Cleaning agent composition for removing resin mask

Abstract

One embodiment of the present invention provides a cleaning agent composition which has excellent resin mask removability.　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: the mass ratio A / B of the component A to the component B is 2 to 8 inclusive; and the component C is composed of at least one compound that is selected from among a sulfur-containing compound and a nitrogen-containing compound.

Description

Cleaning composition for removing resin masks

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

[0002] In recent years, personal computers and various electronic devices have become increasingly power-efficient, faster, and more compact, leading to increasingly finer wiring on package substrates and other components. While metal masking has traditionally been the primary method used to form such fine wiring and connection terminals such as pillars and bumps, its limited versatility and difficulty in meeting the demands of increasingly finer wiring have led to a shift to newer methods. One such new method is to use a dry film resist as a thick resin mask instead of a metal mask. This resin mask is ultimately peeled off and removed using an alkaline stripping cleaner.

[0003] A semiconductor device can be obtained by applying a resist onto a semiconductor substrate, forming a pattern by exposure and development, then etching the unmasked areas of the semiconductor substrate using the resist pattern as a mask to form a fine circuit, and then stripping the photoresist from the semiconductor substrate, or by similarly forming a fine circuit and then stripping the remaining resist residue from the semiconductor substrate by ashing. As such a resist stripping cleaner, Japanese Patent Laid-Open Publication No. 2005-55701 (Patent Document 1) discloses a cleaning agent for resist stripping, which is an amine, a compound having a Hansen solubility parameter of 18 to 33 MPa, 1 / 2 A resist stripper composition containing an organic solvent such as the above, a sugar, and 0 to 5% by weight of water has been proposed.

[0004] In one aspect, the present disclosure provides a composition comprising a polyhydric alcohol (component A), an amine (component B), and a solubility parameter (SP) of 18 to 33 MPa. 1 / 2 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.

[0005] In one aspect, the present disclosure relates to a cleaning 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.

[0006] In one aspect, the present disclosure relates to a method for producing a semiconductor element, the method comprising the step of removing a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning composition of the present disclosure.

[0007] In one aspect, the present disclosure relates to a method for manufacturing a semiconductor element, including a step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning method of the present disclosure.

[0008] In the manufacturing process of semiconductor devices, residues of resin masks attached to semiconductor substrates, metal wiring, interlayer insulating film thin films, etc. can cause poor connections between semiconductor chips and other components or damage to electronic components, resulting in defective products and reduced semiconductor chip yields. Therefore, cleaning compositions are required to have high resin mask removability (stripping ability). The cleaning composition proposed in Patent Document 1 had room for improvement in its resin mask removability. Generally, when the resin mask is a negative resist, it is more difficult to strip than a positive resist, and stripping of the negative resist requires harsh conditions (e.g., contact with a treatment agent (cleaning agent) at high temperature for a long period of time). Therefore, cleaning compositions are required to be able to strip negative resists under mild treatment conditions, i.e., to have excellent resin mask removability.

[0009] Therefore, the present disclosure provides a cleaning composition for stripping resin masks that has excellent resin mask removability, a cleaning method, and a method for producing semiconductor elements.

[0010] This disclosure is based on the discovery that resin masks can be efficiently removed from objects 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 specific proportions.

[0011] In one aspect, the present disclosure provides a composition comprising a polyhydric alcohol (component A), an amine (component B), and a solubility parameter (SP) of 18 to 33 MPa. 1 / 2(excluding components A and B) (component C), 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 compound selected from the group consisting of sulfur-containing compounds and nitrogen-containing compounds.

[0012] The present disclosure provides a cleaning composition that has excellent resin mask removal properties (stripping properties). The use of the cleaning composition of the present disclosure enables the production of high-quality semiconductor device circuits, particularly compound semiconductor device circuits.

[0013] Although the details of the mechanism of action by which the effects of the present disclosure are manifested are partially unknown, it is presumed as follows. The resin material forming the resin mask generally contains acidic functional groups such as phenolic resins. In the present disclosure, it is believed that the reaction of amines (component B) with acidic functional groups in the resin mask (resist) increases the solubility of the resin mask (resist) in a specific organic solvent (component C), thereby promoting peeling. Furthermore, it is believed that the combined use of a polyhydric alcohol (component A) and an amine (component B) in a specific ratio promotes the penetration of amines (component B) into the resin mask (resist), thereby improving peelability. However, the present disclosure need not be interpreted as being limited to this mechanism.

[0014] In the present disclosure, a resin mask refers to a mask that protects the surface of a material from processes such as etching, plating, and heating, i.e., 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 processes, a resist layer that has been subjected to at least one of exposure and development processes (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 when exposed to light or an electron beam. Resists are broadly classified into negative and positive types based on how they react with light or an electron beam. Negative resists have the property of decreasing solubility in a developer when exposed to light, and in a layer containing negative resist (hereinafter also referred to as a "negative resist layer"), the exposed portion is used as a resin mask after exposure and development processes. Positive resists have the property of increasing solubility in a developer upon exposure. After exposure and development, the exposed portions of a layer containing the positive resist (hereinafter also referred to as a "positive resist layer") are removed, and the unexposed portions are used as a resin mask. By using a resin mask with such properties, fine connections on a circuit board, such as metal wiring, metal pillars, and solder bumps, can be formed. In one or more embodiments, the resin material forming the resin mask can be a film-like photosensitive resin, a resist film, or a photoresist. General-purpose resist films can be used. Examples of resin masks include polyhydroxystyrene resin films, acrylic acid-based polymer films, and polyimide-based polymer films. Examples of polyimide-based polymer films used as resin masks include solvent-soluble polyimide films, such as alkali-soluble polyimide films. The thickness of the resin mask is selected based on the unevenness of the outermost surface of the front side of the semiconductor substrate, but it is sufficient if it can completely protect the front side of the semiconductor substrate. The thickness of the resin mask is, for example, 1 μm or more and 100 μm or less, and is preferably 3 μm or more and 50 μm or less from the viewpoint of completely protecting the front surface of the semiconductor substrate and from the viewpoint of the hardening time and removal time of the resist used as the resin mask.

[0015] [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 resin mask removability, Component A is preferably a dihydric to pentahydric alcohol, more preferably a dihydric to tetrahydric alcohol, even more preferably a dihydric or trihydric alcohol, and even more preferably a dihydric alcohol. Examples of dihydric alcohols include ethylene glycol and diethylene glycol. From the viewpoint of improving resin mask removability, 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.

[0016] From the viewpoint of improving resin mask removability, 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 same viewpoint, the content of Component A when using the cleaning composition of the present disclosure 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.

[0017] 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 cleaning composition starts to be used for cleaning. In one or more embodiments, the content of each component in the cleaning composition of the present disclosure can be considered to be the blending amount of each component in the cleaning composition of the present disclosure.

[0018] [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 used alone or in combination of two or more types.

[0019] In the above formula (I), R 1 represents a hydrogen atom, a methyl group, an ethyl group, or an aminoethyl group, and R 2 represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group, or an ethyl group, and R 3 represents a hydroxyethyl group or a hydroxypropyl group.

[0020] 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 resin mask removability, at least one of monoethanolamine (MEA) and N-methylmonoethanolamine is preferred as component B.

[0021] 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 viewpoints of improving resin mask removability and suppressing corrosiveness of substrate members. 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 types, the content of component B refers to the total content thereof.

[0022] From the viewpoint of improving resin mask removability, the mass ratio A / B of Component A to Component B (content of Component A / content of Component B) in the cleaning composition of the present disclosure is 8 or less, preferably 6 or less, and more preferably 5 or less, and from the same viewpoint, it is 2 or more, or 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.

[0023] From the viewpoint of improving resin mask removability, the total content of Component A and Component B when using the cleaning composition of the present disclosure is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more, and from the same viewpoint, it 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 Component A and Component B when using the cleaning composition of the present disclosure 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.

[0024] [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).

[0025] 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 to 31.5 MPa 1 / 2 is preferable, and 22 to 30 MPa 1 / 2 is more preferable. In the present disclosure, the Hansen solubility parameter (SP) value is the 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 types, the SP value of component C can be determined by a weighted average from the blending amounts. The above SP value range also applies to mixed organic solvents.

[0026] Component C includes at least one selected from sulfur-containing compounds and nitrogen-containing compounds. 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 nitrogen-containing compounds 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.

[0027] From the viewpoint of improving resin mask removability, 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 even more 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, from the viewpoint of improving resin mask removability, the content of dimethyl sulfoxide in the cleaning composition of the present disclosure is preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 67% by mass or less.

[0028] From the viewpoint of improving resin mask removability, 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 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 types, the content of component C refers to the total content thereof.

[0029] 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 resin mask removability. 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.

[0030] 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 still 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 still more preferably 50 or less. More specifically, from the same viewpoint, the mass ratio C / B in the cleaning composition of the present disclosure is 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 still more preferably 40 or more and 50 or less.

[0031] From the viewpoint of improving resin mask removability, the total content of Components A and C in the cleaning composition of the present disclosure during use 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 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 Components A and C in the cleaning composition of the present disclosure during use 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 believed that by incorporating Components A and C so that the total content falls within the specified range, it is possible to increase the solubility of the resin mask (resist) while suppressing corrosiveness of the substrate member.

[0032] From the viewpoint of improving resin mask removability, the total content of Component A, Component B, and Component C during use of the cleaning composition of the present disclosure is preferably 93% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, still more preferably 99% by mass or more, 99.5% by mass or more, or even more preferably 100% by mass.

[0033] [Sugars (Component D)] In one or more embodiments, the cleaning composition of the present disclosure may further contain a sugar (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, and D-fructose; disaccharides such as sucrose; trisaccharides such as raffinose; tetrasaccharides such as stachyose; linear sugar alcohols such as erythritol, xylitol, dulcitol, ribitol, D-sorbitol, D-mannitol, and L-iditol; and cyclic sugar alcohols such as cyclitol, myo-inositol, and quercitol.

[0034] From the viewpoint of inhibiting the corrosion 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.

[0035] 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% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoints of improving resin mask removability and corrosion inhibition, and from the same viewpoints, is preferably 3% by mass or less, more preferably 2.8% by mass or less, and even more preferably 2.5% by mass or less. More specifically, the content of component D during use of the cleaning composition of the present disclosure is preferably 0.01% by mass or more and 3% by mass or less, more preferably 0.1% by mass or more and 2.8% by mass or less, and even more preferably 0.5% by mass or more. When component D is a combination of two or more types, the content of component D refers to the total content of those components.

[0036] [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"). In one or more embodiments, the cleaning composition of the present disclosure may not contain water. Because semiconductors, particularly compound semiconductors such as GaAs, are susceptible to corrosion in the stripping step, it is preferable that the cleaning composition of the present disclosure does not contain water (a component). In one or more embodiments, examples of component E include ion-exchanged water, RO water, distilled water, pure water, and ultrapure water.

[0037] 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 components A, B, C, and optional components (component D and other components described later). From the viewpoints of improving resin mask removability and inhibiting corrosion, the content of component E when using the cleaning composition of the present disclosure is 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., absent).

[0038] [Other Components] In one or more embodiments, the cleaning composition of the present disclosure may further contain other components as necessary, within the scope of not impairing 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, antifoaming agents, and antibacterial agents.

[0039] [Method for producing detergent composition] In one or more embodiments, the detergent composition of the present disclosure can be produced by blending component A, component B, component C, and, if necessary, the above-mentioned optional components (component D, component E, other components) using a known method. For example, the detergent composition of the present disclosure can be produced by blending at least component A, component B, and component C. Accordingly, the present disclosure relates to a method for producing a detergent 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, if necessary, the above-mentioned optional components (component D, component E, other components) simultaneously or in any order. In the method for producing a detergent composition of the present disclosure, the preferred amount of each component to be blended can be the same as the preferred content of each component in the detergent composition of the present disclosure described above.

[0040] The cleaning composition of the present disclosure may be in a form that can be 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 can be diluted before use so that each component has the above-described content (i.e., the content at the time of cleaning).

[0041] 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.

[0042] [Object to be Cleaned] In one or more embodiments, the cleaning composition of the present disclosure may be used to clean an object to be cleaned having a resin mask attached thereto. In one or more embodiments, examples of the object to be cleaned having a resin mask attached thereto 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 semiconductor substrates 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, or the like. Examples of metal wiring include wiring made of gold, aluminum, copper, tungsten, titanium, tantalum, chromium, and the like, with gold and aluminum wiring being particularly suitable. The metal wiring used may be an alloy containing different metals or a pure metal, and the wiring shape is not limited. Examples of insulating films include silicon nitride (SiN) films. In one or more embodiments, the insulating film is an interlayer insulating film.

[0043] Examples of objects to be cleaned include electronic components and their manufacturing intermediates. Examples of electronic components include at least one component selected from printed circuit boards, wafers, and metal plates such as copper plates and aluminum plates. The manufacturing intermediates are intermediate products in the manufacturing process of electronic components, including intermediate products after resin mask treatment.

[0044] 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 this disclosure, soldering refers to applying solder to resin mask-free areas on a substrate and then heating to form solder bumps. In this disclosure, plating refers to performing at least one plating treatment selected from copper plating, aluminum plating, nickel plating, and tin plating on resin mask-free areas on a substrate. The resin mask-free areas refer to areas in a resist pattern (a patterned resin mask) formed by developing a resin mask laminated on a substrate, where the resin mask has been removed by the development treatment. Thus, in one aspect, the present disclosure relates to use of the cleaning composition of the present disclosure as a cleaner in the production of electronic components.

[0045] In one or more embodiments, the object to be cleaned is a substrate having a resist pattern (a patterned resin mask) formed by developing a resin mask laminated on the substrate, which 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 hardened resist layer is formed on the substrate, and a solder bump or a plating layer formed in a resin mask-free portion.

[0046] 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, in terms of cleaning effect. The resin mask may be, for example, a negative resin mask or a positive resin mask. In the present disclosure, a negative resin mask is formed using a negative resist, and examples thereof include a negative resist layer that has been subjected to exposure and / or development. In the present disclosure, a positive resin mask is formed using a positive resist, and examples thereof include a positive resist layer that has been subjected to exposure and / or development.

[0047] [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") that includes a step of peeling a resin mask from an object to which the resin mask is attached using a cleaning composition of the present disclosure (hereinafter also simply referred to as the "peeling step"). Examples of the object to be cleaned include the objects to be cleaned described above. In one or more embodiments, the peeling step includes contacting the object to be cleaned with the cleaning composition of the present disclosure. The cleaning method of the present disclosure can improve the removability (peeling ability) of the resin mask.

[0048] Examples of a method for stripping a resin mask from an object to be cleaned using the cleaning composition of the present disclosure, or a method for contacting an object to be cleaned with the cleaning composition of the present disclosure, include a method of contacting the object by immersion in a cleaning bath containing the cleaning composition, a method of contacting the object by spraying the cleaning composition (shower method), and an ultrasonic cleaning method in which ultrasonic waves are applied during immersion. The cleaning composition of the present disclosure can be used for cleaning as is without dilution. Examples of objects to be cleaned include the objects described above. In one or more embodiments, the cleaning method of the present disclosure can be used with a stripping device (cleaning device) such as a batch type, shower type, or single-wafer type.

[0049] 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, followed by 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, followed by rinsing with water.

[0050] In the cleaning method of the present disclosure, ultrasonic waves are preferably applied when the cleaning composition of the present disclosure comes into contact with the object to be cleaned, since this allows the cleaning power of the cleaning composition of the present disclosure to be more easily exerted. The ultrasonic waves are more preferably of a relatively high frequency. From the same viewpoint, the ultrasonic irradiation conditions are, for example, preferably 26 to 72 kHz and 80 to 1500 W, more preferably 36 to 72 kHz and 80 to 1500 W.

[0051] In the cleaning method of the present disclosure, the temperature of the cleaning composition is preferably 40° C. or higher, 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., still more preferably 65° C. or lower, and still more preferably 60° C. or lower, from the viewpoint of reducing the effect on the substrate.

[0052] [Method for Manufacturing Semiconductor Device] 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 (removal 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 objects to be cleaned described above. The semiconductor device manufacturing method of the present disclosure enables the production of high-quality semiconductor device circuits, particularly compound semiconductor device circuits. In one or more embodiments, the semiconductor device manufacturing method of the present disclosure includes the following steps (1) to (4). The apparatus, technique, etc. used in each of the following steps (1) to (4) are not particularly limited and may be any known method. (1) A lithography process comprising applying a resist to the surface (front side surface of the semiconductor substrate) of a semiconductor substrate having metal wiring and an interlayer insulating film on the surface, followed by patterning, exposure, and development. (2) An etching process for shaping the semiconductor substrate, the metal wiring, and the thin film of the interlayer insulating film. (3) An ion implantation process. (4) A 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): the lithography process and / or the above-mentioned step (4): the resist stripping process. Resist applied to semiconductor, particularly compound semiconductor, substrates, resist remaining after dry etching, and resist residue remaining after ashing after dry etching can be easily stripped at low temperature and in a short time. In one or more embodiments, the cleaning composition and cleaning method of the present disclosure may be used in the lift-off process in the compound semiconductor device manufacturing process.

[0053] [Method for Manufacturing Electronic Components] In one aspect, the present disclosure relates to a method for manufacturing electronic components (hereinafter also referred to as the "method for manufacturing 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 or cleaning method of the present disclosure. Examples of the object to be cleaned include the objects described above. In one or more embodiments, the method for manufacturing electronic components of the present disclosure may include a step of performing at least one of soldering and plating using a resin mask on at least one electronic component selected from a printed circuit board, a wafer, and a metal plate before the cleaning step. In the method for manufacturing electronic components of the present disclosure, cleaning using the cleaning method of the present disclosure improves resin mask removability (peeling ability), enabling the production of highly reliable electronic components. Furthermore, the cleaning method of the present disclosure facilitates removal of the resin mask attached to electronic components, thereby shortening the cleaning time and improving the production efficiency of electronic components.

[0054] [Kit] In one or more embodiments, the kit of the present disclosure is a kit for producing the cleaning composition of the present disclosure. The kit of the present disclosure can provide a cleaning composition that can improve resin mask removability. One embodiment of the kit of the present disclosure is a kit (two-liquid cleaning composition) that includes a solution containing Component A (first liquid) and a solution containing Components B and C (second liquid) in a mutually unmixed state, and the first liquid and the second liquid are mixed upon use. Each of the first liquid and the second liquid may contain the optional components described above, as necessary.

[0055] In one or more embodiments, the present disclosure further relates to the following cleaning composition for removing resin masks, cleaning method, and method for manufacturing semiconductor devices: <1> A cleaning agent composition for removing resin masks, comprising a polyhydric alcohol (component A), an amine (component B), and a solvent having a Hansen solubility parameter SP value of 18 to 33 MPa, 1 / 2wherein 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. <2> The cleaning composition according to <1>, wherein the mass ratio A / B of component A to component B is 1.5 or more and 6 or less. <3> The cleaning composition according to <1> or <2>, wherein component A is at least one of ethylene glycol and diethylene glycol. <4> The cleaning composition according to any one of <1> to <3>, wherein component B is an alkanolamine. <5> The cleaning composition according to any one of <1> to <4>, wherein component B is at least one of monoethanolamine and N-methylmonoethanolamine. <6> The cleaning composition according to any one of <1> to <5>, wherein component C is at least one selected from dimethyl sulfoxide and N-methyl-2-pyrrolidone. <7> The cleaning composition according to any one of <1> to <6>, wherein component C is a mixed organic solvent consisting essentially of a sulfur-containing compound and a nitrogen-containing compound. <8> The cleaning composition according to any one of <1> to <7>, wherein component C consists essentially of dimethyl sulfoxide and N-methyl-2-pyrrolidone. <9> The cleaning composition according to any one of <1> to <8>, wherein the content of component A is 4% by mass or more and 16% by mass or less. <10> The cleaning composition according to any one of <1> to <9>, wherein the content of component B is 0.5% by mass or more and 8% by mass or less. <11> The cleaning composition according to any one of <1> to <10>, wherein the total content of components A and C is 90% by mass or more and 99.5% by mass or less. <12> The detergent composition according to any one of <1> to <11>, further comprising a saccharide (component D), wherein the content of component D is 0.01% by mass or more and 3% by mass or less. <13> The cleaning composition according to <12>, wherein the molecular weight of component D is from 35 to 700. <14> The cleaning composition according to any one of <1> to <13>, wherein the content of water (component E) is 3 mass% or less. <15> A cleaning method comprising a 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 any one of <1> to <14>.<16> A method for producing a semiconductor element, comprising a 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 any one of <1> to <14>. <17> A method for producing a semiconductor element, comprising a step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning method according to <15>.

[0056] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to these examples in any way.

[0057] 1. Preparation of Cleaning Compositions of Examples 1 to 9 and Comparative Examples 1 and 2 The components shown in Tables 1 and 2 were blended in the amounts (% by mass, active ingredient) shown in Tables 1 and 2, and the blended mixture was stirred and mixed to prepare the cleaning compositions of Examples 1 to 9 and Comparative Examples 1 and 2.

[0058] The following substances were used to prepare the cleaning compositions of Examples 1 to 9 and Comparative Examples 1 and 2. (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 [manufactured by Nippon Shokubai Co., Ltd.] N-methylethanolamine [manufactured by Nippon Nyukazai Co., Ltd., amino alcohol MMA] (Component C) Dimethyl sulfoxide [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] N-methyl-2-pyrrolidone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (Component D) Sorbitol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., D-sorbitol] (Component E) Water [pure water of 1 μS / cm or less produced using a water purification system G-10DSTSET manufactured by Organo Corporation]

[0059] 2. Evaluation of Cleaning Compositions The cleaning compositions prepared in Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated as follows.

[0060] [Test Piece for Evaluating Strippability] 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, exposed to i-line light at a wavelength of 365 nm, and then post-baked at 130° C. for 5 minutes. The resist was then treated with CF4 gas, a reactive ion etching gas, to prepare a test piece.

[0061] [Removability Evaluation] Test pieces were immersed in each of the cleaning compositions prepared in Examples 1 to 9 and Comparative Examples 1 and 2 at 60°C for 30 minutes. Subsequently, as a rinse step, the test pieces were immersed in water at room temperature for 1 minute while shaking twice, and then blown dry with nitrogen gas. The appearance of the test pieces was observed with a field-emission scanning electron microscope at 5,000x and 50,000x magnifications. The presence or absence of resist residue on the insulating film (Si3N4) and GaAs substrate, and the state of the stripped resist were evaluated based on the following evaluation criteria. The results are shown in Tables 1 and 2. <Evaluation Criteria> 3: No resist residue was found on the substrate, and the stripped resist was dissolved in the cleaning composition. 2: No resist residue was found on the substrate, but the stripped resist was floating in the cleaning composition. 1: Resist residue was found on the substrate. The strippability evaluation results showed the following conditions for the resist residue on the substrate and the state of the stripped resist. Example 1: No resist residue was found 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 dissolved in the cleaning composition. Example 3: There was no resist residue on the substrate, and the resist partially peeled off and floated in the cleaning composition, before finally dissolving. Examples 4 to 9: There was no resist residue on the substrate, and the stripped resist dissolved in the cleaning composition. Comparative Examples 1 and 2: There was resist residue on the substrate.

[0062] [GaAs Etching Property Evaluation] An insulating film (Si3N4) with a height of 90 nm and a width of 10 nm was formed on a GaAs substrate in the form of stripes spaced 350 μm apart. The etching amount of GaAs was determined by the following steps (1) to (4), and the GaAs etching property was evaluated based on 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 substrate was immersed in the cleaning composition (Examples 5 to 7) at 70°C for 13 hours. (3) The step 2 after immersion (total thickness of the insulating film and the etched portion) was measured using an atomic force microscope. (4) The etching amount was calculated using the following formula: Etching amount = (step 2) - (step 1) <Evaluation criteria> ◎: Etching amount less than 10 nm ○: Etching amount 10 nm or more but less than 50 nm △: Etching amount 50 nm or more

[0063]

[0064]

[0065] 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 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 exceeded 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, sugar), was superior in corrosion inhibition effect for GaAs compared to Examples 5 and 7, which did not contain sugar (component D). The cleaning composition of Example 7, which contained water (component E), was inferior in corrosion inhibition effect for GaAs substrates compared to Examples 5 and 6, which did not contain water (component E).

[0066] According to the present disclosure, a cleaning composition capable of improving resin mask removability can be provided. Furthermore, use of the cleaning composition of the present disclosure can improve the performance and reliability of manufactured semiconductor elements, thereby improving the productivity of semiconductor devices.

Claims

1. Polyhydric alcohol (component A), amines (component B), and a Hansen solubility parameter SP value of 18 to 33 MPa 1 / 2 a 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 a sulfur-containing compound and a nitrogen-containing compound.

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

3. The cleaning composition according to claim 1 or 2, wherein component B is an alkanolamine.

4. The cleaning composition according to any one of claims 1 to 3, wherein component B is at least one of monoethanolamine and N-methylmonoethanolamine.

5. A cleaning composition according to any one of claims 1 to 4, wherein component C is a mixed organic solvent comprising a sulfur-containing compound and a nitrogen-containing compound.

6. A cleaning composition described in any one of claims 1 to 5, wherein the content of component A is 4 mass% or more and 16 mass% or less.

7. A cleaning composition described in any one of claims 1 to 6, wherein the content of component B is 0.5 mass% or more and 8 mass% or less.

8. A cleaning composition described in any one of claims 1 to 7, wherein the total content of components A and C is 90 mass% or more and 99.5 mass% or less.

9. A detergent composition according to any one of claims 1 to 8, further comprising a saccharide (component D), the content of component D being 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. A cleaning composition according to any one of claims 1 to 10, 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, using the cleaning composition according to any one of claims 1 to 11.

13. A method for manufacturing a semiconductor device, 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 composition according to any one of claims 1 to 11.

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, using the cleaning method of claim 12.

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