl gallate, ethyl gallate, propyl gallate, and butyl gallate. And the ethnic group formed by a mixture of them. 4. The photoresist stripper composition of claim 1, wherein the linear polyhydric alcohol comprises at least three hydroxyl groups. 5. The photoresist stripper composition of claim 1, wherein the linear polyhydric alcohol is selected from the group consisting of glycerol, erythritol, sorbitol, mannitol, xylitol, and a group of equal parts. 6. The photoresist stripper composition of claim 1, wherein the alkyl ammonium hydroxide is selected from the group consisting of tetrakis ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and a group of such mixtures. 7. The photoresist stripper composition of claim 1, wherein the aprotic polar solvent is selected from the group consisting of ruthenium, osmium-dimercaptocarbamide, hydrazine, hydrazine-II 15 201204828 decyl acetamide , Ν, Ν'-diethyl acetamide, dimethyl sulfoxide, N-methyl decylamine, N, Ν'-dimercapto lactam, N-mercaptopyrrolidone, 7-butyrolactone a group of propylene carbonate, 1,3-dimercapto-2-imidazolidinone, and mixtures thereof. 8. The photoresist stripper composition of claim 1, further comprising a glycol and a triazole. 9. The photoresist stripper composition of claim 8, wherein the diol is selected from the group consisting of diethylene glycol decyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, dipropylene glycol A group of methyl ether, hexanediol, polyethylene glycol having a weight average molecular weight ranging from 100 to 400, and mixtures thereof. 10. The photoresist stripper composition of claim 8, wherein the triazole is selected from the group consisting of benzotriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, and nitrobenzotriazole. a group of dihydroxypropylbenzotriazoles, and mixtures thereof. 16 201204828 IV. Designation of representative drawings: (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: