TWI702285B - Treatment solution, method of cleaning substrate and method of manufacturing semiconductor device - Google Patents

Abstract

The subject of the present invention is to provide a treatment solution with excellent residue removal performance and corrosion resistance performance, and also excellent residue removal performance and corrosion resistance performance after repeated temperature environment changes. In addition, the subject of the present invention is also to provide a method for cleaning a substrate and a method for manufacturing a semiconductor element. The processing liquid of the present invention is a processing liquid for semiconductor elements, containing at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salt, water and an anticorrosive agent, and is counted by a light scattering type liquid particle counter of 0.05 μm or more The number of counted bodies of the size of is 1 to 2000 per 1 ml of the treatment solution.

Description

Processing liquid, method for cleaning substrate, and method for manufacturing semiconductor element

The invention relates to a processing solution, a method for cleaning a substrate, and a method for manufacturing a semiconductor element.

Semiconductor devices such as Charge-Coupled Device (CCD) and memory are manufactured by using photolithography technology to form fine electronic circuit patterns on a substrate. Specifically, a photoresist film is formed on a laminate of a metal film (for example, Co, W), an etching stop film, and an interlayer insulating film as a wiring material on a substrate, and a photolithography step and a dry etching step are performed. (For example, plasma etching treatment) to manufacture a semiconductor element.

In addition, a dry ashing step (for example, plasma ashing treatment) for peeling off the resist film is performed as necessary.

After the dry etching step, residues such as dry etching residues are attached to the metal film and/or the interlayer insulating film of the substrate. Therefore, the treatment of removing these residues by the treatment liquid is usually performed.

For example, Patent Document 1 discloses the use of a compound containing water and hydroxylamine salt And a composition of an anticorrosive agent as the treatment liquid (first invention etc.).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4880416

As described above, the treatment solution is sometimes used to remove residues attached to the metal film and/or the interlayer insulating film. Therefore, first of all, the above-mentioned treatment liquid is required to have excellent residue removal performance (residue removal performance). In addition, the treatment liquid is also required to suppress the occurrence of corrosion of the metal film or the interlayer insulating film (excellent corrosion resistance) when removing the residue.

In addition, the treatment liquid is refrigerated and stored at a predetermined temperature when not in use, and the treatment liquid is taken out from the refrigerated storage during use and restored to room temperature for use. Therefore, even after repeated changes in the temperature environment, the residue removal performance and corrosion resistance of the treatment liquid are required to be excellent.

However, the inventors of the present invention referred to the method and composition described in Patent Document 1 to prepare the treatment liquid, and learned that after repeated changes in the temperature environment of the treatment liquid, the residue removal performance and corrosion resistance of the treatment liquid were insufficient .

Therefore, the object of the present invention is to provide a treatment solution that is excellent in residue removal performance and corrosion resistance, and also excellent in residue removal performance and corrosion resistance after repeated temperature environment changes. In addition, the object of the present invention is also to provide a method for cleaning a substrate and a method for manufacturing a semiconductor element.

As a result of diligent research on the above subject, the inventors have found that by using a treatment solution containing an anticorrosive agent and having a size of 0.05 μm or more, the number of counted objects is 1 to 2000 per 1 ml of treatment solution. The desired performance, thus completing the present invention.

That is, the inventors of the present invention found that the problem can be solved by the following configuration.

[1] A treatment liquid, which is a treatment liquid for semiconductor elements, contains at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, water, and an anticorrosive agent, and is counted by a light scattering type liquid particle counter The number of counted objects with a size of 0.05 μm or more is 1 to 2000 per 1 ml of the treatment liquid.

[2] The treatment liquid according to [1], wherein the corrosion inhibitor is selected from the group consisting of triazole compounds, mercapto group-containing compounds, maleic anhydride, phthalic anhydride, ammonium thiosulfate, and tetramethyl At least one compound in the group consisting of guanidine and gallate.

[3] The treatment liquid according to [1] or [2], wherein the corrosion inhibitor contains a triazole compound, and the triazole compound contains a compound selected from the group consisting of benzotriazole, carboxybenzotriazole, 5- At least one compound of methyl-benzotriazole and triazole.

[4] The treatment liquid according to any one of [1] to [3], wherein the anticorrosive agent includes a triazole compound and a mercapto group-containing compound, and the triazole compound includes a benzotriazole , Carboxybenzotriazole, 5-methyl- At least one compound of benzotriazole and triazole, and the mercapto group-containing compound comprises a compound selected from 2-mercapto-5-methylbenzimidazole, 3-mercapto-1,2-propanediol, 2-mercaptothiazoline, At least one compound of 3-(2-aminophenylthio)-2-hydroxypropyl mercaptan and 3-(2-hydroxyethylthio)-2-hydroxypropyl mercaptan.

[5] The treatment liquid according to any one of [2] to [4], wherein the triazole compound contains 5-methyl-benzotriazole.

[6] The treatment liquid according to any one of [1] to [5], wherein the anticorrosive agent includes a triazole compound and a mercapto group-containing compound, and the mercapto group-containing compound is relative to the triazole The mass ratio of the compound is 0.1-50.

[7] The treatment liquid according to any one of [1] to [6], which further contains Fe ions in an amount of 10 mass ppt to 10 mass ppm.

[8] The treatment liquid according to any one of [1] to [7], which is used for cleaning and contains Cu, Co, W, AlO _x , AlN, AlO _x N _y , WO _x , Ti , TiN, ZrO _x , HfO _x and TaO _x any one or more metal hard mask substrates.

[9] A method for cleaning a substrate, comprising: a treatment liquid preparation step A, preparing the treatment liquid according to any one of [1] to [8]; and a cleaning step B, using the treatment Liquid to clean a substrate with a metal hard mask containing any one or more of Cu, Co, W, AlO _x , AlN, AlO _x N _y , WO _x , Ti, TiN, ZrO _x , HfO _x and TaO _x .

[10] The method for cleaning a substrate according to [9], further comprising: a drain recovery step C, recovering the drain of the treatment liquid used in the washing step B; and a washing step D. Using the draining liquid, clean the newly prepared ones containing Cu, Co, W, AlO _x , AlN, AlO _x N _y , WO _x , Ti, TiN, ZrO _x , HfO _x and TaO _x The metal hard mask substrate; and the drain recovery step E, recovering the drain used in the washing step D; and repeat the washing step D and the drain recovery step E to repeat Use the drainage.

[11] The method for cleaning a substrate according to [9] or [10], which includes removing from at least one of the hydroxylamine compound and the water before the treatment liquid preparation step A The metal ion removal step F of Fe ions, or after the treatment liquid preparation step A and before the washing step B, includes a metal ion removal step G of removing Fe ions in the treatment liquid.

[12] The method for cleaning a substrate according to any one of [9] to [11], which includes, before the treatment liquid preparation step A, a neutralization step I of neutralizing the water, or After the processing liquid preparation step A and before the washing step B, a neutralization step J of neutralizing the processing liquid is included.

[13] A method of manufacturing a semiconductor element, which includes using the treatment liquid as described in any one of [1] to [8] to clean a product containing Cu, Co, W, AlO _x , AlN, AlO _x Step of a substrate with a metal hard mask of any one or more of N _y , WO _x , Ti, TiN, ZrO _x , HfO _x and TaO _x .

As shown below, according to the present invention, it is possible to provide a treatment solution having excellent residue removal performance and corrosion resistance performance, and also excellent residue removal performance and corrosion resistance performance after repeated temperature environment changes. In addition, according to the present invention, a method for cleaning a substrate and a method for manufacturing a semiconductor element can also be provided.

1: substrate

2: Metal film

3: Etch stop layer

4: Interlayer insulating film

5: Metal hard mask

6: hole

10: Layers

11: inner wall

11a: section wall

11b: bottom wall

12: Dry etching residue

1 is a schematic cross-sectional view showing an example of a laminate applicable to the substrate cleaning method of the present invention.

Hereinafter, the processing liquid of the present invention will be described.

In addition, in the present invention, the numerical range represented by "~" means a range that includes the numerical values described before and after "~" as the lower limit and the upper limit.

In addition, in the present invention, 1 Å (Angstrom) corresponds to 0.1 nm.

In the expression of the group (atom group) in this specification, within the range that does not impair the effect of the present invention, expressions that do not describe substituted and unsubstituted include groups that do not have substituents, and also include groups that have substituents. . For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). The meaning of each compound is also the same.

In addition, the "radiation" in this specification refers to, for example, the bright line spectrum of a mercury lamp, the extreme ultraviolet and extreme ultraviolet (EUV (Extreme ultraviolet) light), X-rays, electron beams, etc.

In addition, in this specification, the term “light” means actinic rays or radiation. Unless otherwise specified, the "exposure" in this specification includes not only exposure using mercury lamps, excimer lasers such as extreme ultraviolet light, X-rays, EUV light, etc., but also using electron beams, ion beams, and other particle beams.的画。 The drawing.

In addition, in this specification, "(meth)acrylate" means both or either of acrylate and methacrylate, and "(meth)acrylic" means both or either of acrylic acid and methacrylic acid By.

In addition, in this specification, "single body" and "monomer" have the same meaning. Monomers in this specification are classified into oligomers and polymers, and unless otherwise specified, they refer to compounds having a weight average molecular weight of 2,000 or less. In this specification, the term "polymerizable compound" refers to a compound having a polymerizable functional group, and may be a single body or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

In addition, in this specification, when talking about "preparation", it means not only the preparation of specific materials by synthesis or blending, etc., but also the procurement of prescribed substances.

[Treatment solution]

The treatment liquid of the present invention is a treatment liquid for semiconductor devices, which contains at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salt, water and an anticorrosive agent, and is counted by a light scattering type liquid particle counter The number of counted objects with a size of 0.05 μm or more in the liquid is 1 to 2000 per 1 ml of the treatment liquid.

The treatment liquid of the present invention has excellent residue removal performance and anti-corrosion performance, and also excellent residue removal performance and anti-corrosion performance after repeated environmental temperature changes.

Although the details of this cause are not yet clear, it is roughly estimated as follows.

The details of the counted body of a predetermined size contained in the treatment liquid will be described later, but the counted body contained in the treatment liquid of the present invention is considered to be various solids (for example, organic solids, inorganic solids) or bubbles (For example, bubbles containing dissolved oxygen) and the like.

In the present invention, it is estimated that the counted objects of a predetermined size contained in the treatment liquid are those having excellent residue removal performance of the treatment liquid, and those having excellent residue removal performance after repeated environmental temperature changes. In particular, organic solids and bubbles containing dissolved oxygen function as an oxidizing agent. Therefore, it is estimated that the residue removal performance of the treatment liquid containing the above-mentioned object to be counted is more excellent.

In addition, when a solid substance is present as a kind of the object to be counted in the treatment liquid, bubbles containing dissolved oxygen adhere to the solid substance and tend to remain in the treatment liquid. Since the solid matter easily reaches the residue, it is presumed that if the solid matter is contained in the treatment liquid as a kind of object to be counted, it becomes easier to function as an oxidizing agent of the dissolved oxygen attached to the solid matter.

As described above, the treatment liquid containing a predetermined number of objects of a predetermined size has excellent residue removal performance. Therefore, when the residue attached to the metal film or the interlayer insulating film is removed using the treatment solution, the dissolved substance of the residue is contained in the treatment solution at a high concentration. Therefore, it is considered that the components constituting the metal film or the interlayer insulating film can be prevented from dissolving in the treatment liquid. As a result, it is estimated that the treatment Excellent anti-corrosion performance after environmental temperature changes.

On the other hand, the inventors of the present invention have learned that if the number of objects to be counted is more than 2,000, the corrosion protection performance becomes insufficient, or the residue removal performance and corrosion protection performance after repeated environmental temperature changes become insufficient. It is believed that the reason for the insufficiency of the corrosion resistance and the insufficiency of the corrosion resistance after repeated environmental temperature changes is that the counted body attached to the metal film or the interlayer insulating film dissolves from the metal film or the interlayer insulating film. The effect of the ingredients becomes stronger. In addition, it is believed that the reason for the insufficient residue removal performance after repeated environmental temperature changes is that the number of objects to be counted increases due to the repetition of temperature environment changes, and the increased objects to be counted adhere to the metal film and/or interlayer insulation The film becomes a new residue.

Furthermore, the inventors of the present invention have learned that if the number of objects to be counted is 0, the residue removal performance and the corrosion resistance performance become insufficient, or the corrosion resistance performance after repeated environmental temperature changes becomes insufficient. It is considered that the reason why the residue removal performance becomes insufficient is that the removal effect of the residue by the counted body is not effective. In addition, it is considered that the reason why the corrosion resistance becomes insufficient is that since the dissolved substances of the residues are reduced in the treatment liquid, the components constituting the metal film or the interlayer insulating film are easily dissolved in the treatment liquid. Furthermore, it is considered that the reason why the corrosion protection performance becomes insufficient after repeated environmental temperature changes is due to the degradation of the corrosion protection performance of the treatment liquid caused by the environmental temperature changes.

Hereinafter, the components contained in the treatment liquid and the components that can be contained will be described.

<Hydroxyamine compound>

The treatment liquid of the present invention contains at least one hydroxyl group selected from hydroxylamine and hydroxylamine salt. Base amine compound. The hydroxylamine compound promotes the decomposition and solubilization of the residue, and can suppress the corrosion of the cleaning object.

Here, the "hydroxyamine" in the hydroxylamine and the hydroxylamine salt of the treatment liquid of the present invention refers to a broad sense of hydroxylamines including substituted or unsubstituted alkylhydroxyamines, etc., and any of them can be obtained The effect of the application.

The hydroxylamine is not particularly limited, and preferred forms include unsubstituted hydroxylamine and hydroxylamine derivatives.

The hydroxylamine derivative is not particularly limited, and examples thereof include O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, and N,O- Dimethylhydroxylamine, N-ethylhydroxylamine, N,N-diethylhydroxylamine, N,O-diethylhydroxylamine, O,N,N-trimethylhydroxylamine, N,N-di Carboxyethylhydroxylamine, N,N-disulfoethylhydroxylamine, etc.

The salt of hydroxylamine is preferably an inorganic or organic acid salt of the hydroxylamine, more preferably a salt of an inorganic acid formed by bonding nonmetals such as Cl, S, N, P and hydrogen with hydrogen, and more preferably hydrochloric acid , Sulfuric acid, nitric acid, any acid salt.

The salt of hydroxylamine used to form the treatment liquid of the present invention is preferably hydroxylamine nitrate (also called Hydroxylamine Nitrate, HAN), hydroxylamine sulfate (also called Hydroxylamine Sulfate, HAS), and hydroxylamine hydrochloride. Salt (also known as Hydroxylamine Hydrochloride, HAC), hydroxylamine phosphate, N,N-diethylhydroxylamine sulfate, N,N-diethylhydroxyamine nitrate, and mixtures of these.

In addition, organic acid salts of hydroxylamine can also be used, and examples thereof include hydroxylamine citrate, hydroxylamine oxalate, and fluorinated hydroxylamine.

Furthermore, the treatment liquid of the present invention may also be in a form containing both hydroxylamine and its salt. These compounds may be used alone, or two or more of them may be appropriately used in combination.

Among the above, from the viewpoint that the desired effect of the present application can be significantly obtained, hydroxylamine and hydroxylamine sulfate are preferred, and hydroxylamine sulfate is more preferred.

Relative to the total mass of the treatment liquid, the content of the hydroxylamine compound is preferably 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 25% by mass, and still more preferably 1% by mass to 20% by mass. By setting it as said range, the desired effect of this application can be obtained remarkably.

<water>

The treatment liquid of the present invention contains water as a solvent. The content of water is not particularly limited, and it is usually contained in the range of 20% to 98% by mass, preferably 60% to 98% by mass, and more preferably 70% to 95% by mass relative to the mass of the entire treatment liquid.

As the water, ultrapure water used in semiconductor manufacturing is preferred.

<Anti-corrosion agent>

The treatment liquid of the present invention contains an anticorrosive agent. The anti-corrosion agent can inhibit the corrosion of the metal film and the interlayer insulating film when removing the residue.

As an anti-corrosion agent, from the viewpoint of further improving the anti-corrosion performance of the treatment liquid, it is preferably selected from the group consisting of triazole compounds, mercapto group-containing compounds, maleic anhydride, phthalic anhydride, ammonium thiosulfate, and tetramethyl At least one compound in the group consisting of guanidine and gallate.

The anticorrosive agent can be used alone or in combination of two or more.

Among these anti-corrosion agents, the anti-corrosion performance of the treatment liquid can be further improved. From a point of view, the treatment liquid more preferably contains a triazole compound. The triazole compound has a planar structure and adheres to the metal film and the interlayer insulating film at the planar structure portion, so it is estimated that the adhesion to the metal film and the interlayer insulating film is excellent. Thereby, it is estimated that the anti-corrosion performance of the treatment liquid is easily exerted.

It is more preferable that the treatment liquid contains both a triazole compound and a mercapto group-containing compound. Thereby, the corrosion resistance of the treatment liquid is further improved, and the corrosion resistance of the treatment liquid after repeated temperature environment changes becomes better. It is presumed that the reason is that the mercapto group contained in the mercapto group-containing compound supplements the adhesion force of the triazole compound, whereby the anticorrosive performance of the treatment liquid is easily exerted.

As a triazole compound, the triazole compound which has a benzene ring structure (namely, a benzotriazole compound), the triazole compound which does not have a benzene ring structure, etc. are mentioned, for example.

Examples of benzotriazole compounds include: benzotriazole (BTA), carboxybenzotriazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chloro Benzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthotriazole, Tolyltriazole, 5-phenyl-benzotriazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-Amino-benzotriazole, 5-methyl-benzotriazole, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5- Ethylbenzotriazole, 4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole, 5-isopropylbenzotriazole, 4-n-butyl Benzotriazole, 5-n-butylbenzotriazole, 4-isobutylbenzotriazole, 5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole Triazole, 4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-methoxybenzotriazole, 5-hydroxybenzotriazole Triazole, dihydroxypropyl benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-tertiary butylbenzotriazole, 5 -(1',1'-Dimethylpropyl)-benzotriazole, 5-(1',1',3'-trimethylbutyl)benzotriazole, 5-n-octylbenzo Triazole and 5-(1',1',3',3'-tetramethylbutyl)benzotriazole, etc.

Examples of triazole compounds having no benzene ring structure include triazole (specifically, 1,2,3-triazole and 1,2,4-triazole), 3-amino-1,2,4 -Triazole, 3,5-diamino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4- Triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3 -Mercapto-4-methyl-1,2,4-triazole and 3-isopropyl-1,2,4-triazole, etc.

From the viewpoint of further improvement in corrosion resistance, the treatment liquid preferably contains at least one compound selected from the group consisting of benzotriazole, carboxybenzotriazole, 5-methyl-benzotriazole and triazole, and more preferably Contains 5-methyl-benzotriazole.

When a triazole compound is contained as an anticorrosive agent, the content of the triazole compound is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass relative to the total mass of the treatment liquid. When the content of the triazole compound is within the above range, the corrosion resistance is further improved.

Examples of compounds containing a mercapto group include 2-mercapto-5-methylbenzimidazole, 3-mercapto-1,2-propanediol, 2-mercaptothiazoline, and 3-(2-aminophenylthio) -2-hydroxypropyl mercaptan, 3-(2-hydroxyethylthio)-2-hydroxypropyl mercaptan, 2-mercaptobenzothiazole (2-Mercaptobenzothiazole, 2-MBT), 1-phenyl- 5-mercaptotetrazole, 5-amino-1,3,4-thiadiazole-2-thiol and 2,5-dimercapto-1,3-thiadiazole ascorbic acid, etc.

Among the compounds containing mercapto groups, the treatment liquid preferably contains a compound selected from 2- Mercapto-5-methylbenzimidazole, 3-mercapto-1,2-propanediol, 2-mercaptothiazoline, 3-(2-aminophenylthio)-2-hydroxypropyl mercaptan and 3-( At least one compound of 2-hydroxyethylthio)-2-hydroxypropyl mercaptan.

By combining these preferred mercapto group-containing compounds with the triazole compound (especially at least one compound selected from benzotriazole, carboxybenzotriazole, 5-methyl-benzotriazole and triazole) ) In combination, the corrosion resistance of the treatment liquid is further improved, and the corrosion resistance of the treatment liquid after repeated temperature environmental changes becomes better.

The mercapto group-containing compound in the present invention does not include a compound having a mercapto group and a triazole group. In the present invention, a compound having a mercapto group and a triazole group is classified as the triazole compound.

When the mercapto group-containing compound is included as the corrosion inhibitor, the content of the mercapto group-containing compound is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 5% by mass relative to the total mass of the treatment liquid. When the content of the mercapto group-containing compound is within the above range, the corrosion resistance is further improved.

When the corrosion inhibitor includes the triazole compound and the mercapto group-containing compound, the mass ratio of the mercapto group-containing compound to the triazole compound (the content of the mercapto group-containing compound/the content of the triazole compound) is better It is 0.1-50, more preferably 0.1-20, and still more preferably 0.1-10. When the mass ratio is within the above range, the residue removal performance and corrosion resistance performance after long-term refrigerated storage of the treatment liquid becomes excellent.

Relative to the total mass of the treatment liquid, the content of the corrosion inhibitor is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 5% by mass, and still more preferably 0.1 Mass%~3% by mass. When the content of the anti-corrosion agent is within the above-mentioned range, the effect obtained by containing the anti-corrosion agent is further exhibited.

<counted body>

In the present invention, the number of objects to be counted with a size of 0.05 μm or more counted by the light scattering type liquid particle counter is 1 to 2000 per 1 ml of the treatment liquid.

Here, the object to be counted of the present invention is not particularly limited as long as it is detected with a size of 0.05 μm or more by a light scattering type liquid particle counter.

The light scattering type in-liquid particle counter irradiates a sample fluid (processing liquid in the present invention) with a beam of light to form a particle detection area, and uses a light receiving element to receive scattered light caused by an object to be counted passing through the particle detection area , Detect the counted body in the sample fluid, and count the number of counted bodies.

In addition to solids, the light-scattering type in-liquid particle counter may detect bubbles or the like containing gas (dissolved oxygen, etc.) as the object to be counted.

It is presumed that the object to be counted in the present invention is specifically impurities contained in the raw material of the treatment liquid (such as dust, dust, organic solids, inorganic solids, and other solids), which are mixed as contaminants in the preparation of the treatment liquid Impurities (such as dust, dust, organic solids, inorganic solids, and other solids), bubbles mixed in the raw materials of the treatment liquid, and bubbles mixed in the preparation of the treatment liquid.

As the light scattering type liquid particle counter, a device based on the liquid particle counter "KS-18F" (manufactured by Rion Co., Ltd.) was used. The measurement conditions of the treatment liquid by the light scattering type in-liquid particle counter are as described in the column of Examples described later.

The number of counted objects with a size of 0.05 μm or more contained in the treatment solution of the present invention is 1 to 2000, preferably 1 to 1000, more preferably 1 to 400, and still more preferably 1 Above and less than 300, particularly preferably 1 to 100.

When the number of the counted objects is within the above range, the residue removal performance and corrosion resistance of the treatment liquid are excellent, and the residue removal performance and corrosion resistance of the treatment liquid after repeated environmental temperature changes become excellent.

On the other hand, if the number of the counted bodies is 0, the residue removal performance and the corrosion resistance of the treatment liquid become insufficient, or the corrosion resistance of the treatment liquid after repeated environmental temperature changes becomes insufficient. In addition, if the number of the counted bodies becomes more than 2000, the corrosion resistance of the treatment liquid becomes insufficient, or the residue removal performance and corrosion resistance of the treatment liquid after repeated environmental temperature changes become insufficient .

In the present invention, the size of the object to be counted by the light scattering type liquid particle counter is 0.05 μm or more.

The upper limit of the size of the object to be counted is not particularly limited, but it is usually 10 μm or less. Furthermore, the detection of objects with a size of less than 0.05 μm involves technical difficulties.

In view of its intended use, the treatment liquid of the present invention preferably does not contain particles of 0.1 μm or more (specifically, coarse particles such as impurities). This can prevent the coarse particles contained in the treatment liquid itself from becoming residues.

As a method of removing coarse particles, for example, treatment such as filtration described later can be cited. In addition, particles larger than 10μm can be measured using a laser diffraction particle size distribution measuring device. set.

<Fe ion>

The treatment liquid of the present invention preferably contains Fe ions at 10 mass ppt to 10 mass ppm. Thereby, even if the treatment liquid is used after long-term refrigeration and storage, the residue removal performance of the treatment liquid is excellent. It is presumed that the reason is that Fe ions act as an oxidizing agent and can maintain the residue removal performance of the treatment liquid.

Relative to the total mass of the treatment liquid, the content of Fe ions is preferably 10 mass ppt to 10 mass ppm, more preferably 10 mass ppt to 1,000 mass ppb, and still more preferably 10 mass ppt or more and less than 1,000 mass ppt.

<Other ingredients>

The treatment liquid of the present invention may contain other components than the above. Examples of other components include chelating agents, water-soluble organic solvents, pH adjusters, quaternary ammonium hydroxides, and alkanolamines.

(Chelating agent)

The treatment liquid may also contain a chelating agent. The chelating agent chelates the oxidized metal contained in the residue. Therefore, by adding a chelating agent, reusability is further improved.

The chelating agent is not particularly limited, but is preferably a polyamino polycarboxylic acid.

Polyaminopolycarboxylic acid is a compound having multiple amine groups and multiple carboxylic acid groups, for example, including: mono- or polyalkylene polyamine polycarboxylic acid, polyaminoalkane polycarboxylic acid, polyaminoalkanol Polycarboxylic acid and hydroxyalkyl ether polyamine polycarboxylic acid.

As a preferred polyamine-based polycarboxylic acid chelating agent, for example, butanediamine Tetraacetic acid, Diethylenetriamine Pentaacetic Acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraaminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N,N,N' ,N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (Ethylene Diamine Tetraacetic Acid, EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediacetic acid, ethyl Diamine dipropionic acid, 1,6-hexamethylene-diamine-N,N,N',N'-tetraacetic acid, N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N -Diacetic acid, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclododecane-tetraacetic acid, diaminopropanoltetraacetic acid and (hydroxyethyl)ethylenediaminetriacetic acid. Among them, preferred are diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA), and trans-1,2-diaminocyclohexanetetraacetic acid. These compounds can be formulated individually or in combination of two or more.

In the treatment liquid, the content of the chelating agent is preferably 0.01% by mass to 5% by mass, and more preferably 0.01% by mass to 3% by mass relative to the total mass of the treatment liquid of the present invention.

(Water-soluble organic solvent)

The treatment liquid of the present invention may also contain a water-soluble organic solvent. Since the treatment liquid contains a water-soluble organic solvent, the solubilization of the added components and organic residues can be promoted, and the anti-corrosion effect can be further improved.

The water-soluble organic solvent is not particularly limited. For example, water-soluble alcohols, water-soluble ketones, water-soluble esters, and water-soluble ethers (for example, glycol diethers) can be used. Any of these water-soluble organic solvents.

As water-soluble alcohols, for example, alkylene glycols (including alkylene glycols), alkoxy alcohols (including glycol monoethers), saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, and Low molecular weight alcohol with ring structure.

Examples of alkanediols include diols, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-diol, 1,4-butanediol Alcohol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol and alkylene glycol.

Examples of alkylene glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.

Examples of alkoxy alcohols include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol and water-soluble Glycol monoether.

As the glycol monoether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl Base ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethyl Glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol , Propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether and ethylene glycol mono Benzyl ether, diethylene glycol monobenzyl ether.

Examples of saturated aliphatic monohydric alcohols include methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tertiary butanol, 2-pentanol, and tertiary pentyl alcohol. Alcohol and 1-hexanol.

Examples of unsaturated non-aromatic monohydric alcohols include aryl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.

Examples of the low-molecular-weight alcohol containing a ring structure include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

Examples of water-soluble ketones include acetone, propanone, cyclobutanone, cyclopentanone, diacetone alcohol, 2-butanone, 5-hexanedione, and 1,4-cyclohexanedione , 3-hydroxyacetophenone, 1,3-cyclohexanedione and cyclohexanone.

Examples of water-soluble esters include glycol monoesters such as ethyl acetate, ethylene glycol monoacetate, and diethylene glycol monoacetate, as well as propylene glycol monomethyl ether acetate and ethylene glycol monomethyl Glycol monoether monoesters such as ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol monoethyl ether acetate.

Among these, ethylene glycol monobutyl ether, tris(propylene glycol) methyl ether, and diethylene glycol monoethyl ether are preferable.

Among the water-soluble organic solvents, from the viewpoint of further enhancing the anticorrosive effect, water-soluble alcohols are preferred, alkanediols, diols, and alkoxy alcohols are more preferred, and alkoxy alcohols are particularly preferred.

The water-soluble organic solvent may be used alone, or two or more of them may be appropriately used in combination.

The content of the water-soluble organic solvent is preferably 0.1% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass, relative to the total mass of the treatment liquid of the present invention.

(pH adjuster)

The pH of the treatment liquid of the present invention is not particularly limited, but it is preferably greater than or equal to the pKa of the conjugate acid of hydroxylamine and hydroxylamine salt. With the pKa or higher of the conjugate acid of hydroxylamine and hydroxylamine salt, the residue removal performance is dramatically improved. In other words, when the ratio of hydroxylamine and hydroxylamine salt in a molecular state in the treatment liquid is large, the effect of the present invention can be remarkably obtained. For example, the pKa of the conjugate acid of hydroxylamine is about 6.

The treatment liquid of the present invention is preferably set to pH 3-11. In order to adjust the pH of the treatment solution Within the above range, it is desirable that the treatment liquid contains a pH adjuster.

If the pH of the treatment liquid is within the above range, both the corrosion rate and the residue removal performance are more excellent.

As a measuring method of pH, a well-known pH meter can be used for measurement.

As the pH adjuster, a well-known one can be used, but it is generally preferable that it does not contain metal ions. For example, ammonium hydroxide, monoamines, and imines (for example, 1,8-diazabicyclo[5.4.0] Undecane-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene), 1,4-diazabicyclo[2.2.2]octane, guanidine salts (such as carbonic acid) Guanidine) etc., in order to obtain the desired effect of the present application, any of these can be used. Among them, from the viewpoint of remarkably obtaining the desired effect of this application, ammonium hydroxide and imines (for example, 1,8-diazabicyclo[5.4.0]undecane-7-ene , 1,5-diazabicyclo[4.3.0]non-5-ene).

The pH adjuster may be used alone, or two or more of them may be appropriately used in combination.

As long as the treatment liquid can achieve the desired pH, the amount of the pH adjuster is not particularly limited, but usually in the treatment liquid, the concentration of 0.1% to 5% by mass relative to the total mass of the treatment liquid is ideal Containing, it is more desirable to be 0.1% by mass to 2% by mass.

(Quaternary ammonium hydroxide)

The treatment liquid of the present invention may also contain quaternary ammonium hydroxides. By adding quaternary ammonium hydroxides, the residue removal performance can be further improved. In addition, it can also function as a pH adjuster.

The quaternary ammonium hydroxides are preferably compounds represented by the following general formula (4) Things.

(In formula (4), R ^4A to R ^4D each independently represent an alkyl group having 1 to 6 carbons, a hydroxyalkyl group having 1 to 6 carbons, a benzyl group, or an aryl group).

In formula (4), R ^4A ~ R ^4D each independently represent an alkyl group having 1 to 6 carbon atoms (such as methyl, ethyl, butyl, etc.), a hydroxyalkyl group having 1 to 6 carbon atoms (such as hydroxymethyl , Hydroxyethyl, hydroxybutyl, etc.), benzyl or aryl (for example, phenyl, naphthyl group, naphthalene group, etc.). Among them, alkyl, hydroxyethyl, and benzyl are preferred.

As the compound represented by formula (4), specifically, it is preferably selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylhydroxyethylammonium hydroxide , At least one quaternary ammonium hydroxide from the group consisting of methyl tris (hydroxyethyl) ammonium hydroxide, tetra (hydroxyethyl) ammonium hydroxide, trimethyl benzyl ammonium hydroxide and choline. Among them, in the present invention, it is more preferable to use at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, benzyltrimethylammonium hydroxide, and choline. Quaternary ammonium hydroxide can be used alone or in combination Two or more are used.

In the treatment liquid, relative to the total mass of the treatment liquid of the present invention, the content of the quaternary ammonium hydroxide is preferably 0.1% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass, and still more preferably 0.5% by mass %~5 mass%.

(Alkanolamines)

The treatment liquid may also contain alkanolamines from the viewpoint of promoting the solubilization of the additive components and the organic residues and preventing corrosion.

Alkanolamines may be any one of primary amine, secondary amine, or tertiary amine, preferably monoamine, diamine, or triamine, more preferably monoamine. The alkanol group of the amine preferably has 1 to 5 carbon atoms.

In the treatment liquid of the present invention, a compound represented by the following formula (5) is preferred.

Formula (5): R ¹ R ² -N-CH ₂ CH ₂ -OR ³

(In formula (5), R ¹ and R ² each independently represent a hydrogen atom, a methyl group, an ethyl group, and a hydroxyethyl group, and R ³ each independently represents a hydrogen atom, or a hydroxyethyl group. However, the formula contains at least 1 Alkyl)

As alkanolamines, there are specifically monoethanolamine, diethanolamine, triethanolamine, tertiary butyldiethanolamine, isopropanolamine, 2-amino-1-propanol, and 3-amino-1-propanol , Isobutanolamine, 2-amino-2-ethoxy-propanol, and 2-amino-2-ethoxy-ethanol also known as diglycolamine. Alkanolamines can be used alone or in combination of two or more.

In the treatment liquid, relative to the total mass of the treatment liquid of the present invention, the content of alkanolamines is preferably 0.1% by mass to 80% by mass, more preferably 0.5% by mass to 50% by mass, and still more preferably 0.5% by mass. 20% by mass.

(Other additives)

Within the range in which the effects of the present invention are obtained, the treatment liquid of the present invention may contain other additives. Examples of other additives include surfactants, defoamers, and the like.

<Set and Concentrate>

The treatment liquid of the present invention may also be a set obtained by dividing the raw material into a plurality of pieces. For example, a form in which a liquid composition containing a hydroxylamine compound in water is prepared as the first liquid, and a liquid composition containing other components in water is prepared as the second liquid. As an example of its use, it is preferable to mix the two liquids to prepare a treatment liquid, and thereafter apply it to the form of the treatment in a timely manner. Organic solvents etc. may be contained in any one. This prevents deterioration of liquid performance due to decomposition of the hydroxylamine compound or other components, and can effectively exert the desired effect. The content of each component in the first liquid and the second liquid can be appropriately set as the content after mixing based on the aforementioned content.

In addition, the treatment liquid can also be prepared as a concentrated liquid. In this case, it can be diluted with water when used.

<container>

The processing liquid of the present invention (regardless of whether it is a set or not) can be filled in any container, stored and transported, and then used as long as corrosiveness and the like are not a problem. As the container, for semiconductor applications, one having high cleanliness and less elution of impurities is preferred. As Usable containers include: "Clean Bottle" series manufactured by Aicello Chemical (Co., Ltd.), "Pure Bottle" manufactured by Kodama Plastics (Stock) "Etc., but not limited to these containers. The inner wall of the container or its accommodating portion is preferably made of a resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or is rust-proof . Metal elution prevents the formation of treated metals.

As the different resin, a fluorine resin (perfluoro resin) can be particularly preferably used. In this way, by using a container in which the inner wall of the accommodating portion is made of fluorine-based resin, compared with the case of using a container in which the inner wall of the accommodating portion is made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin, ethylene can be suppressed. Or the elution of propylene oligomers.

As a specific example of a container in which the inner wall of such a storage portion is a fluorine-based resin, for example, a FluoroPure (Perfluoroalkoxy, PFA) composite barrel manufactured by Entegris, etc. may be cited. In addition, pages 4 of Japanese Patent Publication No. 3-502677, etc., page 3 of International Publication No. 2004/016526, etc., and pages 9 and 16 of International Publication No. 99/46309 may also be used. The container described in the page, etc.

<filter>

The treatment liquid of the present invention is preferably filtered with a filter for the purpose of adjusting the number of the objects to be counted to a desired number, or for removing foreign substances or reducing defects. As long as it has been used for filtering purposes, etc., there are no special restrictions Use locally. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon, polyolefin resins (including high density, ultra-high molecular weight) such as polyethylene and polypropylene (PP), etc. filter. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

When using filters, different filters can also be combined. At this time, the filtration with the first type filter may be performed only once, or may be performed two or more times. When different filters are combined to perform filtration two or more times, it is preferable that the pore size after the second time is equal to or larger than the pore size of the first filtration. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, available from Japan Pall Co., Ltd., Advantec Toyo Co., Ltd., Japan Interge Co., Ltd. (formerly Mykrolis, Japan) Co., Ltd. or Kitz Microfilter Co., Ltd. to choose from various filters provided.

For the second type of filter, a filter formed of the same material as the first type of filter can be used.

For example, filtration by the first type of filter can be performed using a mixed liquid containing a part of the components of the treatment liquid, the remaining components are mixed therein to prepare the treatment liquid, and then the second filtration is performed.

<Metal concentration>

The treatment liquid of the present invention is preferably a metal other than Fe contained in the liquid as an impurity (Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn gold The ion concentration of the genus element) is 5 ppm or less (preferably 1 ppm or less). In particular, in the manufacture of top-notch semiconductor devices, because it is assumed that a higher purity treatment liquid is required, the metal concentration is preferably lower than the ppm level, that is, the ppb level or less, and more preferably the ppt level (so The stated concentrations are based on quality), and it is particularly preferred that it contains substantially no.

As a method of reducing the metal concentration, for example, in at least one of the stage of the raw material used in the production of the treatment liquid and the stage after the preparation of the treatment liquid, sufficient distillation or filtration using an ion exchange resin can be cited.

As another method of reducing the metal concentration, there can be mentioned: Regarding the "container" that contains the raw materials used in the manufacture of the treatment liquid, the use of the "container" that contains the treatment liquid has less elution of impurities as shown in the section describing the container for the treatment liquid Container. In addition, a method such as applying a fluorine-based resin lining to the inner wall of the pipe so that the metal component does not elute from the "piping" when preparing the treatment liquid or the like can also be cited.

<Use>

The processing liquid of the present invention is a processing liquid for semiconductor elements. In the present invention, the so-called "semiconductor device use" refers to use in the manufacture of semiconductor devices. The treatment solution of the present invention can also be used in any step for manufacturing semiconductor elements, for example, it can be used in the treatment of resist films, etching residues, anti-reflection films, and ashing residues present on the substrate.

The treatment liquid is specifically used in the form of a cleaning solution (eluent) used in the removal of residues such as etching residues attached to the metal film or interlayer insulating film, and various types of resists for pattern formation. The solution used in the removal of the etchant film and the permanent film (such as color filters, transparent insulating films, resin lenses) Wait for the solution removed from the semiconductor substrate. Furthermore, the semiconductor substrate from which the permanent film has been removed may be used again in the use of the semiconductor element. Therefore, the removal of the permanent film is included in the manufacturing process of the semiconductor element.

The treatment liquid of the present invention is particularly preferably used for metal hardening materials having any one or more of Cu, Co, W, AlO _x , AlN, AlO _x N _y , WO _x , Ti, TiN, ZrO _x , HfO _x and TaO _x Cleaning of the masked substrate (hereinafter, also referred to as "masked substrate").

<Method of Manufacturing Treatment Liquid>

Regarding the treatment liquid of the present invention, its production method is not particularly limited. It can be manufactured by thoroughly mixing predetermined raw materials using a mixer such as a mixer. In addition, a method of preparing to a set pH in advance and then mixing, or a method of preparing to a set pH after mixing can be used. Furthermore, it is also possible to use the method of manufacturing the concentrate containing the said compound, and diluting at the time of use, and adjusting to a predetermined concentration. In addition, it can also be used after diluting the concentrated liquid and adjusting to the set pH. In addition, a predetermined amount of pure water for dilution may be added to the concentrated liquid, or a predetermined amount of concentrated liquid may be added to the pure water for dilution.

The manufacturing method of the treatment liquid of the present invention preferably includes a method for mixing predetermined raw materials and then counting by a light scattering type in-liquid particle counter to count the number of objects to be counted with a size of 0.05 μm or more per 1 ml. Number of steps. The step to set the number of counted objects with a size of 0.05 μm or more counted by a light scattering type liquid particle counter to a predetermined number can be implemented by the following methods: use a filter to perform purification such as filtration Steps, at the same time or at any time by light The scattering-type liquid particle counter counts the number of objects to be counted, and the preparation of the treatment liquid is completed at the point when the number of objects to be counted contained in the treatment liquid reaches a desired value. As a filter used for purification such as filtration of the treatment liquid of the present invention, in terms of efficiently removing counted objects with high negative charges in the treatment liquid of the present invention containing alkaline compounds and water, it is preferably Positively charged nylon filter.

In addition, the counting of objects to be counted by the light-scattering type in-liquid particle counter can be performed in batches, or in-line, that is, the light-scattering type in-liquid particle counter is integrated into the processing liquid production line and continuously Count.

In addition, with regard to a normal processing liquid, the number of counted objects with a size of 0.05 μm or more counted by a light scattering type liquid particle counter is often more than 2000 per 1 ml of the processing liquid.

In addition, the treatment liquid of the present invention may be a set obtained by dividing the raw material into a plurality of pieces. For example, a form in which a liquid composition containing a basic compound in water is prepared as the first liquid, and a liquid composition containing other components in water is prepared as the second liquid. As an example of its use, it is preferable to mix the two liquids to prepare a treatment liquid, and thereafter apply it to the form of the treatment in a timely manner. Organic solvents etc. may be contained in any one. Thereby, the deterioration of the liquid performance caused by the decomposition of the basic compound or other components is not caused, and the effect of the present invention can be effectively exhibited. The content of each component in the first liquid and the second liquid can be appropriately set as the content after mixing based on the aforementioned content.

[How to clean the substrate]

The cleaning method of the substrate of the present invention includes: a treatment liquid preparation step A for preparing the treatment liquid; and a washing step B, using the treatment liquid to clean the substrates containing Cu, Co, W, AlO _x , AlN, AlO _x N _y , WO _x , Ti, TiN, ZrO _x , HfO _x, and TaO _x for a metal hard mask substrate.

<Washing object>

The cleaning target of the substrate cleaning method of the present invention is any object that contains Cu, Co, W, WO _x , AlO _x , AlN, AlO _x N _y , Ti, TiN, ZrO _x , HfO _x, and TaO _x . There is no particular limitation on the substrate of more than one metal hard mask.

Furthermore, the metal hard mask is formed in a pattern and has a predetermined opening.

In addition, the cleaning target of the substrate cleaning method of the present invention includes, for example, a laminate having at least a metal film, an interlayer insulating film, and a metal hard mask in this order on the substrate. The laminate further has a hole formed from the surface (opening portion) of the metal hard mask toward the substrate by going through a dry etching step or the like to expose the surface of the metal film.

The manufacturing method of the laminate with holes as described above is not particularly limited. Generally, the following methods can be cited: a metal hard mask is used as a mask, and a substrate, a metal film, an interlayer insulating film, and a metal hard mask are sequentially provided The pre-processed laminate is subjected to a dry etching step, and the interlayer insulating film is etched in a manner that the surface of the metal film is exposed, thereby providing holes penetrating the metal hard mask and the interlayer insulating film.

In addition, the manufacturing method of a metal hard mask is not specifically limited, For example, the following method is mentioned. First, the metal film containing predetermined components is formed, and the resist film of a predetermined pattern is formed on it. Second, the resist film is used as a mask to etch the metal film to produce a metal hard mask.

In addition, the laminate may have layers other than the above-mentioned layers, and examples thereof include an etching stop film, an anti-reflection layer, and the like.

A schematic cross-sectional view showing an example of a laminate as a cleaning target object of the substrate cleaning method of the present invention is shown in FIG. 1.

The laminate 10 shown in FIG. 1 sequentially has a metal film 2, an etching stop layer 3, an interlayer insulating film 4, and a metal hard mask 5 on a substrate 1. The metal is formed on a predetermined position by a dry etching step, etc. The hole 6 of the film 2 is exposed. That is, the cleaning object shown in FIG. 1 has the substrate 1, the metal film 2, the etching stop layer 3, the interlayer insulating film 4, and the metal hard mask 5 in this order, and is positioned at the opening of the metal hard mask 5 The laminate has a hole 6 extending from the surface to the surface of the metal film 2. The inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a including an etch stop layer 3, an interlayer insulating film 4, and a metal hard mask 5, and a bottom wall 11b including the exposed metal film 2, and dry etching residue 12 is attached.

The cleaning method of the substrate of the present invention can be preferably used for cleaning for the purpose of removing the dry etching residue 12. That is, the dry etching residue 12 has excellent removal performance, and also has excellent corrosion protection performance for the inner wall 11 (for example, the metal film 2 and the like) of the cleaning target.

In addition, the cleaning method of the substrate of the present invention may be performed on the laminate that has been subjected to the dry ashing step after the dry etching step.

Hereinafter, the constituent materials of each layer of the laminate will be described.

(Metal hard mask)

The metal hard mask is not particularly limited as long as it contains any one or more of Cu, Co, W, AlO _x , AlN, AlO _x N _y , WO _x , Ti, TiN, ZrO _x , HfO _x and TaO _x . Here, x and y are numbers represented by x=1~3 and y=1~2, respectively.

Examples of the material of the metal hard mask include TiN, WO ₂ , and ZrO ₂ .

(Interlayer insulating film)

The material of the interlayer insulating film is not particularly limited, and examples thereof include: preferably, the dielectric constant k is 3.0 or less, and more preferably 2.6 or less.

Specific examples of the material of the interlayer insulating film include organic polymers such as SiO ₂ , SiOC-based materials, and polyimide.

(Etch stop layer)

The material of the etching stop layer is not particularly limited. Specific examples of the material of the etching stop layer include metal oxides such as SiN, SiON, SiOCN-based materials, and AlO _x .

(Metal film)

The wiring material forming the metal film is not particularly limited, and examples thereof include metals, metal nitrides, and alloys. Specifically, for example, copper, titanium, titanium-tungsten, titanium nitride, tungsten, cobalt, tantalum, tantalum compound, chromium, chromium oxide, aluminum, etc. can be mentioned. From the viewpoint of enjoying the effects of the treatment liquid of the present invention, as the wiring material, cobalt and tungsten are particularly desirable.

(Substrate)

The "substrate" mentioned here includes, for example, a semiconductor substrate including a single layer and a semiconductor substrate including multiple layers.

The material constituting the semiconductor substrate comprising a single layer is not particularly limited, and it is usually preferable to include III-V compounds such as silicon, silicon germanium, GaAs, or any of these combination.

When it is a semiconductor substrate containing multiple layers, the structure is not particularly limited. For example, the semiconductor substrate such as silicon may have an exposed integrated circuit structure such as interconnect features such as metal wires and dielectric materials. . Examples of metals and alloys used in the interconnection structure include aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten, but they are not limited to These metals and alloys. In addition, the semiconductor substrate may also have an interlayer dielectric layer, a layer of silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide.

Hereinafter, the treatment liquid preparation step A and the washing step B are respectively described in detail.

(Processing solution preparation step A)

The treatment liquid preparation step A is a step of preparing the treatment liquid. The components used in this step are as described above.

The procedure of this step is not particularly limited. For example, the following method can be cited: adding a hydroxylamine compound, an anticorrosive agent, and other optional components to water, and stirring and mixing, thereby preparing a treatment liquid. Furthermore, when each component is added to water, it can be added at once, or it can be divided into multiple times and added.

In addition, it is preferable that each component contained in the processing liquid is classified into a semiconductor grade or a high purity grade based on this. In addition, it is preferable to use a component with a large amount of impurities at the time of the raw material that has been subjected to foreign matter removal by filtration, and ion-exchange resin or the like to reduce ion components.

Furthermore, in order to bring the number of the objects to be counted contained in the treatment liquid into a desired range, it is preferable to perform treatment such as the filtration.

(Washing step B)

Examples of the substrate with a mask to be cleaned in the cleaning step B include the above-mentioned laminates. As described above, a laminate with holes formed with a dry etching step can be exemplified. Furthermore, in the laminate, dry etching residues adhered to the holes.

In addition, the laminate that has been subjected to the dry ashing step after the dry etching step may be used as the cleaning target.

The method of bringing the processing liquid into contact with the masked substrate is not particularly limited, and examples include: a method of immersing the masked substrate in the processing liquid added to the tank, and spraying the processing liquid onto the masked substrate The method on the substrate, the method of pouring the processing liquid on the substrate with the mask, or any combination of these. From the viewpoint of the removability of residues, a method of immersing a substrate with a mask in a processing liquid is preferred.

The temperature of the treatment liquid is preferably set to 90°C or lower, more preferably 25°C to 80°C, further preferably 30°C to 75°C, particularly preferably 40°C to 65°C.

The washing time can be adjusted according to the washing method used and the temperature of the treatment liquid.

When washing using the immersion batch method (a batch method in which multiple pieces of washing objects are immersed in a treatment tank to be processed), the washing time is, for example, within 60 minutes, preferably 1 minute to 60 minutes. More preferably, it is 3 minutes to 20 minutes, and still more preferably 4 minutes to 15 minutes.

When washing is performed in a piece-by-piece manner, the washing time is, for example, 10 seconds to 5 minutes, preferably 15 seconds to 4 minutes, more preferably 15 seconds to 3 minutes, and further preferably 20 seconds to 2 minutes.

Furthermore, in order to further improve the cleaning ability of the treatment liquid, a mechanical stirring method may also be used.

As a mechanical stirring method, for example, a method of circulating a processing liquid on a substrate with a mask, a method of flowing or spraying a processing liquid on a substrate with a mask, and stirring by ultrasonic or megasonic waves The method of processing liquid, etc.

(Rinse step B2)

The substrate cleaning method of the present invention may further include a step of cleaning the substrate with a mask by using a solvent after the cleaning step B (rinsing step B2).

The rinsing step B2 is preferably performed immediately after the washing step B, and a step of washing with a rinsing solvent for 5 seconds to 5 minutes. The rinsing step B2 can be performed using the mechanical stirring method.

Examples of the rinsing solvent include: deionized (DI: De Ionize) water, methanol, ethanol, isopropanol, N-methylpyrrolidone, γ-butyrolactone, dimethylsulfene, ethyl lactate And propylene glycol monomethyl ether acetate, but not limited to these rinse solvents. Alternatively, an aqueous rinse with pH>8 (diluted aqueous ammonium hydroxide, etc.) can also be used.

As the rinse solvent, ammonium hydroxide aqueous solution, DI water, methanol, ethanol and isopropanol are preferred, ammonium hydroxide aqueous solution, DI water and isopropanol are more preferred, and ammonium hydroxide aqueous solution and DI water are more preferred.

As a method of contacting the rinsing solvent with the substrate with the mask, the method of contacting the substrate with the mask with the processing liquid described above can be similarly applied.

The temperature of the rinsing solvent in the rinsing step B2 is preferably 16°C to 27°C.

The treatment liquid can also be used as the rinsing solvent in the rinsing step B2.

(Drying step B3)

The substrate cleaning method of the present invention may include a drying step B3 of drying the masked substrate after the rinsing step B2.

The drying method is not particularly limited. As the drying method, for example, a spin drying method, a method of flowing a dry gas on a substrate with a mask, a method of heating the substrate with a heating means such as a hot plate or an infrared lamp, and Marangoni drying ( marangoni drying method, rotagoni drying method, isopropyl alcohol (IPA) drying method, or any combination of these.

Although the drying time depends on the specific method used, it is usually preferably 30 seconds to several minutes.

(Metal ion removal step F, metal ion removal step G)

The cleaning method of the substrate of the present invention preferably includes metal ion removal step F for removing Fe ions from at least one of the hydroxylamine compound and water before the preparation step A of the treatment liquid, or the preparation of the treatment liquid After step A and before performing the washing step B, a metal ion removal step G for removing Fe ions in the treatment liquid is included.

Preferably, by implementing the metal ion removal step F or the metal ion removal step G, the content of Fe ions in the treatment liquid used in the cleaning step B is adjusted to 10 mass ppt to the total mass of the treatment liquid. 10 mass ppm.

As a specific method of metal ion removal step F and metal ion removal step G The method is not particularly limited, and examples include distillation or purification using ion exchange membranes.

By first adjusting the content of Fe ions in the treatment liquid to the above-mentioned range, the cleaning performance of the treatment liquid can be maintained well over time, and the reusability is also excellent. In addition, by appropriately adjusting the content ratio of the total content of Fe ions in the treatment liquid to the content of the hydroxylamine compound, the residue removal performance of the treatment liquid is further improved, and the reusability is also more excellent.

(Removal of coarse particles step H)

The substrate cleaning method of the present invention preferably includes a coarse particle removal step H for removing coarse particles in the treatment liquid after the treatment liquid preparation step A and before the washing step B is performed.

By reducing or removing the coarse particles in the treatment liquid, the amount of the coarse particles remaining on the masked substrate after the cleaning step B can be reduced. As a result, it is possible to suppress pattern damage caused by coarse particles on the masked substrate, and it is also possible to suppress the influence on the decrease in yield or reliability of the device.

As a specific method for removing coarse particles, for example, a method of filtering and purifying the treatment liquid that has passed the treatment liquid preparation step A using a particle removal membrane having a predetermined particle diameter.

Furthermore, the definition of coarse particles is as described above.

(Static elimination step I, static elimination step J)

The cleaning method of the substrate of the present invention preferably includes the neutralization step I of removing electricity before the treatment liquid preparation step A, or after the treatment liquid preparation step A and the cleaning step B Before, including removing the treatment liquid Electricity elimination step J.

Since the treatment liquid of the present invention contains a hydroxylamine compound, it has a function of reducing metals. Therefore, the material of the wetted part for supplying the processing liquid to the substrate with the mask is preferably a resin that does not elute metal from the processing liquid. The resin has low electrical conductivity and is insulating, so for example, when the treatment liquid is passed through a resin pipe, or it is filtered and refined by a resin particle removing membrane and a resin ion exchange resin membrane At this time, there is a possibility that the charged potential of the treatment liquid will increase and cause a static electricity disaster.

Therefore, in the substrate cleaning method of the present invention, it is preferable to implement the neutralization step I or the neutralization step J to reduce the charged potential of the treatment liquid. In addition, by performing static elimination, it is possible to further suppress adhesion of foreign matter (coarse particles, etc.) to the substrate or damage (corrosion) to the substrate to be processed.

As a method of neutralization, specifically, the method of contacting a conductive material with water or a processing liquid is mentioned.

The contact time for the water or the treatment liquid to contact the conductive material is preferably 0.001 second to 1 second, more preferably 0.01 second to 0.1 second.

Specific examples of resins include: High Density Polyethylene (HDPE), High Density Polypropylene (PP), 6,6-nylon, Polytetrafluoroethylene (PTFE), tetrafluoroethylene and perfluoroethylene Alkyl vinyl ether copolymer (PFA), polychlorotrifluoroethylene (Polychlorotrifluoroethylene, PCTFE), ethylene. Chlorotrifluoroethylene copolymer (Ethylene Chlorotrifluoroethylene, ECTFE), ethylene. Tetrafluoroethylene copolymer (Ethylene Tetrafluoroethylene, ETFE), tetrafluoroethylene. Fluorinated Ethylene Propylene (FEP) etc.

As the conductive material, stainless steel, gold, platinum, diamond, glassy carbon, etc. are preferred.

When the treatment liquid of the present invention has a reusable composition, the cleaning method of a substrate using the treatment liquid of the present invention can reuse the drained liquid of the treatment liquid used in the cleaning step B, and then be used for other materials with Cleaning of the substrate of the mask.

When the substrate cleaning method of the present invention is a form of reusing the treatment liquid for draining, it preferably includes the following steps.

It includes: the treatment liquid preparation step A; the washing step B; the drain recovery step C, which recovers the drain liquid of the treatment liquid used in the washing step B; the washing step D, the use of the recovered treatment The drain of the liquid, clean the newly prepared metal hardened metals containing any one or more of Cu, Co, W, AlO _x , AlN, AlO _x N _y , WO _x , Ti, TiN, ZrO _x , HfO _x and TaO _x The substrate of the mask; and the drain recovery step E, which recovers the drain of the treatment liquid used in the washing step D; and repeat the washing step D and the drain recovery step E.

In the form of reusing the drain, the meanings of the treatment liquid preparation step A and the cleaning step B are the same as the treatment liquid preparation step A and the cleaning step B described in the form. In addition, the preferred form is also the same. In addition, when reusing the drain In the form, it is preferable to also have the metal ion removal step F, the metal ion removal step G, the coarse particle removal step H, the neutralization step I, and the neutralization step J described in the foregoing configuration.

The meaning of the cleaning step D in which the substrate is cleaned by using the drained liquid of the recovered treatment liquid is the same as the cleaning step B in the above-mentioned embodiment, and the preferred embodiment is also the same.

The drainage recovery means in the drainage recovery step C and the drainage recovery step E are not particularly limited. The recovered drained liquid is preferably stored in the resin container in the neutralization step J. In this case, the same neutralization step as the neutralization step J may also be performed.

In addition, it is preferable to implement the step of adjusting the number of the counted bodies contained in the recovered treatment liquid after at least one of the drained liquid recovery step C and the drained liquid recovery step E and before the washing step D. The adjustment of the number of objects to be counted can be carried out, for example, by filtration treatment of the recovered treatment liquid.

[Method of manufacturing semiconductor element]

The manufacturing method of the semiconductor element of the present invention includes using the treatment liquid of the present invention to clean the materials containing Cu, Co, W, AlO _x , AlN, AlO _x N _y , WO _x , Ti, TiN, ZrO _x , HfO _x And the cleaning step of the substrate of the metal hard mask of any one or more of TaO _x .

The manufacturing method of the semiconductor element of the present invention only needs to include at least the cleaning step, and the meaning of the cleaning step is the same as that of the cleaning step B. In addition, the preferred mode is also the same. The manufacturing method of the semiconductor element may include steps other than the washing step, for example, may include the rinsing step B2 and the drying step B3.

Furthermore, usually after the cleaning step, after removing the unnecessary metal hard mask, one or more additional circuits are formed on the substrate, or for example, assembly (such as cutting and bonding) and packaging are performed. (For example, wafer sealing) to form a semiconductor wafer.

Examples of semiconductor elements include flash memory, logic devices, and the like.

[Example]

Hereinafter, the processing liquid of the present invention will be described in detail using examples. However, the present invention is not limited to this.

<Preparation of Treatment Solution>

First, the components shown in the first table and the second table are mixed in the ratio shown in the first table and the second table to obtain a mixed liquid. In addition, in Table 1 and Table 2, the concentration (mass %) of each component used is as described in the table, and the remainder is water.

Here, each component shown in Table 1 and Table 2 is classified into a semiconductor grade or a high purity grade based on this. In addition, regarding components with many impurities at the time of the raw materials, foreign matter removal by filtration, ion exchange resins and the like were used to reduce ion components.

In addition, the water (ultrapure water) used was prepared using the method described in paragraph 0074 to paragraph 084 of JP 2011-110515 A. Furthermore, the method is a method including a metal ion removal step, and it was confirmed that the amount of Fe ions was 1 mass ppt or less. In addition, the content of Fe ions was measured by an inductively coupled plasma mass analyzer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).

Then, while purifying the obtained mixed liquid by circulating filtration, an in-liquid particle counter (manufactured by Rion Co., Ltd., model: KS-18F, light source: semiconductor laser excited solid laser (wavelength 532nm, rated output) Power (500mW), flow rate: 10ml/min), and count objects of 0.05 μm or more in size contained in 1ml of the mixed solution.

When the number of objects to be counted contained in the mixed liquid reaches a desired value, the mixed liquid is filled into a recovery container (a clean bottle manufactured by Acelu Chemical). In this way, the mixed liquid filled in the recovery container was used as each treatment liquid of the Examples and Comparative Examples. In addition, the size of the object to be counted contained in the treatment liquid (mixed liquid) adjusted by the method is 0.05 μm or more and less than 0.1 μm.

Here, the in-liquid particle counter is used after calibration with a polystyrene latex (PSL) standard particle liquid. In addition, the number of counted objects is shown in Table 1 and Table 2 as the "number of objects on the solution preparation day".

Furthermore, regarding the treatment liquid of the examples in Table 2, the hydroxylamine compound and solvent contained in the treatment liquid are purified (metal ion removal step F), and the prepared treatment liquid is purified (metal At least one timing of the ion removal step G), the Fe ion concentration is adjusted to a desired value.

Specifically, the ion exchange resin membrane (IonKleen SL product No. DFA1SRPESW44 manufactured by Japan Pall Co., Ltd.) was applied at a flow rate of 0.3L/min~0.6L/min, and the surface area of the membrane was 1100cm ² , The number of filters: 1 to 2) is adjusted by passing the treatment liquid into it.

The content of Fe ions relative to the total mass of the treatment solution in the treatment solution was measured by an inductively coupled plasma mass analyzer (manufactured by Yokogawa Analysis System, Agilent 7500cs).

The various components used in the treatment liquid are shown below.

<water>

Ultra-pure water

<Hydroxyamine compound>

HA: Hydroxylamine (manufactured by BASF)

HAS: Hydroxylamine sulfate (manufactured by BASF)

HAC: Hydroxylamine hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.)

HAN: Hydroxylamine nitrate (manufactured by Sigma-Aldrich)

<Anti-corrosion agent 1, anti-corrosion agent 2>

5M-BTA (5-methyl-1H-benzotriazole, manufactured by Tokyo Chemical Industry Co., Ltd.)

BTA (Benzotriazole, manufactured by Tokyo Chemical Industry Co., Ltd.)

Carboxybenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

Phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)

Tetramethylguanidine (manufactured by Tokyo Chemical Industry Co., Ltd.)

3-(2-Aminophenylthio)-2-hydroxypropyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.)

3-mercapto-1,2-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Evaluation Test>

(Evaluation of residue removal performance)

Using each prepared treatment liquid, the residue removal performance was evaluated. In addition, in the following evaluation, a model film containing TiO ₂ as a kind of residue was prepared, and the etching rate was evaluated to evaluate the residue removal performance. That is, when the etching rate is high, it can be said that the residue removal performance is excellent, and when the etching rate is low, it can be said that the residue removal performance is poor.

Furthermore, a model film (TiO ₂ film) containing TiO ₂ was provided with a film thickness of 1000 Å on the Si substrate.

(a) Evaluation of residue removal performance within 24 hours after solution preparation

The TiO ₂ film was etched within 24 hours after the treatment liquids of the examples and comparative examples were prepared. Specifically, the TiO ₂ film was immersed in the treatment solutions of the Examples and Comparative Examples for 5 minutes, and the etching rate (Å/min) was calculated based on the difference in film thickness of the TiO ₂ film before and after immersion in the treatment solution.

Furthermore, the film thickness of the TiO ₂ film before and after the treatment was measured by using an ellipsometry (spectroscopic ellipsometry, trade name "Vase", manufactured by JA Woollam Japan) The measurement is performed in the range of 250nm-1000nm, and the measurement angle is 70 degrees and 75 degrees.

The calculated etching rate (Etching Rate, ER) of the TiO ₂ film was evaluated according to the following evaluation criteria.

A: 5(Å/min)≦ER

B: 3(Å/min)≦ER<5(Å/min)

C: 1(Å/min)≦ER<3(Å/min)

D: ER<1(Å/min)

(b) Evaluation of residue removal performance after thermal cycle test

Each treatment liquid was enclosed in a container (a clean bottle manufactured by Acelul Chemical). Then, the following thermal cycle test was performed: the container filled with the treatment liquid was left standing at 5°C for 12 hours, and then the container filled with the treatment liquid was left standing at 30°C for 12 hours as 1 Cycle and repeat 90 times. The thermal cycle test in the column of Examples corresponds to a test in which a temperature environment change is repeated.

Using the treatment solution after the thermal cycle test, the residue removal performance evaluation test was performed in the same procedure as in the "(a) Evaluation of residue removal performance within 24 hours after solution preparation". In addition, the evaluation criteria are the same as the above-mentioned "(a) Evaluation of residue removal performance within 24 hours after solution preparation".

(c) Evaluation of residue removal performance after long-term cold storage

Regarding each treatment liquid described in Table 2, the residue removal performance after long-term refrigeration storage was evaluated.

Specifically, each treatment liquid described in Table 2 was enclosed in a container (a clean bottle manufactured by Acelu Chemical). Then, long-term refrigerated storage in which the container filled with the treatment liquid was allowed to stand at 5°C for 6 months was performed.

Using the treatment solution after long-term refrigerated storage, the residue removal performance evaluation test was performed in the same procedure as the "(a) Evaluation of residue removal performance within 24 hours after solution preparation". In addition, the evaluation criteria are the same as the above-mentioned "(a) Evaluation of residue removal performance within 24 hours after solution preparation".

(Evaluation of anti-corrosion performance)

Using each of the prepared treatment liquids, the corrosion resistance performance was evaluated. In addition, in the following evaluations, a film containing SiO _x (a model of an insulating film), a film containing Co (a wiring model, hereinafter also referred to as "Co film"), and a film containing Cu (a wiring model, also hereinafter also It is called "Cu film") and a film containing W (tungsten) (wiring model, also referred to as "W film" below).

In addition, the film thickness of each film is 1000 Å.

(a) Evaluation of anti-corrosion performance within 24 hours after solution preparation

. SiO _x film

It was used within 24 hours after preparing each treatment liquid of the Examples and Comparative Examples to perform the etching treatment of the SiO _x film. Specifically, the SiO _x film was immersed in the treatment liquids of the Examples and Comparative Examples for 10 minutes, and the etching rate (Å/min) was calculated based on the difference in film thickness of the SiO _x film before and after immersion in the treatment liquid.

Furthermore, the film thickness of the SiO _x film before and after the treatment was measured using an ellipsometer (spectroscopic ellipsometer, trade name "Vance", manufactured by JA Volan, Japan), with a measurement range of 250nm-1000nm, a measurement angle of 70 degrees and The measurement is performed at 75 degrees.

The calculated etching rate (ER) of the SiO _x film was evaluated according to the following evaluation criteria. When the etching rate is low, it can be said that the corrosion resistance is excellent, and when the etching rate is high, it can be said that the corrosion resistance is poor.

A: ER≦1(Å/min)

B: 1(Å/min)<ER≦3(Å/min)

C: 3(Å/min)<ER≦6(Å/min)

D: 6(Å/min)<ER≦10(Å/min)

E: 10(Å/min)<ER≦30(Å/min)

F: 30(Å/min)<ER

. Co film, Cu film, W film

It was used within 24 hours after preparing the respective treatment solutions of the examples and comparative examples, and the Co film, the Cu film, and the W film were etched separately. Specifically, each film was immersed in the treatment solutions of the Examples and Comparative Examples for 10 minutes, and the sheet resistance value (Ω/□) of each film before and after immersion in the treatment solution was changed ((the value of each film after immersion) Sheet resistance value)-(sheet resistance value of each film before immersion)) was converted into a film thickness difference, and an etching rate (Å/min) was calculated to evaluate the corrosion resistance performance.

Furthermore, the sheet resistance value (Ω/□) is based on a sheet resistance tester (manufactured by Hitachi International Electric Engineering Co., Ltd., model: VR-120S, four-point probe KS-TC-200-MT-200g) The voltage value when a current of 30 mA was passed through each film was calculated.

When the etching rate is low, it can be said that the corrosion resistance is excellent, and when the etching rate is high, it can be said that the corrosion resistance is poor.

A: ER≦1(Å/min)

B: 1(Å/min)<ER≦3(Å/min)

C: 3(Å/min)<ER≦6(Å/min)

D: 6(Å/min)<ER≦10(Å/min)

E: 10(Å/min)<ER≦30(Å/min)

F: 30(Å/min)<ER

(b) Evaluation of anti-corrosion performance after thermal cycle test

Each treatment liquid was enclosed in a container (a clean bottle manufactured by Acelul Chemical). Then, the following thermal cycle test was performed: the container filled with the treatment liquid was left standing at 5°C for 12 hours, and then the container filled with the treatment liquid was left standing at 30°C for 12 hours as 1 Loop, repeat it 90 times.

Using the treatment solution after the thermal cycle test, the corrosion resistance evaluation test was carried out in the same procedure as in the "(a) Evaluation of corrosion resistance performance within 24 hours after solution preparation". In addition, the evaluation criteria are also the same as the above-mentioned "(a) Evaluation of anti-corrosion performance within 24 hours after solution preparation".

(c) Evaluation of corrosion resistance after long-term cold storage

For each treatment liquid described in Table 2, the corrosion resistance performance after long-term cold storage was evaluated.

Specifically, each treatment liquid described in Table 2 was enclosed in a container (a clean bottle manufactured by Acelu Chemical). Then, long-term refrigerated storage in which the container filled with the treatment liquid was allowed to stand at 5°C for 6 months was performed.

Using the treatment solution after long-term refrigeration storage, the corrosion protection performance evaluation test was performed in the same procedure as the "(a) Evaluation of corrosion protection performance within 24 hours after solution preparation". In addition, the evaluation criteria are the same as the above-mentioned "(a) Evaluation of anti-corrosion performance within 24 hours after solution preparation".

<Evaluation Results>

The results of the evaluation test are shown in Table 1 and Table 2.

[Table 1]

It can be seen that the treatment liquid of the example shown in Table 1 has excellent residue removal performance and anti-corrosion performance (evaluation of the treatment liquid within 24 hours after the preparation of the solution), and after repeated temperature environment changes (after the thermal cycle test) Evaluation of the treatment solution) has excellent residue removal performance and corrosion resistance.

In addition, according to the comparison of Example 1, Example 5, Example 11, Example 13 to Example 16, it is shown that the use of triazole compounds as an anticorrosive agent (Example 1, Example 5, Example 11, implementation Example 13), the corrosion resistance is more excellent. In addition, according to the comparison of Example 1, Example 5, Example 11, and Example 13, it is shown that by using a triazole compound and a mercapto group-containing compound as an anticorrosive agent (Example 1, Example 5), the corrosion resistance is better. Excellent. In addition, according to the comparison between Example 1 and Example 5, according to the comparison between Example 11 and Example 13, it is shown that the use of 5-methyl-benzotriazole in the triazole compound (Example 1, Example 11), more excellent corrosion resistance.

In addition, according to the comparison between Example 1 and Example 11 and the comparison between Example 5 and Example 13, it is shown that by using a triazole compound and a mercapto group-containing compound as a corrosion inhibitor (Example 1, Example 5), The anti-corrosion performance is even better after repeated temperature environment changes.

According to the comparison of Example 1 to Example 3, it can be seen that the number of counted bodies contained in the treatment liquid is within the range of 1 to 1000 pcs/ml (Example 1, Example 2), repeating After the temperature environment changes, the residue removal performance is better.

According to the comparison of Examples 1 to 3, it is shown that the number of counted bodies contained in the treatment liquid is in the range of 1/ml~1000/ml (Example 1, Example 2), the anti-corrosion performance is more excellent, the number of counted bodies contained in the treatment solution is in the range of 1 piece/ml-100 pieces/ml (Example 1), the anti-corrosion performance is particularly excellent.

The treatment liquids of the examples shown in Table 2 all showed excellent residue removal performance and anti-corrosion performance (evaluation of the treatment liquid within 24 hours after the preparation of the solution).

In addition, although it is not shown in the second table, it was confirmed that the residues of the treatment liquid of the example shown in the second table were removed after repeated temperature environment changes (evaluation of the treatment liquid after the thermal cycle test) Excellent performance and corrosion resistance.

In addition, as shown in the evaluation results in Table 2, the comparison of Example 17 to Example 24 shows that the Fe ion concentration contained in the treatment liquid is within the range of 10 mass ppt to 10 mass ppm (Example 17 , Example 18, Example 20, Example 21, Example 22, Example 24), the residue removal performance after long-term refrigeration storage is excellent. In addition, it is shown that the concentration of Fe ions contained in the treatment solution is within the range of 10 mass ppt to 1,000 mass ppb (Example 17, Example 18, Example 21, and Example 22), and the residue after long-term cold storage Excellent removal performance. Furthermore, it was shown that when the concentration of Fe ions contained in the treatment solution was 10 mass ppt or more and less than 1,000 mass ppt (Example 17, Example 21), the residue removal performance after long-term cold storage was further improved . Based on this result, even in the case of applying a metal ion removal step to the processing liquid after the processing liquid is produced, the same effect can be expected.

According to the comparison of Examples 25 to 29, the content ratio (mass ratio) of the compound containing mercapto group to the triazole compound contained in the treatment liquid as an anticorrosion agent (mass ratio of the compound containing mercapto group/triazole The mass of the compound) is Within the range of 0.1-50 (Example 26, Example 27, and Example 28), the residue removal performance and corrosion resistance performance after long-term refrigeration storage are further improved. In addition, it was shown that by having the content ratio in the range of 0.1 to 20 (Example 26 and Example 27), the residue removal performance and corrosion resistance performance after long-term refrigerated storage were further improved. Furthermore, it was shown that when the content ratio was in the range of 0.1 to 10 (Example 26), the residue removal performance and corrosion resistance performance after long-term cold storage were further improved.

In addition, although not shown in the table, it can be confirmed that the treatment liquids of the examples are all hard to metals containing any of AlO _x , AlN, AlO _x N _y , Ti, TiN, ZrO _x , HfO _x , and TaO _x The mask shows excellent residue removal performance.

On the other hand, the treatment liquid of Comparative Example 1 did not contain an anticorrosive agent, and therefore showed poor corrosion resistance (evaluation of the treatment liquid within 24 hours after the solution was prepared).

The treatment solution of Comparative Example 2 did not contain the specified object, so it showed poor residue removal performance and corrosion resistance (evaluation of the treatment solution within 24 hours after the solution was prepared), after repeated temperature environment changes (after thermal cycle test) The corrosion protection performance of the evaluation of the treatment liquid becomes insufficient.

<Evaluation of Static Elimination>

Regarding the treatment solutions of Example 5 and Example 6, the grounded material SUS316 was used to neutralize electricity and the immersion time was set to 20 minutes. Except for this, the same method was used to determine the residue removal performance within 24 hours after the solution was prepared. Evaluation, various evaluations of corrosion resistance (Co film, W film, SiO _x film) within 24 hours after solution preparation.

Regarding the results of the evaluation, for any of the treatment liquids, the residue removal performance did not change when it passed through the neutralization step and when it did not. On the other hand, the various evaluations of the anti-corrosion performance of the Co film, the anti-corrosion performance of the W film, and the anti-corrosion performance of the SiO _x film have achieved better results in the anti-corrosion performance after the anti-static step than when the anti-static step is passed.

From this result, it can be seen that the anticorrosive performance of the treatment liquid is more excellent by passing through the neutralization step.

<Reuse Test>

Using the treatment liquid of Example 1, the operation described in the evaluation of the residue removal performance within 24 hours after the solution preparation was continuously performed 25 times. At this time, each time one of the films was processed, the treatment liquid was not changed, and 25 of the films were immersed in the same treatment liquid one by one.

Thereafter, the treatment liquid of Example 1 was recovered in the tank, and the residue removal performance within 24 hours after the preparation of the solution was evaluated again. This series of treatments is referred to as a reuse test (residue removal performance).

In addition, with regard to the treatment liquids of Example 3, Example 17, and Example 20, the same reuse test (residue removal performance) as the treatment liquid of Example 1 was also performed.

In addition, the treatment liquid of Example 1 was used to continuously perform the operations described in the evaluation of the corrosion protection performance (only the Co film, the W film, and the SiO _x film) within 24 hours after the solution preparation was performed 25 times. At this time, each time one of the films was processed, the treatment liquid was not changed, and 25 of the films were immersed in the same treatment liquid one by one.

Thereafter, the treatment liquid of Example 1 was recovered in the tank, and the corrosion resistance performance (only the Co film, W film, and SiO _x film) was evaluated within 24 hours after the solution preparation. This series of treatments is referred to as a reuse test (anti-corrosion performance).

In addition, with respect to the treatment liquids of Example 3, Example 17, and Example 20, the same repeated use test (corrosion resistance) as the treatment liquid of Example 1 was also performed.

The results of the evaluation of the reuse test showed that in the treatment solutions of Example 1 and Example 17, when the reuse test was performed, and when the reuse test was not performed, the residue removal performance within 24 hours after the solution was prepared The evaluation and various evaluations of the corrosion resistance (Co film, W film, SiO _x film) within 24 hours after the solution preparation are the same.

On the other hand, in the treatment solution of Example 3, when the repeated use test was performed, the residue removal performance and the corrosion resistance of the Co film were "B". Otherwise, the same results as when the repeated use test was not performed were obtained. the result of.

In addition, in the treatment solution of Example 20, when the reuse test was performed, the residue removal performance and the corrosion resistance of the Co film and the W film were "B". In addition, the results obtained when the reuse test was not performed The same result.

From this result, it can be seen that the processing liquid of the present invention can suppress performance degradation even when the substrate is repeatedly processed, and is excellent in reusability.

1‧‧‧Substrate

2‧‧‧Metal film

3‧‧‧Etching stop layer

4‧‧‧Interlayer insulation film

5‧‧‧Metal hard mask

6‧‧‧Hole

10‧‧‧Layer

11‧‧‧Inner wall

11a‧‧‧Section Wall

11b‧‧‧Bottom wall

12‧‧‧Dry etching residue

Claims (12)

A treatment liquid, which is a treatment liquid for semiconductor elements, contains at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salt, water, and an anticorrosive agent, and is counted by a light scattering type liquid particle counter of 0.05 μm or more The number of counted bodies of the size of is 50 to 1600 per 1 ml of the treatment liquid, wherein the content of the hydroxylamine compound is 0.01% by mass to 30% by mass relative to the total mass of the treatment liquid, relative to The total mass of the treatment liquid, the content of the anti-corrosion agent is 0.01% by mass to 5% by mass, and the anti-corrosion agent is selected from the group consisting of triazole compounds, compounds containing mercapto groups, maleic anhydride, phthalic anhydride, and sulfur At least one compound in the group consisting of ammonium sulfate, tetramethylguanidine and gallate. The treatment liquid according to the first item of the patent application, wherein the corrosion inhibitor comprises a triazole compound, and the triazole compound comprises a compound selected from benzotriazole, carboxybenzotriazole, 5-methyl-benzotriazole At least one compound of azole and triazole. The treatment liquid according to the first item of the patent application, wherein the anticorrosive agent comprises a triazole compound and a compound containing a mercapto group, and the triazole compound comprises a compound selected from the group consisting of benzotriazole, carboxybenzotriazole, 5-methyl At least one compound selected from the group consisting of 2-mercapto-benzotriazole and triazole, and the mercapto-containing compound includes 2-mercapto-5-methylbenzimidazole, 3- Mercapto-1,2-propanediol, 2-mercaptothiazoline, 3-(2-aminophenylthio)-2-hydroxypropyl mercaptan and 3-(2-hydroxyethylthio)-2-hydroxyl At least one compound in propyl mercaptan. The treatment liquid according to the first item of the patent application, wherein the triazole compound contains 5-methyl-benzotriazole. The treatment liquid according to the first item of the patent application, wherein the anticorrosive agent includes a triazole compound and a mercapto group-containing compound, and the mass ratio of the mercapto group-containing compound to the triazole compound is 0.1-50. The treatment liquid described in item 1 of the scope of patent application further contains Fe ions of 10 mass ppt to 10 mass ppm. The treatment liquid described in the first item of the scope of patent application, which is used for cleaning and contains Cu, Co, W, AlO _x , AlN, AlO _x N _y , WO _x , Ti, TiN, ZrO _x , HfO _x and TaO _x is any one or more of a metal hard mask substrate, where, x, y, respectively by x = 1 ~ 3, y = 1 to 2 representation. A method for cleaning a substrate, comprising: a treatment liquid preparation step A, preparing the treatment liquid as described in any one of items 1 to 7 in the scope of the patent application; and a cleaning step B, using the treatment liquid, Wash the substrate with a metal hard mask containing any one or more of Cu, Co, W, AlO _x , AlN, AlO _x N _y , WO _x , Ti, TiN, ZrO _x , HfO _x and TaO _x , where, x and y are numbers represented by x=1~3 and y=1~2 respectively. The method for cleaning a substrate as described in item 8 of the scope of the patent application further includes: a drain recovery step C, recovering the drain of the treatment liquid used in the cleaning step B; and a cleaning step D, Use the drain to clean the newly prepared metals containing any one or more of Cu, Co, W, AlO _x , AlN, AlO _x N _y , WO _x , Ti, TiN, ZrO _x , HfO _x and TaO _x Hard mask substrate, where x and y are numbers represented by x=1~3 and y=1~2 respectively; and the drain recovery step E, which recovers all used in the cleaning step D The drain; and repeat the washing step D and the drain recovery step E to reuse the drain. The method for cleaning a substrate as described in item 8 or item 9 of the scope of patent application, which includes removing Fe ions from at least one of the hydroxylamine compound and the water before the treatment liquid preparation step A The metal ion removal step F of the treatment liquid, or after the treatment liquid preparation step A and before the washing step B, includes a metal ion removal step G of removing Fe ions in the treatment liquid. The method for cleaning a substrate as described in item 8 or item 9 of the scope of the patent application includes, before the treatment liquid preparation step A, the electricity removal step I of removing electricity from the water, or the preparation of the treatment liquid After step A and before performing the washing step B, a neutralization step J of neutralizing the treatment liquid is included. A method for manufacturing a semiconductor element, which includes using the treatment liquid as described in any one of items 1 to 7 of the scope of the patent application to clean the materials containing Cu, Co, W, AlO _x , AlN, AlO _x N _y , WO _x , Ti, TiN, ZrO _x , HfO _x, and TaO _x for the steps of a substrate with a metal hard mask. Here, x and y are respectively x=1~3, y=1~2 The number represented.

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