Cleaning agent composition for removing resin mask

Abstract

To provide a cleaning agent composition which has excellent resin mask removability.SOLUTION: One embodiment of the present disclosure relates to a cleaning agent composition for removing a resin mask, the cleaning agent composition containing a polyhydric alcohol (component A), an amine (component B), and an organic solvent (excluding the component A and the component B) which has a Hansen solubility parameter SP value of 18-33 MPa1 / 2 (component C), wherein: a mass ratio A / B of the component A to the component B is 2 to 8 inclusive; and the component C is at least one selected from sulfur-containing compounds and nitrogen-containing compounds.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a cleaning composition for stripping a resin mask and a cleaning method using the same. [Background technology]

[0002] In recent years, personal computers and various electronic devices have become more energy efficient, faster, and smaller, and the wiring on package substrates mounted on these devices is becoming finer year by year. Until now, the metal mask method has been mainly used to form such fine wiring and connection terminals such as pillars and bumps, but due to its low versatility and the difficulty of responding to the miniaturization of wiring, etc., other new methods are being used. One of the new methods is to use a dry film resist as a thick resin mask instead of a metal mask. This resin mask is finally peeled off and removed, and an alkaline stripping cleaner is used for this purpose.

[0003] A semiconductor element can be obtained by applying a resist onto a semiconductor substrate, forming a pattern by exposure and development, then using the resist pattern as a mask to etch the unmasked areas of the semiconductor substrate to form a fine circuit, and then peeling the photoresist off of the semiconductor substrate, or by forming a fine circuit in a similar manner and then peeling off the remaining resist residue from the semiconductor substrate by ashing. As such a resist stripping cleaner, Patent Document 1 describes an amine having a Hansen solubility parameter of 18 to 33 MPa. 1 / 2 A resist stripper composition containing the organic solvent, sugar, and 0 to 5% by weight of water has been proposed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2005-55701 A Summary of the Invention [Problem to be solved by the invention]

[0005] In the manufacturing process of semiconductor elements, the residue of the resin mask attached to the semiconductor substrate, metal wiring, interlayer insulating film thin film, etc., causes a connection failure between the semiconductor chip and other components and destruction of electronic components, resulting in defective products and a decrease in the yield of semiconductor chips. Therefore, the cleaning composition is required to have high resin mask removability (peelability). The cleaning composition proposed in Patent Document 1 had room for improvement in the removability of the resin mask. In general, when the resin mask is a negative resist, it is more difficult to peel off than a positive resist, and harsh conditions (for example, contact with a treatment agent (cleaning agent) at high temperature for a long time) are required to peel off the negative resist. Therefore, the cleaning composition is required to be able to peel off the negative resist under mild treatment conditions, that is, to have excellent resin mask removability.

[0006] Therefore, the present disclosure provides a cleaning composition for stripping a resin mask, which has excellent resin mask removability, a cleaning method, and a method for producing a semiconductor element. [Means for solving the problem]

[0007] In one embodiment, the present disclosure relates to a composition comprising a polyhydric alcohol (component A), an amine (component B), and a solubility enhancer having a Hansen solubility parameter SP value of 18 to 33 MPa. 1 / 2 The cleaning composition for stripping a resin mask comprises an organic solvent (excluding components A and B) (component C) represented by the formula (I) in which the mass ratio A / B of component A to component B is 2 or more and 8 or less, and component C is at least one compound selected from the group consisting of sulfur-containing compounds and nitrogen-containing compounds.

[0008] In one aspect, the present disclosure relates to a cleaning method including a step of peeling off a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning composition of the present disclosure.

[0009] In one aspect, the present disclosure relates to a method for producing a semiconductor element, the method including a step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning composition of the present disclosure.

[0010] In one aspect, the present disclosure relates to a method for manufacturing a semiconductor element, comprising a step of peeling off a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning method of the present disclosure. Effect of the Invention

[0011] According to the present disclosure, a cleaning composition having excellent resin mask removing ability can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present disclosure is based on the discovery that a resin mask can be efficiently removed from an object to be cleaned by using a cleaning composition containing a polyhydric alcohol (component A), an amine (component B), and a specific organic solvent (component C) in a specific ratio.

[0013] In one embodiment, the present disclosure relates to a composition comprising a polyhydric alcohol (component A), an amine (component B), and a solubility enhancer having a Hansen solubility parameter SP value of 18 to 33 MPa. 1 / 2 wherein the mass ratio A / B of component A to component B is 2 or more and 8 or less, and component C is at least one selected from a sulfur-containing compound and a nitrogen-containing compound.

[0014] According to the present disclosure, a cleaning composition having excellent resin mask removability (peelability) can be provided. Furthermore, by using the cleaning composition of the present disclosure, it becomes possible to manufacture high-quality semiconductor device circuits, particularly compound semiconductor device circuits.

[0015] Although the details of the mechanism of action by which the effects of the present disclosure are expressed are unclear, it is presumed as follows. Generally, the resin material forming the resin mask often contains an acidic functional group, such as a phenol resin. In the present disclosure, it is believed that the amines (component B) react with the acidic functional groups in the resin mask (resist), thereby increasing the solubility of the resin mask (resist) in a specific organic solvent (component C), and thus promoting the peeling. Furthermore, it is believed that the use of a polyhydric alcohol (component A) and an amine (component B) in a specific ratio in combination promotes the penetration of the amines (component B) into the resin mask (resist), thereby enhancing the peeling property. However, the present disclosure need not be construed as being limited to this mechanism.

[0016] In the present disclosure, a resin mask is a mask for protecting a material surface from treatments such as etching, plating, and heating, that is, a mask that functions as a protective film. In one or more embodiments, the resin mask may be a resist layer after exposure and development steps, a resist layer that has been subjected to at least one of exposure and development (hereinafter also referred to as "exposed and / or developed"), or a hardened resist layer. In one or more embodiments, the resin mask is formed using a resist whose physical properties, such as solubility in a developer, change due to light, electron beams, or the like. Resists are broadly divided into negative and positive types based on the reaction method with light or electron beams. A negative resist has a property that its solubility in a developer decreases when exposed to light, and the exposed portion of a layer containing a negative resist (hereinafter also referred to as a "negative resist layer") is used as a resin mask after exposure and development processing. A positive resist has a property that its solubility in a developer increases when exposed to light, and the exposed portion of a layer containing a positive resist (hereinafter also referred to as a "positive resist layer") is removed after exposure and development processing, and the unexposed portion is used as a resin mask. By using a resin mask having such properties, fine connections of a circuit board, such as metal wiring, metal pillars, and solder bumps, can be formed. In one or more embodiments, the resin material for forming the resin mask may be a film-like photosensitive resin, a resist film, or a photoresist. A general-purpose resist film may be used. Examples of the resin mask include a polyhydroxystyrene resin film, an acrylic acid-based polymer film, and a polyimide-based polymer film. Examples of the polyimide-based polymer film used as the resin mask include a solvent-soluble polyimide film, such as an alkali-soluble polyimide film. The thickness of the resin mask is selected depending on the step due to the unevenness of the outermost surface of the front side of the semiconductor substrate, but it is sufficient if the front side of the semiconductor substrate can be completely protected. The thickness of the resin mask is, for example, 1 μm to 100 μm, and is preferably 3 μm to 50 μm from the viewpoint of completely protecting the front side of the semiconductor substrate and the hardening time and removal time of the resist used as the resin mask.

[0017] [Component A: Polyhydric alcohol] The polyhydric alcohol (hereinafter also referred to as "Component A") contained in the cleaning composition of the present disclosure may be a polyhydric alcohol having 2 to 5 hydroxyl groups in the molecule from the viewpoint of improving resin mask removability. However, Component A does not include sugar alcohols. From the viewpoint of improving the removability of the resin mask, the component A is preferably a dihydric or more and pentahydric or less alcohol, more preferably a dihydric or more and tetrahydric or less alcohol, even more preferably a dihydric or trihydric alcohol, and even more preferably a dihydric alcohol. Examples of the dihydric alcohol include ethylene glycol and diethylene glycol. From the viewpoint of improving the removability of the resin mask, Component A is preferably at least one of ethylene glycol and diethylene glycol. Component A may be one type or a combination of two or more types.

[0018] The content of component A when using the cleaning composition of the present disclosure is preferably 4% by mass or more, more preferably 6% by mass or more, and even more preferably 8% by mass or more, from the viewpoint of improving resin mask removability, and from the same viewpoint, it is preferably 16% by mass or less, more preferably 14% by mass or less, and even more preferably 12% by mass or less. From the same viewpoint, the content of component A when using the cleaning composition of the present disclosure is preferably 4% by mass or more and 16% by mass or less, more preferably 6% by mass or more and 14% by mass or less, and even more preferably 8% by mass or more and 12% by mass or less. When component A is a combination of two or more types, the content of component A refers to the total content thereof.

[0019] In the present disclosure, "the content of each component in the cleaning composition at the time of use" refers to the content of each component at the time of cleaning, i.e., at the time when the use of the cleaning composition for cleaning is started. In one or more embodiments, the content of each component in the cleaning composition of the present disclosure can be considered as the blending amount of each component in the cleaning composition of the present disclosure.

[0020] [Component B: Amines] In one or more embodiments, the amines (hereinafter also referred to as "component B") contained in the cleaning composition of the present disclosure include alkanolamines (amino alcohols). Examples of alkanolamines include compounds represented by the following formula (I). Component B may be one type or a combination of two or more types. [ka]

[0021] In the above formula (I), R 1 represents a hydrogen atom, a methyl group, an ethyl group, or an aminoethyl group; R 2 represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group, or an ethyl group; R 3 represents a hydroxyethyl group or a hydroxypropyl group.

[0022] Examples of component B include at least one selected from monoethanolamine (MEA), monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, and N-(β-aminoethyl)diisopropanolamine. Among these, from the viewpoint of improving the removability of the resin mask, at least one of monoethanolamine (MEA) and N-methylmonoethanolamine is preferred as component B.

[0023] The content of component B when using the cleaning composition of the present disclosure is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.6% by mass or more, from the viewpoint of improving the removability of the resin mask and suppressing the corrosiveness of the substrate member, and from the same viewpoint, it is preferably 8% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. From the same viewpoint, the content of component B when using the cleaning composition of the present disclosure is preferably 0.5% by mass or more and 8% by mass or less, more preferably 1% by mass or more and 5% by mass or less, and even more preferably 1.6% by mass or more and 3% by mass or less. When component B is a combination of two or more kinds, the content of component B refers to the total content thereof.

[0024] The mass ratio A / B of components A and B (content of component A / content of component B) in the cleaning composition of the present disclosure is, from the viewpoint of improving resin mask removability, 8 or less, preferably 6 or less, and more preferably 5 or less, and from the same viewpoint, is 2 or more, may be 3 or more, or may be 4 or more. From the same viewpoint, the mass ratio A / B in the cleaning composition of the present disclosure is preferably 1 or more and 8 or less, more preferably 1.5 or more and 6 or less, and even more preferably 2 or more and 5 or less.

[0025] The total content of components A and B in the cleaning composition of the present disclosure when used is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more from the viewpoint of improving resin mask removability, and from the same viewpoint, is preferably 24% by mass or less, more preferably 20% by mass or less, and even more preferably 17% by mass or less. More specifically, the total content of components A and B in the cleaning composition of the present disclosure when used is preferably 5% by mass or more and 24% by mass or less, more preferably 8% by mass or more and 20% by mass or less, and even more preferably 10% by mass or more and 17% by mass or less.

[0026] [Component C: Organic solvent] The cleaning composition of the present disclosure has a Hansen solubility parameter SP value of 18 to 33 MPa. 1 / 2 The component C may be one type or a combination of two or more types (mixed organic solvent).

[0027] The SP value of component C is 18 to 33 MPa from the viewpoint of improving the removability of the resin mask. 1 / 2 20~31.5MPa 1 / 2 is preferable, and 22 to 30 MPa 1 / 2 In the present disclosure, the Hansen solubility parameter SP value is a value described in "Solubility Parameter Values" VII / pp. 675-714 of Polymer Handbook 4th Edition (published by Wiley Interscience). When component C is a mixed organic solvent of two or more kinds, the SP value of component C can be determined by a weighted average from the blending amount. The above SP value range also applies to the mixed organic solvent.

[0028] Component C includes at least one selected from a sulfur-containing compound and a nitrogen-containing compound. Examples of sulfur-containing compounds include compounds having a molecular weight of 200 or less and containing a sulfur atom, such as dimethyl sulfoxide and sulfolane. Examples of the nitrogen-containing compound include compounds having a molecular weight of 200 or less and containing a nitrogen atom, such as amides such as formamide, N-methylformamide, N-ethylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N-ethylacetamide, N,N-dimethylacetamide, and N,N-diethylacetamide; pyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, and N-butyl-2-pyrrolidone; and dimethylimidazolidinone.

[0029] From the viewpoint of improving the removability of the resin mask, component C is at least one selected from a sulfur-containing compound and a nitrogen-containing compound, and is preferably a mixed organic solvent containing a sulfur-containing compound and a nitrogen-containing compound, more preferably a mixed organic solvent consisting of a sulfur-containing compound and a nitrogen-containing compound, and further preferably the sulfur-containing compound is dimethyl sulfoxide and the nitrogen-containing compound is N-methyl-2-pyrrolidone. When component C is a mixed organic solvent containing dimethyl sulfoxide and N-methyl-2-pyrrolidone or a mixed organic solvent consisting of dimethyl sulfoxide and N-methyl-2-pyrrolidone, the content of dimethyl sulfoxide in the cleaning composition of the present disclosure is preferably 75 mass% or less, more preferably 70 mass% or less, and further preferably 67 mass% or less, from the viewpoint of improving the removability of the resin mask.

[0030] The content of component C when using the cleaning composition of the present disclosure is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, from the viewpoint of improving the removability of the resin mask, and from the same viewpoint, it is preferably 99.5% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. From the same viewpoint, the content of component C when using the cleaning composition of the present disclosure is preferably 60% by mass or more and 99.5% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and even more preferably 80% by mass or more and 90% by mass or less. When component C is a combination of two or more kinds, the content of component C refers to the total content thereof.

[0031] The mass ratio A / C of component A to component C (content of component A / content of component C) in the cleaning composition of the present disclosure is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, from the viewpoint of improving the removability of the resin mask. From the same viewpoint, it is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.25 or less, and preferably 0.2 or less. More specifically, the mass ratio A / C in the cleaning composition of the present disclosure is preferably 0.01 or more and 1 or less, more preferably 0.05 or more and 0.5 or less, even more preferably 0.1 or more and 0.2 or less.

[0032] The mass ratio C / B of component C to component B (content of component C / content of component B) in the cleaning composition of the present disclosure is, from the viewpoint of improving resin mask removability, preferably 15 or more, more preferably 20 or more, even more preferably 30 or more, and even more preferably 40 or more, and from the same viewpoint, preferably 100 or less, more preferably 80 or less, even more preferably 60 or less, and even more preferably 50 or less. More specifically, the mass ratio C / B in the cleaning composition of the present disclosure is, from the same viewpoint, preferably 15 or more and 100 or less, more preferably 20 or more and 80 or less, even more preferably 30 or more and 60 or less, and even more preferably 40 or more and 50 or less.

[0033] The total content of component A and component C when using the cleaning composition of the present disclosure is preferably 90% by mass or more, more preferably 93% by mass or more, and even more preferably 96% by mass or more, from the viewpoint of improving the removability of the resin mask, and from the same viewpoint, it is preferably 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less. From the same viewpoint, the total content of component A and component C when using the cleaning composition of the present disclosure is preferably 90% by mass or more and 99.5% by mass or less, more preferably 93% by mass or more and 99% by mass or less, and even more preferably 96% by mass or more and 98% by mass or less. It is considered that the total content of component A and component C can be contained within a predetermined range to increase the solubility of the resin mask (resist) while suppressing the corrosiveness of the substrate member.

[0034] From the viewpoint of improving resin mask removability, the total content of Components A, B, and C during use of the cleaning composition of the present disclosure is preferably 93 mass% or more, more preferably 95 mass% or more, even more preferably 98 mass% or more, still more preferably 99 mass% or more, 99.5 mass% or more, or 100 mass%.

[0035] [Sugars (ingredient D)] In one or more embodiments, the cleaning composition of the present disclosure may further contain a saccharide (hereinafter, also referred to as "Component D") from the viewpoint of inhibiting corrosion of metal wiring and semiconductors. Component D may be one type or a combination of two or more types. Examples of component D include monosaccharides such as D-xylose, D-glucose, L-idose, D-fructose, etc.; disaccharides such as sucrose, etc.; trisaccharides such as raffinose, etc.; tetrasaccharides such as stachyose, etc.; linear sugar alcohols such as erythritol, xylitol, dulcitol, ribitol, D-sorbitol, D-mannitol, L-iditol, etc.; cyclic sugar alcohols such as cyclitol, myo-inositol, quercitol, etc.; and the like.

[0036] From the viewpoint of inhibiting the corrosiveness of the substrate member, the molecular weight of component D is preferably 35 or more, more preferably 70 or more, and even more preferably 150 or more, and from the same viewpoint, it is preferably 700 or less, more preferably 350 or less, and even more preferably 185 or less. From the same viewpoint, the molecular weight of component D is preferably 35 or more and 700 or less, more preferably 70 or more and 350 or less, and even more preferably 150 or more and 185 or less.

[0037] When the cleaning composition of the present disclosure contains component D, the content of component D during use of the cleaning composition of the present disclosure is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and even more preferably 0.5 mass% or more from the viewpoints of improving resin mask removability and inhibiting corrosion, and from the same viewpoints, is preferably 3 mass% or less, more preferably 2.8 mass% or less, and even more preferably 2.5 mass% or less. More specifically, the content of component D during use of the cleaning composition of the present disclosure is preferably 0.01 mass% or more and 3 mass% or less, more preferably 0.1 mass% or more and 2.8 mass% or less, and even more preferably 0.5 mass% or more and 2.5 mass% or less. When component D is a combination of two or more types, the content of component D refers to the total content thereof.

[0038] [Component E: Water] In one or more embodiments, the cleaning composition of the present disclosure may further contain water (hereinafter also referred to as "component E"), or in one or more embodiments, may not contain water. Since semiconductors, particularly compound semiconductors such as GaAs, are easily corroded in the stripping step, it is preferable that the cleaning composition of the present disclosure does not contain water (component). In one or more embodiments, examples of component E include ion-exchanged water, RO water, distilled water, pure water, and ultrapure water.

[0039] When the cleaning composition of the present disclosure contains Component E, the content of Component E in the cleaning composition of the present disclosure can be the remainder excluding Component A, Component B, Component C, and optional components (Component D and other components described later). The content of Component E during use of the cleaning composition of the present disclosure is, from the viewpoints of improving resin mask removability and inhibiting corrosion, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and even more preferably 0% by mass (i.e., not contained).

[0040] [Other ingredients] In one or more embodiments, the cleaning composition of the present disclosure may further contain other components as necessary within a range that does not impair the effects of the present disclosure. Examples of other components include components that can be used in ordinary cleaning agents, such as alcohols other than component A, alkaline agents other than component B, amines other than component B, organic solvents other than component C, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymeric compounds, solubilizers, antioxidants, preservatives, defoamers, antibacterial agents, etc.

[0041] [Method of producing the cleaning composition] In one or more embodiments, the cleaning composition of the present disclosure can be produced by blending component A, component B, component C, and the above-mentioned optional components (component D, component E, other components) as necessary by a known method. For example, the cleaning composition of the present disclosure can be produced by blending at least component A, component B, and component C. Thus, the present disclosure relates to a method for producing a cleaning composition, which includes a step of blending at least component A, component B, and component C. In the present disclosure, "blending" includes mixing component A, component B, component C, and the above-mentioned optional components (component D, component E, other components) as necessary simultaneously or in any order. In the method for producing a cleaning composition of the present disclosure, the preferred blending amount of each component can be the same as the preferred content of each component of the cleaning composition of the present disclosure described above.

[0042] The cleaning composition of the present disclosure may be in a form used for cleaning as it is, or may be prepared as a concentrate to the extent that storage stability is not impaired by separation, precipitation, etc. The concentrate of the cleaning composition may be diluted at the time of use so that each component has the above-mentioned content (i.e., the content at the time of cleaning).

[0043] The pH of the cleaning composition of the present disclosure is preferably 8 or more and 14 or less, more preferably 9 or more and 14 or less, and even more preferably 10 or more and 14 or less, from the viewpoint of improving resin mask removability.

[0044] [Item to be cleaned] In one or more embodiments, the cleaning composition of the present disclosure can be used for cleaning an object to be cleaned having a resin mask attached thereto. In one or more embodiments, examples of the object to be cleaned with a resin mask attached include a semiconductor substrate having metal wiring and a resin mask, a semiconductor substrate having an insulating film and a resin mask, and a semiconductor substrate having metal wiring, an insulating film and a resin mask. Examples of the semiconductor substrate include substrates made of elemental semiconductors such as Si and Ge, compound semiconductors such as GaAs, InP and CdS, and mixed crystal semiconductors such as InGaAs and HgCdTe. In one or more embodiments, the metal wiring refers to metal wiring formed by plating, CVD, PVD, etc. Examples of metal wiring include wiring of gold, aluminum, copper, tungsten, titanium, tantalum, chromium, etc., and among them, gold and aluminum wiring are suitable. The metal wiring used may be an alloy containing different metals or a pure metal, and the wiring shape is not limited. The insulating film may be, for example, a silicon nitride (Si3N4) film, etc. In one or more embodiments, the insulating film is an interlayer insulating film.

[0045] The object to be cleaned may be, for example, an electronic component or an intermediate product thereof. The electronic component may be, for example, at least one component selected from a printed circuit board, a wafer, and a metal plate such as a copper plate or an aluminum plate. The intermediate product may be an intermediate product in the manufacturing process of an electronic component, including an intermediate product after a resin mask treatment.

[0046] Specific examples of objects to be cleaned with a resin mask attached include electronic components in which wiring, connection terminals, etc. are formed on the surface of a substrate by at least one of soldering and plating (copper plating, aluminum plating, nickel plating, tin plating, etc.) using a resin mask. In the present disclosure, soldering refers to providing solder in a resin mask-free portion on a substrate and forming a solder bump by heating. In the present disclosure, plating refers to performing at least one plating treatment selected from copper plating, aluminum plating, nickel plating, and tin plating on a resin mask-free portion on a substrate. The resin mask-free portion refers to a portion in a resist pattern (a resin mask having a pattern shape) formed by developing a resin mask laminated on a substrate, from which the resin mask has been removed by development. Thus, in one aspect, the present disclosure relates to the use of the cleaning composition of the present disclosure as a cleaning agent in the manufacture of electronic components.

[0047] In one or more embodiments, the object to be cleaned is a substrate having a resist pattern (a resin mask having a pattern shape) formed by developing a resin mask laminated on the substrate, and the substrate has undergone at least one of soldering and plating. For example, the object to be cleaned may be a substrate having a resin mask-existing portion where a cured resist layer is formed on the substrate, and a solder bump or a plating layer-existing portion where the resin mask is not present.

[0048] In one or more embodiments, the cleaning composition of the present disclosure can be suitably used for cleaning an object to which a resin mask or a resin mask that has been further plated and / or heated is attached, from the viewpoint of cleaning effect. The resin mask may be, for example, a negative resin mask or a positive resin mask. In the present disclosure, the negative resin mask is formed using a negative resist, and examples of the mask include a negative resist layer that has been exposed and / or developed. In the present disclosure, the positive resin mask is formed using a positive resist, and examples of the mask include a positive resist layer that has been exposed and / or developed.

[0049] [Cleaning method] In one aspect, the present disclosure relates to a cleaning method (hereinafter also referred to as the "cleaning method of the present disclosure") including a step of peeling a resin mask from an object to be cleaned to which the resin mask is attached using the cleaning composition of the present disclosure (hereinafter also simply referred to as the "peeling step"). Examples of the object to be cleaned include the above-mentioned objects to be cleaned. In one or more embodiments, the peeling step includes contacting the object to be cleaned with the cleaning composition of the present disclosure. According to the cleaning method of the present disclosure, the removability (peeling ability) of the resin mask can be improved.

[0050] Examples of the method for peeling off a resin mask from an object to be cleaned using the cleaning composition of the present disclosure, or the method for contacting the object to be cleaned with the cleaning composition of the present disclosure, include a method for contacting the object by immersing the object in a cleaning bath containing the cleaning composition, a method for contacting the object by ejecting the cleaning composition in a spray form (shower method), and an ultrasonic cleaning method for irradiating the object with ultrasonic waves during immersion. The cleaning composition of the present disclosure can be used for cleaning as it is without dilution. Examples of the object to be cleaned include the above-mentioned objects to be cleaned. In one or more embodiments, the cleaning method of the present disclosure can be used in a stripping apparatus (cleaning apparatus) such as a batch type, shower type, or single wafer type.

[0051] In one or more embodiments, the cleaning method of the present disclosure may include a step of contacting the object to be cleaned with the cleaning composition, rinsing with water, and drying. In one or more embodiments, the cleaning method of the present disclosure may include a step of contacting the object to be cleaned with the cleaning composition, and rinsing with water.

[0052] In the cleaning method of the present disclosure, it is preferable to irradiate ultrasonic waves when the cleaning composition of the present disclosure comes into contact with the object to be cleaned, and it is more preferable that the ultrasonic waves have a relatively high frequency, from the viewpoint of making it easier for the cleaning power of the cleaning composition of the present disclosure to be exerted. From the same viewpoint, the ultrasonic irradiation conditions are, for example, preferably 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.

[0053] In the cleaning method of the present disclosure, the temperature of the cleaning composition is preferably 40° C. or higher, and more preferably 50° C. or higher, from the viewpoint of easily exerting the detergency of the cleaning composition of the present disclosure, and is preferably 70° C. or lower, more preferably lower than 70° C., further preferably 65° C. or lower, and further preferably 60° C. or lower, from the viewpoint of reducing the effect on the substrate.

[0054] [Method of manufacturing semiconductor devices] In one or more embodiments, the present disclosure relates to a method for manufacturing a semiconductor device (hereinafter also referred to as the "semiconductor device manufacturing method of the present disclosure"), which includes a step (peeling step) of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning composition of the present disclosure or the cleaning method of the present disclosure. Examples of the object to be cleaned include the above-mentioned objects to be cleaned. The semiconductor device manufacturing method of the present disclosure makes it possible to manufacture a high-quality semiconductor device circuit, particularly a compound semiconductor device circuit. In one or more embodiments, the method for manufacturing a semiconductor device according to the present disclosure includes the following steps (1) to (4). The apparatus, method, etc. used in each of the steps (1) to (4) are not particularly limited and may be any known apparatus, method, etc. (1) A lithography process consisting of applying resist to the surface (front and side surfaces) of a semiconductor substrate having metal wiring and an interlayer insulating film on its surface, followed by patterning, exposure, and development. (2) Etching process for processing the shape of semiconductor substrates, metal wiring, and thin interlayer insulating films (3) Ion implantation process (4) Resist stripping process In one or more embodiments, the cleaning composition and cleaning method of the present disclosure are preferably used in the above-mentioned step (1): lithography step and / or the above-mentioned step (4) resist stripping step. The cleaning composition and cleaning method of the present disclosure can easily strip resist applied to a semiconductor, particularly a compound semiconductor substrate, resist remaining after dry etching, and resist residue remaining after ashing after dry etching at a low temperature and in a short time. In one or a plurality of embodiments, the cleaning composition and the cleaning method of the present disclosure may be used in the lift-off step in the manufacturing process of a compound semiconductor device.

[0055] [Electronic component manufacturing method] In one aspect, the present disclosure relates to a method for producing electronic components (hereinafter also referred to as the "method for producing electronic components of the present disclosure"), which includes a step of peeling a resin mask from an object to be cleaned to which the resin mask is attached (peeling step) using the cleaning composition of the present disclosure or the cleaning method of the present disclosure. Examples of the object to be cleaned include the above-mentioned objects to be cleaned. In one or more embodiments, the method for manufacturing an electronic component of the present disclosure may include, prior to the cleaning step, performing at least one of soldering using a resin mask and plating on at least one electronic component selected from a printed circuit board, a wafer, and a metal plate. In the manufacturing method of electronic components according to the present disclosure, the resin mask removability (peelability) can be improved by performing cleaning using the cleaning method according to the present disclosure, which enables the manufacturing of highly reliable electronic components. Furthermore, the resin mask attached to the electronic components can be easily removed by performing the cleaning method according to the present disclosure, which shortens the cleaning time and improves the manufacturing efficiency of electronic components.

[0056] [kit] In one or more embodiments, the kit of the present disclosure is a kit for producing the cleaning composition of the present disclosure. According to the kit of the present disclosure, a cleaning composition capable of improving resin mask removability can be obtained. One embodiment of the kit of the present disclosure is a kit (two-liquid cleaning composition) that contains a solution (first liquid) containing component A and a solution (second liquid) containing components B and C in a mutually unmixed state, and the first liquid and the second liquid are mixed at the time of use. Each of the first liquid and the second liquid may contain the above-mentioned optional components as necessary. EXAMPLES

[0057] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to these examples in any way.

[0058] 1. Preparation of cleaning compositions of Examples 1 to 9 and Comparative Examples 1 and 2 The cleaning compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were prepared by mixing the components shown in Tables 1 and 2 in the amounts (mass %, active content) shown in Tables 1 and 2 and stirring to mix.

[0059] The cleaning compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were prepared using the following materials. (Component A) Diethylene glycol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] Ethylene glycol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (Component B) Monoethanolamine [Nippon Shokubai Co., Ltd.] N-Methylethanolamine [Amino alcohol MMA, manufactured by Nippon Nyukazai Co., Ltd.] (Component C) Dimethyl sulfoxide [Fujifilm Wako Pure Chemical Industries, Ltd.] N-Methyl-2-pyrrolidone [Fujifilm Wako Pure Chemical Industries, Ltd.] (Component D) Sorbitol [Fujifilm Wako Pure Chemical Industries, Ltd., D-sorbitol] (Component E) Water [Pure water of 1μS / cm or less produced using the Organo Corporation pure water system G-10DSTSET]

[0060] 2. Evaluation of cleaning agent compositions The prepared cleaning compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated as follows.

[0061] [Test piece for evaluating peelability] After forming an insulating film (Si3N4) with a height of 90 nm and a width of 10 μm in stripes spaced 350 μm apart on a GaAs substrate (compound semiconductor substrate), a negative resist (polyhydroxystyrene resin) was applied to the entire surface of the substrate to a dry thickness of 3 μm, and after exposure to i-line spectrum with a wavelength of 365 nm, it was post-baked at 130°C for 5 minutes. After that, it was treated with CF4 gas, a reactive ion etching gas, to create a test piece.

[0062] [Removability evaluation] The test pieces were immersed in the cleaning compositions prepared in Examples 1 to 9 and Comparative Examples 1 and 2 at 60°C for 30 minutes. After that, the test pieces were immersed in water at room temperature for 1 minute while shaking twice as a rinsing process, and then blow-dried with nitrogen gas. The appearance of the test pieces was observed under a field emission scanning electron microscope at magnifications of 5,000 and 50,000, and the presence or absence of resist residue on the insulating film (Si3N4) and GaAs substrate, and the state of the peeled resist were evaluated based on the following evaluation criteria for strippability. The results are shown in Tables 1 and 2. <Evaluation criteria> 3: There is no resist residue on the substrate, and the stripped resist is dissolved in the cleaning composition. 2: There is no resist residue on the substrate, but the stripped resist is floating in the cleaning composition 1: Resist residue on the board As a result of the strippability evaluation, the state of the resist residue on the substrate and the stripped resist was as follows. Example 1: There was no resist residue on the substrate, but the stripped resist was floating in the cleaning composition. Example 2: There was no resist residue on the substrate, and the stripped resist was dissolved in the cleaning composition. Example 3: There was no resist residue on the substrate, and the resist was partially peeled off and floated in the cleaning composition, and then finally dissolved. Examples 4 to 9: There was no resist residue on the substrate, and the peeled resist was dissolved in the cleaning composition. Comparative Examples 1 and 2: Resist residue was found on the substrate.

[0063] [GaAs etching evaluation] An insulating film (Si3N4) with a height of 90 nm and a width of 10 nm was formed in stripes at intervals of 350 μm on a GaAs substrate, and the amount of GaAs etched was determined according to the following procedures (1) to (4). The GaAs etching performance was evaluated according to the following evaluation criteria. The results are shown in Table 2. (1) The initial step 1 (thickness of the insulating film) was measured using an atomic force microscope. (2) The sample was immersed in the cleaning composition (Examples 5 to 7) at 70° C. for 13 hours. (3) After immersion, the step 2 (the total thickness of the insulating film and the etched portion) was measured using an atomic force microscope. (4) The amount of etching was calculated using the following formula: Etching amount = (step 2) - (step 1) <Evaluation criteria> ◎: Etching amount is less than 10 nm ○: Etching amount is 10nm or more and less than 50nm △: Etching amount is 50nm or more

[0064] [Table 1]

[0065] [Table 2]

[0066] As shown in Table 1, the cleaning compositions of Examples 1 to 5 and 8 to 9, in which the mass ratio A / B was 2 or more and 8 or less, were found to be superior in removability (peelability) of a resin mask formed using a negative resist at an immersion temperature of 60°C, compared to Comparative Example 1, in which the mass ratio A / B was more than 8, and Comparative Example 2, in which the mass ratio A / B was 1.0. Furthermore, as shown in Table 2, the cleaning composition of Example 6, which contained sorbitol (component D, saccharide), was found to have a superior corrosion inhibition effect on GaAs compared to Examples 5 and 7, which did not contain saccharide (component D). The cleaning composition of Example 7, which contained water (component E), did not have a good corrosion inhibition effect on GaAs substrates compared to Examples 5 and 6, which did not contain water (component E). [Industrial Applicability]

[0067] According to the present disclosure, a cleaning composition capable of improving the removability of a resin mask can be provided. Furthermore, by using the cleaning composition of the present disclosure, the performance and reliability of the manufactured semiconductor element can be improved, and the productivity of the semiconductor device can be improved.

Claims

1. Polyhydric alcohol (component A), amines (component B), and a Hansen solubility parameter SP value of 18 to 33 MPa 1 / 2 The composition contains an organic solvent (excluding components A and B) (component C), The mass ratio A / B of component A to component B is 2 or more and 8 or less, A cleaning composition for stripping a resin mask, wherein component C is at least one selected from the group consisting of sulfur-containing compounds and nitrogen-containing compounds.

2. 2. The cleaning composition according to claim 1, wherein component A is at least one of ethylene glycol and diethylene glycol.

3. 2. The cleaning composition of claim 1, wherein component B is an alkanolamine.

4. The cleaning composition according to claim 1, wherein component B is at least one of monoethanolamine and N-methylmonoethanolamine.

5. 2. The cleaning composition according to claim 1, wherein component C is a mixed organic solvent comprising a sulfur-containing compound and a nitrogen-containing compound.

6. The cleaning composition according to claim 1, wherein the content of component A is 4% by mass or more and 16% by mass or less.

7. The cleaning composition according to claim 1, wherein the content of component B is 0.5% by mass or more and 8% by mass or less.

8. The cleaning composition according to claim 1, wherein the total content of component A and component C is 90% by mass or more and 99.5% by mass or less.

9. Further containing saccharides (component D), The detergent composition according to claim 1, wherein the content of component D is 0.01% by mass or more and 3% by mass or less.

10. The cleaning composition according to claim 9, wherein the molecular weight of component D is 35 or more and 700 or less.

11. The cleaning composition according to claim 1 , wherein the content of water (component E) is 3 mass % or less.

12. A cleaning method comprising the step of peeling off a resin mask from an object to be cleaned to which the resin mask is attached, by using the cleaning agent composition according to any one of claims 1 to 11.

13. A method for producing a semiconductor device, comprising the step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning composition according to claim 1 .

14. A method for manufacturing a semiconductor device, comprising the step of peeling off a resin mask from an object to be cleaned to which the resin mask is attached, by using the cleaning method according to claim 12.

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