TW200948954A - Cleaning liquid for semiconductor device and cleaning method - Google Patents

Abstract

The present invention provides a cleaning liquid for a semiconductor device, which is used in removing adhesives, such as photoresist, etching residues, an anti-reflection film and ashing residues, and so on, on the surface of being cleaning matter, with low environmental loads, and no corrosion of layer insulating film, and provides method of cleaning semiconductor using the cleaning liquid. The cleaning liquid for semiconductor device with pH 10 to 14 comprises an oxidant, a metal etchant, and a surfactant.

Description

200948954 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a cleaning solution and a cleaning method for a semiconductor device. More specifically, the present invention relates to a process for a semiconductor device, particularly in all steps of semiconductor fabrication, in which the photoresist, etching residue, anti-reflective film, and ash residue remaining on the substrate are removed. A liquid, and a cleaning method for a semiconductor using the cleaning liquid. [Prior Art] A semiconductor device such as a CCD or a memory is manufactured by forming a fine electronic circuit pattern on a substrate by using a photolithography technique. Specifically, the photoresist film is coated on a laminated film of a metal film (for example, copper), an interlayer insulating film, an antireflection film, or the like which is a wiring material formed on a substrate, and is subjected to a photolithography step and dry etching. The steps are made. The photoresist or antireflection film remaining after the photolithography step is subjected to dry ashing treatment. Subsequently, it is produced by a dry etching step and a dry ashing step, and the residue (etch residue, ash residue) remaining on the wiring material or the interlayer insulating film material is generally removed by the cleaning liquid. In recent years, with the increase in the performance of semiconductor devices, there is a need for further miniaturization and high speed of manufacturing. Among them, the cleaning time in the manufacturing process of semiconductor devices is shortened, and the cleaning technology is an important issue. For example, for the performance improvement of a semiconductor device, an interlayer insulating film formed of a low dielectric constant (Low-k) material is used. Since the low dielectric constant raw material has a low k値 and contains a porous (pore), the contact area of the cleaning liquid and the low dielectric constant raw material becomes large in the cleaning step due to the presence of the pores, and the cleaning is performed in 200948954. In the step, the low dielectric constant material is etched because of the cleaning liquid. This causes the shape of the device wiring to be changed, and the performance of the device is thus poor. In addition, in order to reduce the damage to the wiring material, particularly the interlayer insulating film formed of the low dielectric constant material, the thinning and high performance of the semiconductor device have been continued in recent years. The process step' or the process of making a light dry ashing step is changed. Therefore, it is highly desirable to have a cleaning liquid which can sufficiently remove the photoresist or the antireflection film without performing the dry ashing step. © As a cleaning solution for a semiconductor device that removes the above-mentioned photoresist, antireflection film, etch residue, ash residue, etc., for example, it is proposed to be washed by a mixed system of a hospital alcohol amine and an organic solvent. Liquid (refer to Patent Documents 1 and 2). Further, Patent Document 3 discloses a cleaning solution comprising an alkanolamine, hydroxylamine, catechol and water. Further, Patent Document 4 discloses a cleaning liquid comprising an alcohol-based solvent, a halogen-based solvent, and an organic 4-grade ammonium salt. Further, Patent Document 5 discloses a cleaning liquid comprising water, tetramethylammonium hydroxide, hydrogen peroxide, and a nonionic surfactant. Further, Patent Document 6 discloses a cleaning liquid formed of an anticorrosive agent of sodium hydroxide or potassium hydroxide, a water-soluble organic solvent, or a Group 9 or Group 11 metal. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. When the liquid was reviewed, the following problems were found. (1) The anti-reflection film of the cleaning liquid described in Patent Documents 1 to 3, for example, the removal property of the organic siloxane-based anti-reflection film is not sufficient. (2) The cleaning liquid described in Patent Document 4 is insufficient in the removability of a photoresist or an antireflection film (for example, an organic siloxane-based antireflection film). (3) The cleaning liquid described in Patent Document 5 is required to be removed at a high temperature in order to remove a photoresist or an anti-reflection film (for example, an organic siloxane-based anti-reflection film), and it is intended to be long. It is not enough to say that it is not enough to increase production through device manufacturing. (4) The cleaning liquid described in Patent Document 6 can obtain the cleaning performance in a short period of time, but the temperature used is not sufficiently low, and the time required for the time is not short. Further, since the benzotriazole used as the corrosion preventing agent has low biodegradability and high environmental load, there is a problem that an environmental facility such as a waste liquid treatment is expensive. The conventional cleaning solution is not sufficient for the removability of photoresist, etching residue, antireflection film, or ash residue. Further, even if it is removable, it is necessary to perform a long-time cleaning process to complete the etching of the low dielectric constant raw material contained in the semiconductor device, or to use a high environmental load such as the use of a metal corrosion preventing agent containing a hetero ring. The problem exists. 200948954 Therefore, an object of the present invention is to provide a low environmental load, which does not corrode an interlayer insulating film, and which can remove the adhesion of photoresist, etching residue, antireflection film, and ash residue on the surface of the object to be cleaned. A cleaning solution for a semiconductor device and a cleaning method for a semiconductor device using the cleaning solution. [Technical method for solving the problem] As a result of the review by the inventors, the above problem is solved by the following configuration of &lt;1&gt;~&lt;12&gt;. ❹ <1> A cleaning liquid for a semiconductor device comprising an oxidizing agent, a metal etchant, and a surfactant, and having a pH of 10 to 14 (&lt;2&gt;&gt; Wherein the oxidizing agent is hydrogen peroxide. &lt;3&gt; The cleaning solution for a semiconductor device according to <1>, wherein the metal etchant is an amine compound. &lt;4&gt; The cleaning solution for a semiconductor device according to <3>, wherein the amine compound is selected from the group consisting of ethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetra® At least one of the group consisting of acetaminophen and derivatives thereof. The cleaning solution for a semiconductor device according to any one of <1> to <4>, which further comprises an inorganic cerium compound or a 4-grade ammonium hydroxide represented by the general formula (1) 200948954 General formula (1)

Ri R2 - N - R4 r3 OH' wherein RpR4 in the general formula (1) each independently represents an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a benzyl group or an aryl group. <6> The cleaning solution for a semiconductor device according to <5>, wherein the inorganic base compound is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, ruthenium hydroxide, and barium hydroxide. At least one of the groups. The cleaning solution for a semiconductor device according to any one of <1>, wherein the surfactant is a cationic surfactant or a nonionic surfactant. &lt;8&gt; The cleaning solution for a semiconductor device according to <7>, wherein the cationic surfactant is selected from the group consisting of a 4-grade ammonium salt-based surfactant and an alkylpyridine gun-based surfactant. At least one of them. <9> The cleaning solution for a semiconductor device according to <7>, wherein the nonionic interface active agent is selected from the group consisting of a polypropylene oxide polyethylene oxide surfactant and a polyalkylene oxide a styrenated phenyl ether-based surfactant, a polyalkylene oxide alkylphenyl ether surfactant, a polyalkylene oxide tribenzyl phenyl ether surfactant, an acetylene polyalkylene oxide surfactant, And at least one of the group consisting of polyalkylene oxide alkyl ether surfactants. &lt;1〇&gt; A method of cleaning a semiconductor device, which is used for cleaning a semiconductor device with a cleaning solution for a semiconductor device according to any one of the items. &lt;11&gt; A method of cleaning a semiconductor device, which is characterized in that after the dry etching step, the semiconductor device is cleaned using the cleaning device 200948954 liquid according to any one of &lt;1&gt; to &lt;9&gt; Washing steps. &lt;12&gt; The method of cleaning a semiconductor device according to <10> or <11>, wherein the semiconductor device is a semiconductor device comprising an interlayer insulating film having a dielectric constant k of 3.0 or less. Advantageous Effects of Invention According to the present invention, it is possible to remove deposits such as photoresist, etching residue, anti-reflection film, and ash residue on the surface of the object to be cleaned with low environmental load and without etching the interlayer insulating film. Further, the cleaning liquid of the semiconductor crucible device of the present invention (hereinafter also referred to as "cleaning liquid" for short) may have a possibility of removing adhering substances even if the metal corrosion inhibitor is not contained. BEST MODE FOR CARRYING OUT THE INVENTION The etching residue in the present invention refers to a by-product formed during etching, an organic residue derived from a photoresist, a residue containing ruthenium, and a residue containing a metal. Further, the so-called ashing residue in the present invention means a by-product formed during ashing, an organic residue derived from a photoresist, a residue containing ruthenium, and a residue containing a metal. The cleaning liquid of the present invention is a cleaning liquid used in the production of a semiconductor device, and is an aqueous solution containing an oxidizing agent, a metal etchant, and a surfactant, and having a pH of 10 to 14. The following is a description of all the specific aspects. &lt;Oxidant&gt; The cleaning liquid of the present invention contains an oxidizing agent. The oxidizing agent herein is preferably a compound having an oxidizing effect. In particular, from the viewpoint of further improving the removability of the residue and the corrosiveness of the insulating film or the like, it is preferably selected from the group consisting of hydrogen peroxide, ammonium persulfate, hydrochloric acid, chlorous acid, and hypochlorous acid. At least one compound of the group formed by perchloric acid, permanganic acid, iodic acid, hypoiodous acid, periodic acid, and properiodate. In the present invention, in particular, hydrogen peroxide or properiodic acid is more preferable. The oxidizing agents may be used singly or in combination of two or more. The content of the oxidizing agent is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass based on the total mass of the cleaning liquid. If the content of the oxidizing agent is within the above range, it is preferably etched by the metal ruthenium raw material contained in the semiconductor device, which is preferable. &lt;Metal contact agent&gt; The cleaning liquid of the present invention contains a metal etchant. The metal etchant refers to a compound capable of etching a metal, a metal nitride, or an alloy by being added to the cleaning composition liquid. Specific examples thereof include an amine compound, an inorganic acid, an organic acid, a sulfonic acid compound, a heterocyclic ring-containing compound, a sulfonic acid compound, and the like, and from the viewpoint of selectively etching copper, the present invention The use of an amine compound is preferred. The hydrazine compound may, for example, be an amine compound containing a plurality of N atoms, methylamine or ethylamine, such as ammonia or ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethyleneamine or the like. Alkylamines (e.g., preferably having 1 to 16 carbon atoms in the alkyl chain, more preferably 1 to 8), dialkylamines such as dimethylamine and diethylamine (carbon number of each alkyl chain) a trialkylamine such as 1~16 is preferred, 1-8 is more preferred, trimethylamine or triethylamine (the alkyl chain has a carbon number of 1 to 16 is preferred, and 1 to 8 is more preferred). An alcohol amine compound such as monoethanolamine or diethanolamine. From the point of view of selectively etching copper, among them, ethylamine, ethylenediamine, diamethylene-3--10-.200948954 amine, triamethylenetetramine, tetraamethyleneamine are preferred. Ethylenediamine and diethylenetriamine are particularly preferred. The metal etchant content is preferably 0.0000 1 - 10% by mass, and more preferably 0.00001 to 5% by mass, based on the total mass of the cleaning liquid. If the content of the metal etchant is within the above range, the etching of the metal contained in the semiconductor device can be appropriately adjusted, which is preferable. &lt;Intermediate Active Agent&gt; 洗 The washing liquid of the present invention contains a surfactant. As the surfactant, a nonionic, anionic, cationic surfactant, and an amphoteric surfactant can be used. The surfactant used in the present invention adjusts the viscosity of the cleaning liquid by the addition method, and improves the wettability of the object to be cleaned, the removability of the residue, and the corrosiveness to the substrate or the insulating film. From a more excellent point of view, it is preferred to use a nonionic surfactant. A nonionic surfactant can be used, for example, a polyalkylene oxide alkylphenyl ether interfacial surfactant, a polyalkylene oxide alkyl surfactant, polyethylene oxide, and polypropylene oxide. a block polymer-based surfactant, a polyalkylene oxide distyrenated phenyl ether-based surfactant, a polyalkylene tribenzyl phenyl ether-based surfactant, an acetylene-polyalkylene-based surfactant, and the like . Among them, preferred are PAO mercapto ether, PAO lauryl ether, PAO tridecyl ether 'PAO alkylene ether, PAO Yamanashi selected from polyalkylene oxide (hereinafter referred to as PAO) alkyl ether surfactant. Alcoholic anhydride monolaurate, PAO sorbitan monooleate, PAO sorbitan monostearate, tetraoleic acid polyepoxyethylene-11 - 200948954 alkyl sorbitol, PAO alkylamine, PAO extension A polyalkylene oxide alkyl ether surfactant of acetylene glycol. As the polyalkylene oxide, a polymer of polyethylene oxide, polyepoxypropylene or polyepoxybutylene is preferred. Other suitable examples include a polypropylene oxide polyethylene oxide surfactant, a polyalkylene oxide distyrenated phenyl ether surfactant, and a polyalkylene oxide alkylphenyl ether interface. An active agent, a polyalkylene oxide tribenzyl phenyl ether type surfactant, an acetylene polyalkylene oxide type surfactant, a polyalkylene oxide alkyl type surfactant, etc. In addition, as the surfactant to be used in the present invention, the viscosity of the cleaning liquid is adjusted by the addition method, and the wettability of the object to be cleaned, the removability of the residue, and the like of the substrate or the insulating film are improved. A cationic surfactant is preferably used in view of the superiority of both of the corrosive properties. The cationic surfactant is preferably a 4-grade ammonium salt-based surfactant or an alkylpyridine-based surfactant. As the 4-grade ammonium salt-based surfactant, a compound represented by the following general formula (2) is preferred.

Rs N Re r7 X· (In the general formula (2), X represents a hydroxide ion, a chloride ion, a bromide ion, or a nitrate ion. 115 represents an alkyl group having a carbon number of 8 to 18. R* and Rv represent independent An alkyl group having 8 to 18 carbon atoms, an aryl group, a hydroxyalkyl group having 1 to 8 carbon atoms, or a benzyl-12-.200948954 group. R8 represents an alkyl group having a carbon number of 3. In the general formula (2), X· represents a relative anion, and specifically represents a hydroxide ion, a chloride ion, a bromide ion, or a nitrate ion. In the general formula (2), Rs represents an alkyl group having 8 to 18 carbon atoms (preferably having a carbon number of 12 to 18, for example, a hexadecyl group or a stearyl group). R6 and R7 each independently represent an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 8 carbon atoms (e.g., hydroxyethyl group), an aryl group (e.g., phenyl group, etc.), or a benzyl group. In the general formula (2), R* represents an alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, etc.). Specific examples of the compound represented by the general formula (2) include cetyltrimethylammonium chloride, dilauryldimethylammonium chloride, tridecylmethylammonium chloride, and stearylbenzyl chloride. Methylammonium and the like. The relative anion of this compound is not limited to chloride ion, and may be a bromide ion or a hydroxide ion. Further, as the alkylpyridine gun-based surfactant, specifically, a cetylpyridinium chloride or the like can be mentioned. The relative anion of this compound is not limited to chloride ions, but may also be bromide or hydroxide ions. φ The content of the surfactant in the cleaning liquid is preferably 0.0001 to 5% by mass, more preferably 0.0001 to 1% by mass based on the total amount of the cleaning liquid. The surfactant is added to the cleaning solution. In order to improve the wettability of the object to be cleaned by adjusting the viscosity of the cleaning liquid, it is preferable, and it is preferable from the viewpoint of excellent corrosion of the substrate or the insulating film. In general, such surfactants are commercially available. These surfactants can be used singly or in combination of plural kinds. &lt;pH &gt; The pH of the washing liquid of the present invention is 10 to 14, more preferably 11 to -13 to 200948954. When the pH is in the above range, the photoresist, the antireflection film, the etching residue, and the ash residue can be sufficiently removed, which is preferable. As a method of measuring pH, it can be measured using a conventional pH 値 measuring device. The cleaning liquid of the present invention preferably contains a basic compound in order to achieve the above pH. The term "basic compound" means a compound which is made to be present in an aqueous solution to render the aqueous solution alkaline. Specific examples thereof include an inorganic alkali compound such as an alkali metal hydroxide formed of a pair of alkali metal elements and a hydroxyl group, or a fourth-order ammonium hydroxide represented by the general formula (1). ❹

The inorganic alkali compound is particularly preferably an alkali metal hydroxide, and specifically, at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, and hydroxide. An alkali metal hydroxide is preferred. Among them, sodium hydroxide and potassium hydroxide are preferably used from the viewpoint of easy availability. The alkali metal hydroxide compounds or hydrates thereof may be used singly or in combination of two or more. Here, the 4-stage ammonium hydroxide is a compound represented by the following general formula (1) - (1)

Ri R2——N—R4 r3 OH′ (wherein 'Ri~R4 in the general formula (1) each independently represents a courtyard group having a carbon number of 1 to 6, a hydroxyl group having a carbon number of 1 to 6, a nodal group, Or an aryl group.) In the general formula (1), 'Rh4' independently represents a steroid-14-200948954 base having a carbon number of 1 to 6, (for example, methyl, ethyl, butyl, etc.), and a carbon number of 1 to 6 Hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxybutyl, etc.), benzyl, or aryl (e.g., phenyl, naphthyl, etc.). Among them, an alkyl group, a hydroxyethyl group and a benzyl group are preferred. Specifically, it is preferably selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methyltris(hydroxyethyl)ammonium hydroxide, and tetrakis(hydroxyethyl) hydroxide. At least one 4- tolu-amyl hydroxide in the group formed by ammonium, trimethylbenzylammonium hydroxide, and choline; wherein tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydrogen in the present invention is used. More preferably, trimethylbenzylammonium oxide, e or cholesteric. The fourth-grade ammonium hydroxide may be used singly or in combination of two or more kinds. An alkali metal hydroxide or a quaternary ammonium hydroxide may be used in combination of two or more kinds thereof. The content of the inert compound (inorganic hydrazine compound, the quaternary ammonium hydroxide represented by the general formula (1), etc.) is preferably 0.01 to 20% by mass, more preferably, based on the mass of the entire cleaning liquid of the present invention. 0.1 to 10% by mass, and more preferably 0.1 to 5% by mass. When the content of the basic compound is within the above range of ®, the photoresist, the antireflection film, the etching residue, and the ash residue can be sufficiently removed, and the interlayer insulating film or ruthenium mainly composed of SiOC can be suppressed or reduced. Corrosion of the substrate is therefore preferred. &lt;Others&gt; The cleaning liquid of the present invention is an aqueous solution, and the water content is preferably 50 to 98% by mass based on the total mass of the cleaning liquid. Further, as far as possible, the cleaning liquid of the present invention is preferably a heterocyclic-free metal anticorrosive inhibitor such as benzotriazole, and is substantially not contained. -15- 200948954 The cleaning solution of the present invention may contain a water-soluble organic solvent, a fluorine-containing compound, and a chelating agent in order to satisfy the needs. Further properties can be obtained by including these. &lt;Water-soluble organic solvent&gt; The cleaning liquid of the present invention may also contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanedione, sorbitol, xylitol, and the like. Alcohol solvent; ethylene glycol monomethyl ether, diethylene glycol, diethylene glycol monomethyl ether, © ether solvent such as triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether; formazan, monomethyl Indamine, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, N-methylpyrrolidone, etc. a guanamine-based solvent; a sulfur-containing solvent such as dimethyl maple, dimethyl argon, or butyl sulphate, r-butyrolactone, a lactone solvent such as 5-valerolactone, etc. An alcohol, an ether, a guanamine or a sulfur-containing solvent, more preferably 1,6-hexanedione, tetraethylene glycol, propylene glycol, dipropylene glycol monomethyl ether, N-methylpyrrolidone, and dimethyl The water-soluble organic solvent may be used alone or in combination of two or more. The content of the water-soluble organic solvent in the cleaning liquid is preferably from 0 to 40 with respect to the total weight of the cleaning liquid. quality% More preferably, the concentration is 〇20% by mass. It is preferred to add a water-soluble organic solvent to the cleaning liquid to promote the removal of the etching residue. <Fluorine Compound> The cleaning liquid of the present invention The fluorine-containing compound may also contain a fluorine-containing compound, which is hydrofluoric acid, and reacts with ammonia or an organic amine to form a fluoride salt. For example, -16-200948954 ammonium fluoride, acidic ammonium fluoride, methylamine hydrogen fluoride, ethylamine Fluoride salt, propylamine fluoride salt, tetramethylammonium fluoride, tetraethylammonium fluoride, ethanolamine hydrogen fluoride salt, triethylene glycol diamine hydrogen fluoride salt, etc. These may be used alone or in combination of two or more. The content of the fluorine-containing compound in the cleaning liquid is preferably from 0 to 10% by mass based on the total weight of the cleaning liquid, and that the fluorine-containing compound is added to the cleaning liquid to promote the photoresist, the anti-reflection film, and The etching residue and the removal of the ash residue are preferable. © <The chelating agent> The cleaning liquid of the present invention may further contain a chelating agent. Examples of the chelating agent include an amine polycarboxylic acid salt group composed of the following { Ethylenediamine tetraacetate (EDTA), Ethylene triamine pentaacetic acid (DTPA), hydroxyethyl ethylenediamine triacetate (HEDTA), dihydroxyethyl ethylenediamine tetraacetate (DHEDDA), nitric acid acetate (NTA), hydroxyethyl Aminodiacetate (HIDA), /3-alanine diacetate, aspartic acid diacetate, methylglycine diacetate, iminodisuccinate, serine diacetate , hydroxyiminodisuccinate, dihydroxyethylglycinate, aspartate, glutamate, etc., a group of hydroxycarboxylates consisting of {hydroxyacetate, tartrate , a citrate salt, a gluconate salt, etc., a cyclic carboxylate group consisting of a pyromellitate, a benzopolycarboxylate, a cyclopentane tetracarboxylate, etc., an ether carboxylate consisting of Acid group {carboxymethyl propanate, carboxymethyl oxysuccinate, oxydicarbonate, tartaric acid monosuccinate, tartaric acid disuccinate, etc.}, other carboxylates consisting of the following Group {maleic acid derivatives, oxalates, etc.}, organic carboxylic acid (salt) polymer group consisting of {acrylic polymer-17-200948954 and copolymer ( An enoic acid-allyl alcohol copolymer, an acrylic acid-maleic acid copolymer, a hydroxy acrylic acid polymer, a polysaccharide-acrylic acid copolymer, etc., a polycarboxylic acid polymer and a copolymer group composed of the following {maleic acid, clothing a polymer and a copolymer of a monomer such as benic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid, aspartic acid, glutamic acid, etc., glyoxylic acid composed of the following Polymer, polysaccharide group {starch, cellulose, amylose, pectin, carboxymethyl cellulose, etc.}, a phosphonate group consisting of {methyl diphosphonate, amine ginseng (methylene Phosphonate), ethylene diphosphonate, 1-hydroxyethylidene-1,1-diphosphonate, © ethylamine bis(methylene phosphonate), ethylenediamine dimethylene Glycosate, ethylenediaminetetramethylenephosphonate, hexamethylenediaminetetramethylenephosphonic acid, propyldiaminetetramethylenephosphonate, diamethylenetriamine-5 Methyl phosphonate, tri-extension ethyltetramine hexamethylene tartate, and tetra-ethylene pentaamine hemi-methylene ortho-acidate. Further, examples of the salt include an ammonium salt, an alkanolamine (monoethanolamine, triethanolamine, etc.) salt, and the like. These may be used alone or in combination of two or more. The content of the chelating agent in the cleaning liquid 较佳 is preferably a concentration of 0 to 10% by mass based on the total weight of the cleaning liquid. It is preferred to add a chelating agent to the cleaning liquid to promote the removal of the metal-containing residue. &lt;Washing Objects&gt; In the present invention, the material of the semiconductor device having the object to be cleaned is a semiconductor wiring material (germanium, amorphous germanium, polycrystalline germanium, germanium oxide, tantalum nitride, copper, or the like). Titanium, titanium-tungsten, titanium nitride, tungsten, chromium, chromium oxide, aluminum, etc.) or a semiconductor substrate to which a compound semiconductor or the like (. gallium-arsenic, gallium-phosphorus, indium-phosphorus, etc.) is applied, polyimine A printed circuit board such as a resin, a glass substrate used in an LCD or the like, -18 - 200948954, and the like. The cleaning liquid of the present invention can adjust the etching of the metal-containing raw material. On the other hand, it does not corrode the wiring material or the like represented by other niobium oxide. Further, the cleaning liquid of the present invention is suitably used even for a semiconductor device (for example, a semiconductor device substrate) having an interlayer insulating film. The interlayer insulating film preferably has a dielectric constant k of 3.0 or less, more preferably 2.6 or less, and examples of the material of the interlayer insulating film include an organic polymer such as a SiOC material or a polyimide. In addition, a semiconductor device substrate such as an integrated circuit (1C, LSI) or the like can be used as a specific example of the semiconductor device (semiconductor device) of the cleaning liquid of the present invention. In addition, examples of the semiconductor device substrate include a single-layer substrate in which a metal wiring is formed on a surface of a substrate, a multilayer wiring substrate formed by forming a wiring through an interlayer insulating film on the surface thereof, and a multilayer wiring substrate in which a photoresist is laminated. . The cleaning liquid of the present invention does not corrode such materials (wiring materials, interlayer insulating film materials, etc.), and can remove residues. &lt;Washing method&gt; The cleaning method of the present invention comprises: after preparing the cleaning liquid of the present invention (washing liquid preparation step), and cleaning the semiconductor device using the obtained cleaning liquid to remove photoresist and resist The cleaning step of the reflective film, the etching residue, and the ash residue is characterized.

The preparation method of the cleaning liquid of the present invention is not particularly limited. It can be produced by sufficiently mixing an oxidizing agent, an surfactant, an inorganic alkali compound which can be used as needed, a 4-stage hydrogen oxide or the like by using a stirrer such as a mixing agitator. Alternatively, a mixing method adjusted to the set pH -19-200948954 in advance or a method of adjusting to the set pH after mixing may be used. The washing step can be carried out by using any of the conventional methods. The method of bringing the cleaning liquid into contact with the cleaning photoresist or the like may be a dipping method, a spray method, or a single wafer system. More specifically, a immersion method of a semiconductor device (for example, a semiconductor integrated circuit board) in which a cleaning liquid is filled in a cleaning tank, a spray method in which a cleaning liquid is sprayed onto a substrate, and a nozzle are used for cleaning The liquid flows onto the substrate while rotating the substrate at a high speed. ® The temperature of the cleaning solution when the cleaning method of the present invention is carried out can be appropriately selected depending on the method of use, the etching conditions, or the object to be cleaned, and the range of 15 to 100 ° C is preferably 15 to 80 ° C. The range is preferably, and the range of 20 to 551 is more preferable. When it is in the above range, the removability of the residue and the corrosiveness to the substrate or the insulating film and the like are more excellent, the cleaning effect is better and better, and since it can be carried out at a low temperature, no special device is required. Etc., preferably. When the cleaning liquid of the present invention is brought into contact with a semiconductor device having photoresist or the like

Between D, 30 seconds to 30 minutes is better, 30 seconds to 10 minutes is better, and between 30 seconds and 5 minutes is better. Within the above range, the photoresist, the antireflection film, the etching residue, and the ash residue can be sufficiently removed, and since the time required for the cleaning method is short, it is preferable. In the cleaning method of the present invention, it is preferred to remove the photoresist or the like by repeating the cleaning step of the cleaning liquid for two or more times. It is preferable because the cleaning performance of the photoresist or the like can be improved by repeatedly performing the cleaning step of two or more times. Although the washing step can be repeated any number of times until the photoresist is completely removed, the reverse -20-200948954 is preferably 1~3 times, and the cleaning is preferably 1~2. In the above washing step, the washing method of the present invention can use ultrasonic waves as needed. After the photoresist on the object to be cleaned is removed, the semiconductor device can be washed (rinsed) as needed. The rinsing is preferably water or warm water of about 50 ° C, or isopropanol. In the case of using a substrate for a semiconductor device such as a metal wiring such as copper or an interlayer insulating film on the surface, CMP (Chemical Mechanical Polishing) is used. The cleaning step after the cleaning step, the cleaning step after the dry uranium is opened in the interlayer insulating film on the wiring, the cleaning step after the dry ashing treatment on the photoresist, and the like. In a preferred embodiment of the cleaning method of the present invention, the above-described cleaning treatment (cleaning step) is carried out after the dry etching step of the semiconductor device. More specifically, after performing a dry etching process on a desired semiconductor device, in order to remove the etching residue or the photoresist, the semiconductor device is washed using the above-described cleaning solution. In the conventional photolithography technique, after the dry etching treatment, the photoresist is removed, and a specific photoresist stripping solution is subjected to a wet etching treatment or a dry ashing treatment. On the one hand, if the cleaning solution of the present invention is used, the cleaning step can be carried out after the dry etching step without the above-mentioned treatment step, and the photoresist or the etching residue can be removed. Thereby, the interlayer insulating film material (especially the low dielectric constant material) can be less damaged without the dry ashing step, which further simplifies the processing step, and can shorten the manufacturing time of the semiconductor device. Drive down manufacturing costs. -21- 200948954 The cleaning liquid of the present invention can selectively etch the metal, the metal nitride, and the alloy contained in the object to be cleaned while removing the above-described etching residue or ash residue. More specifically, the etching ratio of the metal such as copper or TiN, or the metal nitride, and the alloy can be arbitrarily adjusted by appropriately selecting the constituent components of the cleaning liquid. In general, in the process of a semiconductor device, since various kinds of solutions such as a cleaning solution or an etching solution for wet etching are used, there is a need to replace the solution used in each step or the production line, so that Low productivity or increased costs. About 〇 When the cleaning liquid of the present invention is used, the desired metal can be etched while being washed. Therefore, the steps can be simplified, the production cost can be reduced, and the mass productivity can be improved, and the amount of the solution used in the process (manufacturing process) can be reduced, which is also related to the improvement of the problem such as the waste liquid treatment. The invention will be further described in detail. However, the invention is not limited by any of these embodiments. &lt;Example A &gt;

GW sequentially places copper, SiOC interlayer insulating film (Low-k film: k値2.6), SiCh film (TE0S film), metal hard mask (TiN), anti-reflection film, and photoresist on the germanium substrate. The film is subjected to dry etching by using the exposed and developed photoresist as a mask to form a through hole to obtain a pattern of copper, an interlayer insulating film, a metal hard mask, an antireflection film, and a photoresist exposed on the inner wall surface of the through hole. Wafer. When the cross section of the patterned wafer was confirmed by a scanning electron microscope photograph (SEM: Scanning Electron Microscope), etching residue was confirmed on the wall surface of the via hole. -22-.200948954 <Examples 1 to 9 and Comparative Examples 1 to 3> Next, the cleaning liquids 1 to 12 having the composition observed in Table 1 were prepared (as an example of the surfactant): Kao Co., Ltd. EMULGEN sold, SURFYNOL non-ionic surfactant sold by Nissin Chemical Industry Co., Ltd.) immersed the slice of the pattern wafer (2 cm x 2 cm) in each solution at a temperature adjusted to the temperature shown in Table 1, After the immersion time of Table 1, the slice of the pattern wafer was taken out, and immediately washed with ultrapure water and N: dried. The cross-section and surface of the cut wafer of the patterned wafer after the immersion test were observed by SEM, and the photoresist, the anti-reflective film, the removal of the etching residue, and the corrosiveness of the germanium substrate, the Si〇2 film, and the SiOC interlayer insulating film were observed. The following criteria were used for evaluation. The immersion test was carried out at an immersion temperature of 20 to 5 5 ° C and an immersion time of 30 seconds to 20 minutes. The evaluation results of the removability and uranium properties are summarized in Table 1. The evaluation criteria are as follows. "Removal" A: The photoresist, anti-reflection film, and etching residue are completely removed. ® B: Dissolved with residual photoresist, anti-reflective film, and uranium residue. C: Almost no photoresist, anti-reflection film, or etching residue was removed. "Corrosion" A: No rot was observed on the ruthenium substrate, the Si〇2 film, or the SiOC interlayer insulating film. B: A number of etchings were observed on at least one of the tantalum substrate, the SiCh film, and the SiOC interlayer insulating film. C: A large corrosion is observed in at least one of -23-200948954 materials in the tantalum substrate, the SiCh film, and the SiOC interlayer insulating film. In the above evaluation, it is desirable that the removability and corrosivity are completely A.

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0M.200948954 As shown in Table 1, in Examples 1 to 9 to which the cleaning liquid and the cleaning method of the present invention were applied, there was no corrosion of the substrate or the SiOC-based interlayer insulating film, and the photoresist, the anti-reflection film, and the etching residue were not observed. The removal property of the substance is excellent. In the cleaning using the cleaning solution of the present invention, the immersion temperature and the immersion time can be relatively freely selected, and the cleaning can be carried out at a low temperature and for a short period of time. Even in the forced condition in which the immersion time is prolonged, there is no ruthenium substrate. Corrosion of the SiCH film and the SiOC interlayer insulating film. In Comparative Examples 1 to 3, even when the immersion time and the immersion temperature were adjusted, it was impossible to show sufficient photoresist, antireflection film, and etch residue, and the ruthenium substrate, Si 〇 2 film, and SiOC layer. The insulating film is non-corrosive. &lt;Example B&gt; In the cleaning liquids 1 to 8 prepared in the same manner as in the above-described Example A, a blank wafer in which a TiN film (thickness: about 60 nm) and a Cu film (thickness: about 200 nm) were separately formed was separately formed. The fragment of the (blanket wafer) was calculated from the film thickness before and after the immersion and the immersion time, and the etching rate (A/min) for each film was calculated. The results are shown in Table 2. © In addition, the measurement of the film thickness was carried out using a film thickness measuring device (F20) manufactured by FILMETRICS. Table 2 Example 10 11 12 13 14 15 16 17 Solution No. 1 2 3 4 5 6 7 8 Treatment temperature Jtrc] 20 55 40 25 20 20 55 20 TiN etching rate (A/min) 3.4 24.7 13.5 2.4 0.2 4.2 35.2 8.6 Cu etching rate (Α )η) 0.1 10.3 10.4 3.1 0.1 13.2 32.2 20.7 As shown in Table 2, in Examples 10 to 17 to which the cleaning solution and the cleaning method of the present invention are applied, the etching rates of Cu and TiN can be freely adjusted. . By further adjusting the amount of the oxidizing agent, the amount of the metal etchant, and the processing temperature by further -26-200948954, the desired etching rate can be more adjustably obtained. As described above, in the examples A and B, it is understood that the cleaning liquid of the present invention 1 to 8 can be provided, and the interlayer insulating film contained in the object to be cleaned is not eroded during the cleaning process, and can be removed and washed. The photoresist, the antireflection film, and the etching residue in the object can simultaneously selectively etch the cleaning liquid of the metal, the metal nitride, and the alloy contained in the object to be cleaned, and the cleaning method thereof. [Simple description of the diagram] No. [Main component symbol description]

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Claims (1)

200948954 VII. Patent application scope: 1. A cleaning solution for a semiconductor device, which comprises an oxidizing agent, a metal etchant, and a surfactant, and has a pH of 10-14. 2. The cleaning solution for a semiconductor device according to the first aspect of the invention, wherein the oxidizing agent is hydrogen peroxide. 3. The cleaning solution for a semiconductor device according to the first aspect of the invention, wherein the metal etchant is an amine compound. 4. The cleaning solution for a semiconductor device according to claim 3, wherein the 0-amine compound is selected from the group consisting of ethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and tetra-strand At least one of the group consisting of acetaminophen and their derivatives. 5. The cleaning solution for a semiconductor device according to any one of claims 1 to 4, further comprising an inorganic base compound or a 4-stage ammonium hydroxide represented by the general formula (1), 1) Ri ❹ R2——N—R4 r3 OH′ wherein the general formula (1) independently represents an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a benzyl group or an aromatic group. base. 6. The cleaning solution for a semiconductor device according to claim 5, wherein the inorganic base compound is selected from the group consisting of lithium hydroxide, sodium hydroxide, barium hydroxide, barium hydroxide, and hydroxide. At least one of the groups. The cleaning solution for a semiconductor device according to any one of claims 1 to 6, wherein the surfactant is a cationic surfactant or a nonionic surfactant. 8. The cleaning solution for a semiconductor device according to claim 7, wherein the cationic surfactant is selected from the group consisting of a 4-grade ammonium salt-based surfactant and an alkylpyridinium-based surfactant. At least one of the groups. 9. The cleaning solution for a semiconductor device according to claim 7, wherein the g nonionic surfactant is selected from the group consisting of a polypropylene oxide polyethylene oxide surfactant and a polyalkylene oxide. a styrenated phenyl ether-based surfactant, a polyalkylene oxide alkylphenyl ether surfactant, a polyalkylene oxide tribenzyl phenyl ether surfactant, an acetylene polyalkylene oxide surfactant, And at least one of the group consisting of polyalkylene oxide alkyl ether surfactants. 10. A method of cleaning a semiconductor device, which comprises cleaning a semiconductor device using a cleaning solution for a semiconductor device according to any one of claims 1 to 9. Ii II. A method of cleaning a semiconductor device, which is characterized in that after the dry etching step %, the cleaning step of cleaning the semiconductor device using the cleaning solution for a semiconductor device according to any one of claims 1 to 9 is carried out. . 12. The method of cleaning a semiconductor device according to claim 10, wherein the semiconductor device is a semiconductor device comprising an interlayer insulating film having a dielectric constant k of 3.0 or less. -29- 200948954 IV. Designation of Representative Representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Λ 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: