TW200817848A - Photoresist-removing solution, and method for treatment of substrate using the same - Google Patents

Abstract

Disclosed is a photoresist-removing solution which causes no corrosion on a substrate having an aluminum-containing metal layer formed thereon or a substrate having a metal layer containing other metal formed thereon, and which can remove a photoresist film effectively. The photoresist-removing solution comprises (A) 0.1 to 10% by mass (inclusive) of a sugar alcohol, (B) 3 to 20% by mass (inclusive) of an alkanolamine, (C) 5 to 40% by mass (inclusive) of water, and (D) 60 to 95% by mass (inclusive) of a water-soluble organic solvent.

Description

200817848 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a resisting liquid for photoresist. (4) There is a method for treating a substrate for a photoresist and a substrate for using the stripping liquid, which is suitable for use in a semiconductor device such as an integrated circuit (ic) or a large integrated circuit (lsi) or In the manufacture of a liquid crystal panel element, the peeling property is excellent. [Prior Art] In the manufacture of semiconductor devices and liquid crystal panel devices such as 1C and LSI, a conductive metal film deposited by chemical vapor deposition (CVD) is formed on a substrate such as a germanium wafer or a glass. Or an insulating film such as a cerium oxide (si〇2) film. Next, a photoresist is uniformly applied to the above-mentioned conductive metal film or insulating film, and selectively exposed and developed to form a photoresist pattern. Then, using this pattern as a mask, the conductive metal film or the insulating film is selectively etched to form a microcircuit, and then the unnecessary photoresist layer is removed by removing the stripping liquid. Regarding the removal of the unnecessary photoresist layer, various organic peeling liquids have been conventionally used in view of safety and peelability. (Refer to Patent Document 1) On the other hand, the material of the conductive metal film deposited by CVD can be used (M1), Al-Si, Al-Cu, and Al-Cu. Aluminum alloy (Al) such as copper (Ai-gi-Cu); titanium (Ti); titanium alloy (Ti alloy) such as titanium nitride (TiN) or titanium tungsten (TiW); tantalum (Ta), tantalum nitride (TaN), tungsten (W), tungsten nitride (WN), copper, etc., these materials are formed on a substrate in a single layer or a plurality of layers. [Patent Document 1] Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. The content of the ethylene glycol monoalkyl ether in the water-soluble organic solvent is only 1 to 30% by mass, and there is a problem that the photoresist solubility is low. Furthermore, among the characteristics of the stripping solution for photoresist, on the one hand, it is necessary to prevent corrosion of the conductive metal film, and on the other hand, it is necessary to remove the metal residue formed by etching, that is, to seek the opposite characteristic for the same kind of metal. . The present invention has been made in view of the above problems, and an object thereof is to provide a resist for a photoresist which does not corrode at least for a substrate on which an aluminum-containing metal layer for a conductive metal film is formed, and which can be effectively removed. Photoresist film. [Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have focused on the amount of components contained in the resist liquid for stripping. As a result, it has been found that the above problems can be solved by including a specific amount of each component, and the present invention has been completed. More specifically, the present invention provides the following. Provided is a photoresist stripping liquid containing (A) a sugar alcohol in an amount of 0.1% by mass or more and 10% by mass or less, (B) an alkanolamine in an amount of 3% by mass or more and 20% by mass or less, and (C) 5% by mass or more and 40% by mass of water. Hereinafter, (D) the water-soluble organic solvent is 60% by mass or more and 95% by mass or less. Further, there is provided a stripping liquid for photoresist according to the above, which is used for peeling off a photoresist film formed on a substrate having an aluminum-containing metal layer. Moreover, a method for processing a substrate comprising: forming a photoresist film on a substrate on which an aluminum-containing metal layer is formed, and then exposing and developing the photoresist film, and then performing dry etching on the substrate, and further The step of removing the residue of the photoresist film and etching the residue is performed by using the resist for the photoresist. [Effects of the Invention] The peeling liquid for photoresist of the present invention is particularly suitable for a substrate on which at least an aluminum-containing metal layer as a conductive metal film is formed, and which does not cause corrosion, and a substrate on which a metal layer containing another metal is formed. Corrosion does not occur and the photoresist film can be effectively removed. [Embodiment] The photoresist stripper (hereinafter also referred to as "peeling liquid") of the present invention contains (A) a sugar alcohol in an amount of 0.1% by mass or more and 10% by mass or less, and (B) an alkanolamine in an amount of 3% by mass or more and 20% by mass. % or less, (C) 5% by mass or more and 40% by mass or less of water, and (D) 60% by mass of a water-soluble organic solvent. / 〇 Above 95% by mass of the photoresist stripping solution. The components are described below. <(A) Sugar alcohol> The peeling liquid of the present invention contains a sugar alcohol (hereinafter also referred to as "(A) component"). Corrosion of the aluminum-containing metal layer formed on the substrate can be prevented by the addition of the sugar alcohol. The sugar alcohol is generally obtained by reducing a carbonyl group called a sugar represented by Cn(H20)m (η and m is an integer of 0 or more). Specifically, for example, 7 200817848 D-sorbitol, arabitol, mannitol, xylitol, erythritol, D-threitol, L-arabitol, ribitol, D-glucitol , galactitol, L-rhamitol, sucrose, starch, and the like. Among them, xylitol and D.sorbitol are preferably used. Further, the sugar alcohol may be used alone or in combination of two or more.

The amount of the component (A) added is 0.1% by mass or more and 10% by mass or less in the peeling liquid. It is preferably 0. 5 mass% or more and 5% by mass or less. Since the amount of the component (A) added is in the above range, excellent barrier properties against a metal layer particularly for the aluminum layer can be obtained. <(B) Alkanolamine> Examples of the alkanolamine (hereinafter also referred to as component (B)) include ethanolamine, N-mercaptoethanolamine, N-ethylethanolamine, N-propylethanolamine, and N-butylene. Ethanolamine, diethanolamine, isopropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine, N-propyl isopropanolamine, 2-aminepropan-1-ol, N-曱Base-2·Aminopropanone-1·Drunk, N-Ethyl-2-Aminepropan Burn- l-Drunk, 1-Aminopropanol-3-D, N-Methyl-1-aminepropan-3-ol , N-ethyl-1-amine propan-3-ol, 1-amine butan-2-ol, N-methyl-1.aminebutan-2-ol, N-ethyl-1-amine butane -2-ol, 2-aminebutan-1-ol, N-methyl-2-aminebutan-1-ol, N-ethyl-2-amine butanol-l-alcohol, 3-amine butyl alcohol -l-alcohol, N-methyl-3-amine butyl alcohol-1, alcohol, N-ethyl-3-amine butyl alcohol-1-ol, 1-amine butan-4-ol, N-mercapto- 1-aminebutane-4-ol, N-ethyl-1-aminebutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-mercaptopropane , 1-amine pentamer-4-ol, 2-amino-4-mercaptoin-l-alcohol, 2-aminehexane-1-ol, 3-amineheptane-4-ol, 1-amine Octane-2-ol, 5-amine octane-4-ol, amphetamine-2,3-diol, 2-aminopropyl -1,3-diol, tris(hydroxymethyl)amine methane, 8 200817848 1,2-diaminepropan-3-ol, 1,3-diaminepropan-2-ol, 2-(2-amino B Oxyl) Ethanol and the like. Among them, at least one selected from the group consisting of isopropanolamine, diethanolamine and N-methylethanolamine, particularly ethanolamine, which is less corrosive to aluminum than other alkanolamines, is preferred. The component (B) may be used alone or in combination of two or more. <(.) Water> Water (hereinafter also referred to as component (C)) is a component which is necessarily contained in the other components of the resisting release liquid of the present invention, but is further adjusted in the present invention. content. The amount of the component (C) added is 5% by mass or more and 40% by mass in the peeling liquid. /〇 below. It is preferably 10% by mass or more and 30% by mass or less. By setting the amount of the component (C) to be added to the above range, excellent release properties to the photoresist layer and the residue, and corrosion resistance to a metal layer such as aluminum can be obtained. Further, since it is within the above range, the sugar alcohol can be dissolved in the peeling liquid. <(D) Water-soluble organic solvent> A water-soluble organic solvent (hereinafter also referred to as "(D) component)" may be an organic solvent which is miscible with water, and is not particularly limited as long as it can dissolve other additives. And can be used arbitrarily. Examples of such a water-soluble organic solvent include sulfoxides such as dimercaptosulfoxide; sulfones such as dimercaptopurine, diethylsulfone, bis(2-hydroxyethyl)sulfone, and tetradecylsulfone. N,N-dimethylformamide, N-methyldecylamine, N,N-dimercaptoacetamide, N-mercaptoacetamide, N,N-diethylacetamide Ethamamines; N-mercapto-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone , indoleamines such as N-hydroxyethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidin 9 200817848 ketone, 1,3 -diethyl-2-imidazolidinone, 1 , imidazolidinone such as 3-diisopropyl-2-imidazolidinone; ethylene glycol, ethylene glycol monodecyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl A diethylene glycol monoalkyl ether (alkyl group is a lower alkyl group having a carbon number of 1 to 6) such as a monoether or a diethylene glycol monobutyl ether, and a derivative thereof. Among them, at least one selected from the group consisting of diethylene glycol monobutyl ether, N. fluorenyl-2-pyrrolidone, and dimethyl fluorene is excellent in improving the peeling property of the photoresist. The component (C) may be used alone or in combination of two or more. The amount of the component (D) added is 60% by mass or more and 95% by mass or less in the peeling liquid. It is preferably 65 mass% or more and 80 mass% or less. When the amount of the component (D) added is in the above range, high photoresist solubility can be obtained, so that excellent photoresist layer peeling performance can be obtained. Further, since the amount of the component (D) is large, the steam purification of the solvent is facilitated, so that the recovery and recovery of the solvent is facilitated, and the cost of the stripper can be reduced. Further, although the peeling liquid of the present invention contains the above-mentioned added amounts of the components (A) to (D), the desired effect can be obtained, but an anti-corrosive agent may be added as desired. Such anti-corrosion agents can be classified into three types: anti-corrosive agents, anti-adhesive agents, and anti-reagents. The above-mentioned reducing corrosion inhibitor may, for example, be an aromatic mercapto compound such as catechol, tert-butyl phthalate, gallnut or gallic acid. Further, the above-mentioned adsorptive corrosion inhibitor may, for example, be benzotriazole, 5,6-dimercaptobenzotriazole, 1·hydroxybenzotriazole, 1-methylbenzotriazole, 1 -aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxydecylbenzotriazole, 10 200817848 1-benzotriazole methylcarboxylic acid, 5-benzotriazolecarboxylic acid, i -Methoxy-benzotriazole, 1-(2,2-dihydroxyethyl)-benzotriazole, 1-(2,3-dihydroxypropyl)-benzotriazine, or bismuth Sale > Feiba Specialty Chemicals Co., Ltd. (Ciba Specialty

Chemicals) "Irgamat" series products 2,2,-{[(4-methyl-1H-benzotris-l-)yl]imido}diethanol, 2,2,-{[(5 · mercapto-1H-benzotriazin-1-yl)methyl]imino}diethanol, methyl-1Η-benzotris-l-yl)methyl]imino}diethyl, Or a triazole compound such as 2,2,-{[(4-methyl-1Η-benzotris-l-yl)methyl]iminoindole bispropane 0 has both reducing and surface adsorption As the anticorrosive agent, for example, a compound containing a hydrogenthio group such as hydrazine glycerol or 2-hydrazine ethanol can be mentioned. In the above-mentioned corrosion inhibitor, it is preferable to use an anticorrosive agent containing a hydroxyl group-containing or hydroquinone compound, wherein at least one selected from the group consisting of an aromatic hydroxy compound and a hydrogen-containing sulfur-based compound is preferred from the viewpoint of high corrosion resistance. By selecting such an anticorrosive agent having high corrosion resistance, it is possible to obtain a desired anti-surname performance by only adding a trace amount, so that the stripping liquid of the present invention can be recovered and distilled. The stripping liquid of the present invention is suitably used for a photoresist which can be developed in an alkaline aqueous solution including a negative type and a positive type resist. Such a photoresist may, for example, be (i) a positive type resist containing a naphthoquinonediazide compound and a novolac resin, (ii) a compound containing an acid generated by exposure, decomposed by an acid, and an alkaline aqueous solution. a compound having an increased solubility and a positive resist of an alkali-soluble resin, (iii) a compound containing an acid which is formed by exposure, and a soluble resin having a group which can be decomposed by an acid and which has an increased solubility in an aqueous alkaline solution Positive photoresist, and (iv) a compound containing a compound which generates acid due to light, a bridging agent, and a negative resist of a soluble resin 11 200817848, etc., but are not limited thereto. The use form of the stripping liquid of the present invention is to form a photoresist pattern by using a lithography technique, thereby selectively etching a conductive metal film (especially an aluminum-containing metal layer) or an insulating film as a mask to form a microcircuit. , stripping the photoresist pattern and the residue generated by the remainder. The formation, exposure, development, and surname processing of the photoresist layer are conventional methods and are not particularly limited. Further, the etching may be performed by wet etching or dry etching. The peeling treatment using the peeling liquid of the present invention is usually carried out by a dipping method or a shower. Although the peeling time can be given a sufficient time, although it is not particularly limited, it is preferable to carry out the peeling treatment in a short time. Further, after the release treatment, a conventional rinsing treatment and drying treatment using pure water, a lower alcohol or the like may be carried out. [Examples] Hereinafter, the examples of the invention are described, but the examples are merely illustrative of the invention, and the invention is not limited thereto. (Examples 1 to 6 and Comparative Examples 1 to 5) [Removability of Photoresist Film] Photoresist TFR-H (manufactured by Tokyo Ohka Kogyo Co., Ltd.) for thin film transistor (TFT) was deposited on a wafer. The pattern was formed and post-bake was performed at 150 ° C for 90 seconds. The wafer having the photoresist pattern was immersed in a photoresist stripping solution as shown in Table 1 below, heated to 50 ° C, and immersed in 12 200817848 for 2 minutes, by carrying an & scanning electron microscope (SEM). The photograph was observed for the peeling property of the photoresist, and was evaluated according to the following evaluation criteria. The results are shown in Table 1. 〇 (Evaluation) 〇·· Complete removal of Δ: Residual part of residue X: Most of the residue remaining [Aluminum repellency (impregnation method)] A wafer with an aluminum layer will be formed' The peeling liquid for photoresist used in the following Table 1 was subjected to an impregnation treatment at 50 ° C for 30 minutes, and the resistance value of the L sheet was measured. The result is the amount of etching (corrosion) of aluminum, and the evaluation criteria for the corrosion resistance of aluminum are evaluated by the evaluation criteria described below. The results are shown in Table 1. In addition, the measurement of the resistance value of the thin film was measured using VR-70 (I International Electric Co., Ltd.). (Evaluation) 〇No corrosion at all # Δ Corrosion is scattered everywhere X Severe rot occurs # [Aluminum corrosion resistance (spray method)] A wafer with an aluminum layer is formed to be heated to 50 °C as follows The peeling liquid for photoresist shown in Table 1 was sprayed at a pressure of 0.1 MPa for 30 minutes, and then the sheet resistance value was measured. From the results, the etching amount (corrosion amount) of aluminum was determined, and the corrosion resistance to aluminum was measured by the following evaluation criteria. The results are shown in Table 1. Further, for the measurement of the sheet resistance value, the same measuring apparatus as the above-described aluminum corrosion resistance test was used. 13 200817848 (Evaluation) 〇: No corrosion at all △: Corrosion is scattered everywhere X: Severe corrosion occurs [Table 1]

(A) Ingredient (B) Ingredient (C) Ingredient (D) Ingredient Corrosion Repellent Aluminum Anticorrosive Dipping Method Spray Method Example 1 XYL(5) MIPA (10) Water (20) BDG(65) 〇〇 〇 Example 2 XYL(5) DGA (10) Water (20) BDG (65) 〇〇〇 Example 3 XYL (5) NMEA (10) Water (20) BDG (65) 〇〇〇 Example 4 XYL ( 3) MIPA (5) Water (20) BDG (72) 〇〇〇 Example 5 XYL(2) MIPA (5) Water (20) BDG (73) 〇〇〇 Example 6 XYL(l) MIPA (5) Water (20) BDG(74) 〇〇〇Comparative Example 1 XYL(5) MIPA (10) BDG(85) X 〇〇Comparative Example 2 XYL(5) Water (20) BDG(75) X 〇〇Comparative Example 3 MIPA (10) Water (20) BDG(70) 〇Δ X Comparative Example 4 MIPA (10) Water (70) BDG(15) PG(5) 〇XX Comparative Example 5 MIPA (10) Water (20) BDG (65 PG(5) 〇〇X XYL : lignin MIPA: isopropanolamine NMEA: N-methylethanolamine DGA: diglycolamine BDG: diethylene glycol monobutyl ether PG: propylene glycol As shown in Table 1, In the peeling liquids of Examples 1 to 6, it was confirmed that aluminum was excellent in corrosion resistance and excellent in peeling resistance of light. On the other hand, in Comparative Example 2 of 14 200817848, there was no residue in the corrosion inhibitor. Use Comparative Example Comparative Example 1 containing no component (C) and the method containing no component (B) were sufficiently peeled off. Further, in Comparative Example 3 containing no component (A), in Comparative Examples 4 and 5 in which propylene glycol was used, it was confirmed that the peeling property and the corrosion resistance of aluminum were not obtained in combination. [Simple description of the diagram] None [Key component symbol description] None 15

Claims (1)

200817848 X. Patent application scope: 1. A peeling liquid for photoresist, comprising: (A) sugar alcohol 0.1% by mass or more and 10% by mass or less, (B) alkanolamine 3 mass% or more and 20% by mass Hereinafter, (C) water is 5% by mass or more and 40% by mass or less, and (D) water-soluble organic solvent is 60% by mass or more and 5% by mass or less. 2. The peeling liquid for photoresist according to claim 1, wherein the component (A) is xylitol. 3. The photoresist stripping solution according to claim 1, wherein the component (B) is self-isopropanolamine, N-mercaptoethanolamine, and 2-(2-aminoethoxy)ethanol. Choose at least one of them. 4. The photoresist stripping solution according to claim 1, wherein the component (D) is from diethylene glycol monobutyl ether, N-fluorenyl-each ketone, dimethyl sulfoxide. Choose to use at least one of them. 5. The photoresist stripper according to claim 1, which is used for peeling off the photoresist on the substrate, the substrate being formed with an aluminum-containing metal layer. A method for processing a substrate, comprising: forming a photoresist film on a substrate on which an aluminum-containing metal layer is formed, and then exposing and developing the photoresist film, and then performing dry etching on the substrate, and further The step of removing the residue of the photoresist film and etching the residue by removing the photoresist for the photoresist according to any one of the first to fifth aspects of the invention. 16 200817848 VII. Designated representative map: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: None / i 4