JP6518788B2 - Method of storing treatment liquid for semiconductor device, treatment liquid container - Google Patents

Description

  The present invention relates to a method of storing a treatment liquid for semiconductor device, and a treatment liquid container.

Semiconductor devices such as CCDs (Charge-Coupled Devices) and memories are manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology. Specifically, a resist film is applied on a laminated film such as a metal film (for example, Co, W) serving as a wiring material formed on a substrate, an interlayer insulating film, etc., and a photolithography process / dry etching process (for example, Manufactured through plasma etching).
In addition, if necessary, after the dry etching step, a photoresist peeling step is mainly performed to peel an organic component such as a photoresist by a peeling means such as a dry ashing step (for example, plasma ashing treatment). Be done.

In the substrate which has undergone the dry etching process, dry etching residue which is a residue component including metal adheres on the metal film and the interlayer insulating film. For this reason, processing which wash-removes this residue with processing solution which has strong reducing power and can solubilize a metal is generally performed.
For example, Patent Document 1 discloses a composition containing hydroxylamine as a reducing agent in a treatment liquid.

JP, 2012-195590, A

On the other hand, when the inventors of the present invention examined the aging performance of the treatment solution containing hydroxylamine described in Patent Document 1, it has been found that the residue removal performance may be deteriorated.
More specifically, the treatment liquid is generally stored refrigerated at a predetermined temperature when not in use, and the treatment liquid is removed from refrigeration storage and returned to room temperature for use. The present inventors repeatedly carry out a series of operations in which the treatment liquid is allowed to stand at room temperature for a predetermined time after storing the treatment liquid in a refrigerated state, the residue removal performance of the treatment liquid is deteriorated. Know that there are
Therefore, there has been a demand for a storage method that suppresses the deterioration of the residue removal performance of the treatment liquid even if the temperature environment changes as described above.

  Therefore, the present invention is a storage method of a processing solution for semiconductor devices containing any one selected from hydroxylamine and hydroxylamine salt, and the processing solution can be used even if the temperature environment change of cold storage and standing at room temperature is repeated. It is an object of the present invention to provide a method of storing a treatment liquid for semiconductor device in which the deterioration of the residue removal performance does not easily occur, and a treatment liquid container.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the deterioration of the residue removal performance of the treatment liquid is correlated with the porosity in the storage container that accommodates the treatment liquid, The present invention has been completed.
That is, it discovered that the said objective could be achieved by the following structures.

(1) A storage method for a semiconductor device processing solution, which stores a semiconductor device processing solution containing at least one selected from hydroxylamine and hydroxylamine salt and water in a storage container. ,
The storage method of the processing liquid for semiconductor devices which sets the porosity in the said storage container as 0.01-30 volume%.
In addition, the porosity is calculated | required by the following formula (1).
Formula (1): porosity = {1-(volume of the processing solution for semiconductor devices in the storage container / container volume of the storage container)} × 100
(2) The method for storing a semiconductor device processing solution according to (1), wherein the semiconductor device processing solution further contains a corrosion inhibitor.
(3) The method for storing a semiconductor device processing solution according to (1) or (2), wherein the semiconductor device processing solution further contains at least one selected from a water-soluble organic solvent and an alkanolamine.
(4) The method for storing a semiconductor device processing solution according to any one of (1) to (3), wherein the semiconductor device processing solution further contains quaternary ammonium hydroxides.
(5) The method for storing a semiconductor device processing solution according to any one of (1) to (4), wherein the semiconductor device processing solution further contains a fluoride.
(6) The method for storing a semiconductor device processing solution according to any one of (1) to (5), wherein the semiconductor device processing solution further contains a chelating agent.
(7) The semiconductor according to any one of (2) to (6), wherein the corrosion inhibitor is at least one selected from the group consisting of compounds represented by Formula (A) to Formula (C) described later. Storage method of treatment solution for device.
(8) The method for storing a semiconductor device processing solution according to any one of (1) to (7), wherein the pH of the semiconductor device processing solution is 6 to 11.
(9) The total content of at least one selected from the hydroxylamine and the hydroxylamine salt in the treatment liquid is 1 to 30% by mass with respect to the total mass of the treatment liquid. The storage method of the process liquid for semiconductor devices in any one of 2.).
(10) A storage method of a processing solution for a semiconductor device according to any one of (1) to (9), wherein the content of Fe ions in the processing solution is 10 mass ppt to 10 mass ppm.
(11) A treatment liquid containing at least a storage container, and at least one selected from hydroxylamine and a hydroxylamine salt and contained in the storage container, water, and a treatment liquid for semiconductor device A treatment liquid container, which is a body, and the porosity in the storage container is 0.01 to 30% by volume.
In addition, the porosity is calculated | required by the following formula (1).
Formula (1): porosity = {1-(volume of the processing solution for semiconductor devices in the storage container / container volume of the storage container)} × 100
(12) The treatment liquid container according to (11), wherein the material of the inner wall of the storage container is a resin.
(13) The material of the inner wall of the storage container is high density polyethylene, high density polypropylene, 6,6-nylon, tetrafluoroethylene, copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, polychlorotrifluoroethylene, ethylene · One or more resins selected from chlorotrifluoroethylene copolymer, ethylene / tetrafluoroethylene copolymer, and tetrafluoroethylene / hexafluoropropylene copolymer, (11) or (12) The treatment liquid container described in.
(14) The treatment liquid container according to any one of (11) to (13), wherein the material of the inner wall of the storage container is a fluorine-based resin containing a fluorine atom in the molecule.
(15) The processing liquid container according to any one of (11) to (14), wherein the storage container has a plurality of openings.

  According to the present invention, it is a storage method of a processing solution for semiconductor devices containing any one selected from hydroxylamine and hydroxylamine salt, and the processing solution can be used even if the temperature environment change of cold storage and standing at room temperature is repeated. It is possible to provide a storage method for a processing solution for semiconductor devices that hardly causes deterioration of the residue removal performance, and a processing solution container.

Hereinafter, the present invention will be described in detail.
Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.
In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
In the present invention, the dry etching residue is a by-product generated by performing dry etching (for example, plasma etching), and for example, an organic residue derived from a photoresist, a Si-containing residue, and a metal. Containing residue. In the following description, the dry etching residue may be simply referred to as "residue".
In the present invention, the dry ashing residue is a by-product generated by performing dry ashing (for example, plasma ashing), and for example, organic residue derived from photoresist, Si-containing residue, and , Metal-containing residue.
Moreover, in the notation of the group (atom group) in the present specification, the notation not describing substitution and non-substitution is one having a substituent together with one having no substituent within a range not to impair the effect of the present invention. Is also included. For example, "hydrocarbon group" includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group having a substituent (substituted hydrocarbon group) . The same is true for each compound.
In addition, the term "preparation" as used herein means including procuring a predetermined material by purchasing or the like, in addition to providing a specific material by synthesis or preparation.

[Method of storing treatment liquid for semiconductor device]
The storage method of the semiconductor device processing solution of the present invention (hereinafter also referred to as “processing solution”) is a semiconductor device processing comprising at least one selected from hydroxylamine and hydroxylamine salt, and water. A storage method of a processing solution for semiconductor devices, which stores the solution in a storage container and stores the solution.
The porosity in the storage container is made 0.01 to 30% by volume.
In addition, the porosity is calculated | required by Formula (1) mentioned above. Formula (1) will be described in detail later.

According to the storage method of the processing liquid for semiconductor devices of the present invention, it is possible to suppress the deterioration of the residual substance removal performance of the processing liquid even if the temperature environment change of cold storage and standing at room temperature is repeated.
This is not clear in detail, but is presumed as follows.
The hydroxylamine (or hydroxylamine salt) in the treatment liquid is not only the oxygen contained in the treatment liquid, but also the upper space where there is no treatment liquid in the storage container containing the treatment liquid (or the treatment liquid and the upper portion It is considered that oxygen in the interface (in the space) causes partial decomposition, and a predetermined decomposition product (hereinafter also referred to as decomposition product X) is generated in the treatment liquid. It is presumed that the presence of a certain amount of the decomposition product X in the treatment liquid is effective in preventing the deterioration of the residue removal performance of the treatment liquid. As described in detail later, the reduction in the residual substance removal performance of the treatment liquid should be confirmed by preparing a model film of the component constituting the residual substance and observing the decrease in the etching rate by the treatment liquid. Can.
When the porosity described above is less than 0.01%, the generation of the decomposable product X is not promoted so much in the first place, and as a result, the amount of the decomposable product X in the processing liquid is small and the performance deterioration of the processing liquid is suppressed It is difficult. On the other hand, when the porosity is more than 30%, although the degradable product X is relatively produced, the obtained degradable product X is further decomposed to become another degradable product easily, and becomes another degradable product. It is presumed that the effect of can not be obtained.
In addition, as described above, the treatment liquid is often used repeatedly with cold storage and treatment at room temperature, but in the case of such temperature environment change, the influence of the porosity described above is particularly important. It is presumed that the performance difference of the processing solution tends to be large.

Hereinafter, the treatment liquid, storage container and storage conditions in the present invention will be described in detail.
(Treatment solution)
The treatment liquid of the present invention contains water and at least one selected from hydroxylamine and hydroxylamine salt.

<Water>
The treatment liquid of the present invention contains water as a solvent. The content of water is preferably 60 to 98% by mass, and more preferably 70 to 95% by mass, based on the total mass of the treatment liquid.
As water, ultrapure water used for semiconductor production is preferable. Although not particularly limited, it is preferable that the ion concentration of metal elements of Fe, Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn be reduced. When used in the preparation of the treatment liquid of the present invention, those adjusted to the ppt order or less are preferable. Examples of the adjustment method include the methods described in paragraphs [0074] to [0084] of JP-A-2011-110515.

<Hydroxylamine compound>
The treatment liquid of the present invention contains at least one selected from hydroxylamine and hydroxylamine salt. Hydroxylamine and its salts promote the decomposition and solubilization of the residue, and also have the effect of preventing corrosion of the object to be treated.

Here, “hydroxylamine” relating to hydroxylamine and hydroxylamine salt in the treatment liquid of the present invention refers to hydroxylamines in a broad sense including substituted or unsubstituted alkylhydroxylamine and the like, and any of them may be used. Can also obtain the effects of the present invention.
The hydroxylamine is not particularly limited, but preferred embodiments include unsubstituted hydroxylamine and hydroxylamine derivatives.
The hydroxylamine derivative is not particularly limited. For example, O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, O-dimethylhydroxylamine, N-ethyl Hydroxylamine, N, N-diethylhydroxylamine, N, O-diethylhydroxylamine, O, N, N-trimethylhydroxylamine, N, N-dicarboxyethylhydroxylamine, and N, N-disulfoethylhydroxylamine Can be mentioned.
The salt of hydroxylamine is preferably the above-mentioned inorganic or organic acid salt of hydroxylamine, and it is a salt of inorganic acid obtained by combining nonmetals such as Cl, S, N and P with hydrogen. It is more preferable that it is a salt of any acid selected from the group consisting of hydrochloric acid, sulfuric acid and nitric acid.
As a salt of hydroxylamine used to form the treatment liquid of the present invention, hydroxyl ammonium nitrate (also referred to as HAN), hydroxyl ammonium sulfate (also referred to as HAS), hydroxyl ammonium hydrochloride (also referred to as HAC) Hydroxyl ammonium phosphate, N, N-diethylhydroxylammonium sulfate, N, N-diethylhydroxylammonium nitrate, and mixtures thereof are preferred.
In addition, organic acid salts of hydroxylamine can also be used, and hydroxyl ammonium citrate, hydroxyl ammonium oxalate, hydroxyl ammonium fluoride and the like can be exemplified.
The treatment liquid of the present invention may be in a form containing both hydroxylamine and a salt thereof.
The hydroxylamines or hydroxylamine salts may be used alone or in combination of two or more.
Among the above, hydroxylamine or hydroxyl ammonium sulfate is preferable, and hydroxyl ammonium sulfate is more preferable, from the viewpoint that the desired effect of the present invention is significantly obtained.

  The content of hydroxylamine and its salt in the treatment liquid is not particularly limited, but is preferably in the range of 0.01 to 40% by mass, more preferably 1 to 30% by mass, with respect to the total mass of the treatment liquid of the present invention. Preferably, 4 to 25% by mass is more preferable, and 12 to 18% by mass is particularly preferable.

<Fluoride>
The treatment liquid of the present invention may contain fluoride. Fluoride promotes the decomposition and solubilization of the residue.
The fluoride is not particularly limited, but hydrofluoric acid (HF), fluorosilicic acid (H ₂ SiF ₆ ), fluoroboric acid, fluorosilicic acid ammonium salt ((NH ₄ ) ₂ SiF ₆ ), hexafluorophosphoric acid Tetramethyl ammonium, ammonium fluoride, ammonium fluoride salt, ammonium bifluoride salt, quaternary ammonium tetrafluoroborate represented by the formula NR ₄ BF ₄ (for example, tetramethyl ammonium tetrafluoroborate, tetrafluoroboronic acid, etc. Tetraethyl ammonium tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate (TBA-BF ₄ ), etc., and quaternary phosphonium tetrafluoroborate represented by the formula PR ₄ BF ₄ etc. It can be mentioned.
The fluorides may be used alone or in combination of two or more.
In the quaternary ammonium tetrafluoroborate represented by the above formula NR ₄ BF ₄ and the quaternary phosphonium tetrafluoroborate represented by the formula PR ₄ BF ₄ , R is the same or different from each other. You may R represents a hydrogen, linear, branched or cyclic alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl and the like), and 6 carbon atoms To 10 aryl groups and the like. These may further contain a substituent.
The fluorides may be used alone or in combination of two or more.
Among the above, ammonium fluoride or fluorosilicic acid is preferable.
When the treatment liquid contains a fluoride, the content thereof is preferably in the range of 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, with respect to the total mass of the treatment liquid of the present invention 0.1 to 1% by mass is more preferable.

<Fe ion>
The present inventors have found that the content of Fe ions contained in the treatment liquid of the present invention has a great influence on various performances. In particular, when the Fe ion interacts with at least one selected from hydroxylamine and a salt thereof, the desired effect of the present invention becomes remarkable. Generally, it is preferable that the amount of metal ions is small, but in the present invention, it is preferable that a specific amount of Fe ions be contained.
The content of Fe ions in the treatment liquid of the present invention is preferably 10 mass ppt to 10 mass ppm, and 1 mass ppb to 1 mass ppm with respect to the total mass of the treatment liquid of the present invention. More preferably, it is more preferably 1 mass ppb to 50 mass ppb, and particularly preferably 1 mass ppb to 5 mass ppb.
By containing Fe ions in the above range, the deterioration of the residue removal performance after aging of the treatment liquid is further suppressed.
Furthermore, the Fe ion content is a mass ratio to the content of at least one selected from hydroxylamine and its salt (in the case where a plurality of compounds selected from hydroxylamine and its salt are contained, the total amount thereof) Is preferably 5 × 10 ^{−2 to} 5 × 10 ⁻¹⁰ , more preferably 5 × 10 ^{−4 to} 5 × 10 ⁻¹⁰ , and 5 × 10 ^{−6 to} 5 × 10 ⁻⁷ Is more preferred. By adopting the above configuration, the residue removal performance of the treatment liquid is further improved.

The Fe ion is usually a component that can be contained as an impurity in solvents, drugs, and the like. Therefore, the solvent contained in the treatment liquid and / or the treatment liquid after preparation can be prepared to a desired amount by purification by means such as distillation and ion exchange resin.
The amount of Fe ions in the processing solution can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).

<Corrosion inhibitor>
The treatment solution of the present invention preferably contains a corrosion inhibitor. The corrosion inhibitor has the function of eliminating the over-etching of the metal (eg, Co, W) to be the wiring film.
The corrosion inhibitor is not particularly limited. For example, 1,2,4-triazole (TAZ), 5-aminotetrazole (ATA), 5-amino-1,3,4-thiadiazole-2-thiol, 3-amino -1H-1,2,4 triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 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-isopropyl-1 , 2,4-triazole, naphthotriazole, 1H-tetrazole-5-acetic acid, 2-mercaptobenzothiazole (2-MBT), 1-phenyl-2-tetrazoli -5-thione, 2-mercaptobenzimidazole (2-MBI), 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, Imidazole, benzimidazole, triazine, methyltetrazole, bismuthiol I, 1,3-dimethyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyl triazine, imidazoline thione, 4 -Methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl phosphate, indazole, adenine, cytosine, guanine, thymine, Phosphate inhibitor , Pyrazoles, propanethiols, silanes, secondary amines, benzohydroxamic acids, heterocyclic nitrogen inhibitors, citric acid, ascorbic acid, thiourea, 1,1,3,3-tetramethylurea, urea Urea derivatives, uric acid, potassium ethylxanthogenate, glycine, dodecylphosphonic acid, iminodiacetic acid, acid, boric acid, malonic acid, succinic acid, nitrilotriacetic acid, sulfolane, 2,3,5-trimethylpyrazine, 2- Ethyl 3,5-dimethylpyrazine, quinoxaline, acetylpyrrole, pyridazine, histadine, pyrazine, glutathione (reduced), cysteine, cystine, thiophene, mercaptopyridine N-oxide, thiamine HCl, tetraethylthiuram disulfide, 2, 5-Dimercapto-1,3-thiadiazole Colvin acid, catechol, t- butyl catechol, phenol, and pyrogallol.

  Furthermore, it is also preferable to include a substituted or unsubstituted benzotriazole as a corrosion inhibitor. As substituted benzotriazole, for example, benzotriazole substituted with an alkyl group, an aryl group, a halogen group, an amino group, a nitro group, an alkoxy group, or a hydroxyl group is preferable. The substituted benzotriazole may be fused with one or more aryl (eg, phenyl) or heteroaryl groups.

The substituted or unsubstituted benzotriazole is, for example, benzotriazole (BTA), 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 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-1H-benzotriazole, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole Azole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole, 5-isopropylbenzotriazole, 4-n-butylbenzotriazole, 5-n- Butylbenzotriazole, 4-isobutylbenzotriazole, 5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole, 4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-methoxybenzotriazole, 5-hydroxybenzotriazole Triazole, dihydroxypropyl benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] -benzotriazole, 5-t-butyl bene Zotriazole, 5- (1 ′, 1′-dimethylpropyl) -benzotriazole, 5- (1 ′, 1 ′, 3′-trimethylbutyl) benzotriazole, 5-n-octylbenzotriazole, and 5- (1 ', 1', 3 ', 3'- tetramethylbutyl) benzotriazole etc. are mentioned.
The corrosion inhibitors may be used alone or in combination of two or more.

  Among them, the corrosion inhibitor is preferably at least one selected from the group consisting of compounds represented by the following formulas (A) to (C) and substituted or unsubstituted tetrazole, and the following formula More preferably, it is at least one selected from the group consisting of compounds represented by (A) to formula (C).

In Formula (A), each of R ^{1A to} R ^5A independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a hydroxyl group, a carboxy group, or a substituted or unsubstituted amino group. However, the structure includes at least one group selected from a hydroxyl group, a carboxy group, and a substituted or unsubstituted amino group.
In Formula (B) above, R ^{1B to} R ^4B each independently represent a hydrogen atom, a substituent or an unsubstituted hydrocarbon group.
In Formula (C) above, R ^1C , R ^2C, and R ^N each independently represent a hydrogen atom, a substituent, or an unsubstituted hydrocarbon group. Also, R ^1C and R ^2C may combine to form a ring.

The hydrocarbon group represented by R ^{1A to} R ^5A in the above formula (A) is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and particularly preferably 1 to 3 carbon atoms), and an alkenyl group (The number of carbon atoms is preferably 2 to 12, and more preferably 2 to 6), an alkynyl group (the number of carbon atoms is preferably 2 to 12, and more preferably 2 to 6), an aryl group (number of carbons is 6 to 22) Is preferable, 6 to 14 is more preferable, 6 to 10 is more preferable, and an aralkyl group (the carbon number is preferably 7 to 23, more preferably 7 to 15, and still more preferably 7 to 11). .
Moreover, as a substituent, for example, a hydroxyl group, a carboxy group, or a substituted or unsubstituted amino group (as a substituent, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms) Is more preferable).
In the formula (A), in the structure, a hydroxyl group, a carboxy group, and a substituted or unsubstituted amino group (as a substituent, an alkyl group having 1 to 6 carbon atoms is preferable, and 1 to 6 carbon atoms And at least one group selected from the group consisting of 3 alkyl groups).

In the formula (A), examples of the substituent or unsubstituted hydrocarbon group represented by R ^{1A to} R ^5A include an unsubstituted hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, a carboxy group or an amino group. The C1-C6 hydrocarbon group etc. which were substituted by group etc. are mentioned.
Examples of the compound represented by the formula (A) include 1-thioglycerol, L-cysteine, thiomalic acid and the like.

The hydrocarbon group and the substituent represented by R ^{1B to} R ^4B in the formula (B) have the same meanings as the hydrocarbon and the substituent represented by R ^{1A to} R ^5A of the above-mentioned formula (A). Examples of the substituted or unsubstituted hydrocarbon group represented by R ^{1B to} R ^4B include hydrocarbon groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group and t-butyl group. Be
As a compound represented by Formula (B), catechol, t-butyl catechol etc. are mentioned, for example.

In the formula (C), the hydrocarbon group and the substituent represented by R ^1C , R ^2C and R ^N are respectively synonymous with the hydrocarbon and the substituent represented by R ^{1A to} R ^5A of the above-mentioned formula (A) is there. Examples of the substituted or unsubstituted hydrocarbon group represented by R ^1C , R ^2C and R ^N include hydrocarbon groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl and butyl. Be
In addition, R ^1C and R ^2C may combine to form a ring, and examples thereof include a benzene ring. When R ^1C and R ^2C combine to form a ring, they may further have a substituent (eg, a hydrocarbon group of 1 to 5 carbon atoms).
Examples of the compound represented by the formula (C) include 1H-1,2,3-triazole, benzotriazole, and 5-methyl-1H-benzotriazole.
Etc.

  As substituted or unsubstituted tetrazole, for example, in addition to unsubstituted tetrazole, a hydroxyl group, a carboxy group as a substituent, or a substituted or unsubstituted amino group (as a substituent, an alkyl group having 1 to 6 carbon atoms is Preferably, the tetrazole which has a C1-C3 alkyl group is more preferable.

  The content of the corrosion inhibitor in the treatment solution is preferably 0.01 to 5% by mass, and more preferably 0.05 to 5% by mass, based on the total mass of the treatment solution of the present invention. And 0.1 to 3% by mass.

Chelating agent
The treatment liquid may further contain a chelating agent. The chelating agent chelates the oxidized metal contained in the residue.
The chelating agent is not particularly limited, but is preferably polyaminopolycarboxylic acid.
The polyaminopolycarboxylic acid is a compound having a plurality of amino groups and a plurality of carboxylic acid groups. Examples of polyaminopolycarboxylic acids include mono- or polyalkylenepolyaminepolycarboxylic acids, polyaminoalkanepolycarboxylic acids, polyaminoalkanol polycarboxylic acids, and hydroxyalkyl ether polyamine polycarboxylic acids.

Examples of polyaminopolycarboxylic acids include butylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetramine hexaacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N ', N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6-hexamethylene-diamine-N, N N ′, N′-tetraacetic acid, N, N-bis (2-hydroxybenzyl) ethylenediamine-N, N-diacetic acid, diaminopropane tetraacetic acid, 1,4,7,10-tetraazacyclododecane-tetraacetic acid , Diaminopropanol tetraacetic acid, and (hydroxyethyl) Examples include tilylenediamine triacetic acid and the like. Among them, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), or trans-1,2-diaminocyclohexanetetraacetic acid is preferable.
The chelating agents may be used alone or in combination of two or more.

  The content of the chelating agent in the treatment liquid is preferably 0.01 to 5% by mass, and more preferably 0.01 to 3% by mass, with respect to the total mass of the treatment liquid of the present invention.

<Water-soluble organic solvent>
The treatment liquid of the present invention preferably contains a water-soluble organic solvent. The water-soluble organic solvent can promote the solubilization of the additive component and the organic substance residue and can further improve the corrosion prevention effect.
The water-soluble organic solvent is not particularly limited, and examples thereof include water-soluble alcohols, water-soluble ketones, water-soluble esters, and water-soluble ethers (eg, glycol diethers).

  As the water-soluble alcohol, for example, alkane diol (including, for example, alkylene glycol), glycol, alkoxy alcohol (including, for example, glycol monoether), saturated aliphatic monohydric alcohol, unsaturated non-aromatic monohydric alcohol, and And low molecular weight alcohols containing a ring structure.

  As the alkanediol, for example, 2-methyl-1,3 propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-diol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, alkylene glycol and the like.

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

  Examples of the alkoxy alcohol include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, and 1-methoxy-2-butanol.

  Examples of glycol monoethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene 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 monobenzyl ether, And diethylene glycol monobenzyl ether and the like.

  As a saturated aliphatic monohydric alcohol, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, and 1-hexanol etc. are mentioned.

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

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

  As water-soluble esters, glycol monoesters such as ethyl acetate, ethylene glycol monoacetate, and diethylene glycol monoacetate, and propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, And glycol monoether monoesters such as ethylene glycol monoethyl ether acetate.

The water-soluble organic solvents may be used alone or in combination of two or more.
Among the water-soluble organic solvents, from the viewpoint of further improving the corrosion prevention effect, water-soluble alcohols are preferable, alkanediols, glycols and alkoxy alcohols are more preferable, alkoxy alcohols are more preferable, ethylene glycol monobutyl ether and tripropylene glycol Particular preference is given to monomethyl ether or diethylene glycol monoethyl ether.

  The content of the water-soluble organic solvent in the treatment liquid is preferably 0.1 to 15% by mass, and more preferably 1 to 10% by mass, with respect 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 is preferably equal to or higher than the pKa of a hydroxylamine and a conjugate acid of a hydroxylamine salt. When the pH of the treatment liquid of the present invention is equal to or higher than the pKa of a hydroxylamine and a conjugate acid of a hydroxylamine salt, the residue removability is dramatically improved. In other words, when the proportion of hydroxylamine and hydroxylamine salt present in the molecular state in the treatment solution is high, the effects of the present invention are significantly obtained. In addition, for example, the pKa of the conjugate acid of hydroxylamine is about 6.
From the above viewpoint, the treatment liquid of the present invention preferably has a pH of 6 to 11. In order to make pH of a process liquid into the said range, it is desirable for a process liquid to contain a pH adjuster. In addition, when the pH of the treatment liquid is within the above range, the corrosion rate and the residue removal performance are both superior.
The lower limit of the pH of the treatment liquid is preferably 6.5 or more, more preferably 7 or more, and still more preferably 7.5 or more, from the viewpoint of washing properties. On the other hand, the upper limit thereof is preferably 10.5 or less, more preferably 10 or less, still more preferably 9.5 or less, and 8.5 or less from the viewpoint of corrosion inhibition. Particularly preferred.
The pH can be measured using a known pH meter.

As a pH adjuster, although a well-known thing can be used, generally it is preferable not to contain a metal ion.
Examples of pH adjusters include ammonium hydroxide, monoamines, imines (eg, 1,8-diazabicyclo [5.4.0] undec-7-ene, and 1,5-diazabicyclo [4.3.0]. And the like], 1,4-diazabicyclo [2.2.2] octane, guanidine salts (eg, guanidine carbonate) and the like. Among them, ammonium hydroxide or imines (eg, 1,8-diazabicyclo [5.4.0] undec-7-ene, and 1,5-diazabicyclo [4.3.0] non-5-ene etc. Is preferred.
The pH adjusters may be used alone or in combination of two or more.

  The content of the pH adjuster is not particularly limited as long as it can achieve the desired pH of the treatment liquid, but in general, it may be 0.1 to 5% by mass with respect to the total mass of the treatment liquid in the treatment liquid. Desirably, 0.1 to 2% by mass is more desirable.

<Aquatic ammonium hydroxides>
Moreover, it is preferable that the process liquid of this invention contains quaternary ammonium hydroxides. The addition of quaternary ammonium hydroxides can further improve the residue removal performance, and can also function as a pH adjuster.
The quaternary ammonium hydroxides are preferably compounds represented by the following general formula (4).

(In Formula (4), R ^{4A to} R ^4D each independently represent an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a benzyl group, or an aryl group.)

In formula (4), R ^{4A to} R ^4D are each independently an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a butyl group, etc.), a hydroxyalkyl group having 1 to 6 carbon atoms ( For example, it represents a hydroxymethyl group, a hydroxyethyl group, a hydroxybutyl group, etc., a benzyl group, or an aryl group (eg, a phenyl group, a naphthyl group, a naphthalene group, etc.). Among them, an alkyl group, a hydroxyethyl group or a benzyl group is preferable.

Specific examples of the compound represented by the formula (4) include tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetraethyl ammonium hydroxide, trimethyl hydroxyethyl ammonium hydroxide, methyl tri (hydroxyethyl) ammonium hydroxide, and tetra methyl ammonium hydroxide. (Hydroxyethyl) ammonium hydroxide, trimethylbenzyl ammonium hydroxide, and at least one quaternary ammonium hydroxide selected from the group consisting of choline are preferable, and in the present invention, tetramethyl ammonium hydroxide, tetraethyl. Ammonium hydroxide, benzyltrimethylammonium hydroxide, choline or tetrabutylammonium hydroxide is more preferred.
The quaternary ammonium hydroxides may be used alone or in combination of two or more.

  The content of quaternary ammonium hydroxides in the treatment liquid is preferably 0.1 to 15% by mass, and more preferably 1 to 10% by mass, based on the total mass of the treatment liquid of the present invention. preferable.

<Alkanolamines>
The treatment liquid preferably contains an alkanolamine from the viewpoint of corrosion prevention while promoting the solubilization of the additive component and the organic residue.
The alkanolamines may be any of primary amines, secondary amines and tertiary amines, preferably monoamines, diamines or triamines, more preferably monoamines. Preferably, the alkanol group of the amine has 1 to 5 carbon atoms.
In the treatment liquid of the present invention, a compound represented by the following formula (5) is preferable.
Equation _{^{(5): R 1 R 2}} -N-CH 2 CH 2 -O-R 3
In formula (5), R ¹ and R ² each independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyethyl group, and R ³ represents a hydrogen atom or a hydroxyethyl group, provided that In which at least one alkanol group is included)
Specific examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, tert-butyldiethanolamine, isopropanolamine, 2-amino-1-propanol, 3-amino-1-propanol, isobutanolamine. 2-amino-2-ethoxy-propanol and 2-amino-2-ethoxy-ethanol, also known as diglycolamine.
The alkanolamines may be used alone or in combination of two or more.

  The content of the alkanolamines in the treatment liquid is preferably 0.1 to 80% by mass, and more preferably 0.5 to 60% by mass with respect to the total mass of the treatment liquid of the present invention. And 0.5 to 20% by mass.

<Other additives>
Other additives may be contained in the treatment liquid of the present invention as long as the effects of the present invention are exhibited. Other additives include, for example, surfactants, antifoam agents, and the like.

<Preferred embodiment of treatment liquid>
Although the following are mentioned as a preferable aspect of the process liquid of this invention, It does not specifically limit to this.
(1) A treatment liquid comprising at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salt, water, a corrosion inhibitor, a chelating agent, and a water-soluble organic solvent.
(2) A treatment liquid comprising at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salt, water, a corrosion inhibitor, and a water-soluble organic solvent and / or alkanolamines.
(3) at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts, quaternary ammonium hydroxides, water, a corrosion inhibitor, a water-soluble organic solvent and / or alkanolamines Treatment solution.
(4) A treatment liquid comprising at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salt, water, and a fluoride.
(5) At least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salt, water, and compounds represented by the following formulas (A) to (C) (each definition in the formula is as described above And at least one member selected from the group consisting of substituted or unsubstituted tetrazole.

(6) In each of the above-mentioned treatment solutions (1) to (5), the Fe ion content is preferably the above-described content, and the Fe ion and hydroxylamine compound content (hydroxylamine and In the case where a plurality of compounds selected from the salts are contained, the content ratio (mass ratio) with the total amount thereof is preferably the above-mentioned content ratio.

<Filtering>
The treatment liquid of the present invention is preferably filtered with a filter for the purpose of removing foreign substances and reducing defects.
The material of the filter is not particularly limited as long as it is conventionally used for filtration applications etc. For example, a fluorocarbon resin such as PTFE (polytetrafluoroethylene), a polyamide such as nylon, etc. And resins and polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultrahigh molecular weight). Among these materials, polypropylene (including high density polypropylene) or nylon is preferable.
The pore diameter of the filter is suitably about 0.001 to 1.0 μm, preferably about 0.02 to 0.5 μm, and more preferably about 0.01 to 0.1 μm. By setting this range, it is possible to reliably remove fine foreign substances such as impurities and aggregates contained in the liquid while suppressing filter clogging.
When using filters, different filters may be combined.
Filtering by each filter may be performed only once or may be performed twice or more. The two or more times of filtering means, for example, a case where the solution is circulated and the two or more times of filtering is performed by the same filter.

The filtering can also be performed by combining different filters as described above. When different filters are combined and filtering is performed twice or more, it is preferable that the second and subsequent pore sizes be the same or larger than the pore size of the first filtering. Moreover, you may combine the 1st filter of the hole diameter which is different within the range mentioned above. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, it is possible to select from among various filters provided by Nippon Pall Co., Ltd., Advantec Toyo Co., Ltd., Nippon Entegris Co., Ltd. (old Japan Microlith Co., Ltd.), Kitz Micro Filter, etc.
The second filter can use a filter formed of the same material as the first filter described above. The pore diameter of the second filter is suitably about 0.01 to 1.0 μm, preferably about 0.1 to 0.5 μm. By setting it as this range, when the component particle is contained in the liquid, the foreign material mixed in the liquid can be removed with the component particle remaining.
For example, only a part of the components of the treatment solution to be finally prepared is mixed in advance to prepare a mixed solution, and the mixed solution is filtered by a first filter, and then the mixture is filtered by the first filter. The remaining components for forming the treatment solution may be added to the filtered mixture, and the mixture may be subjected to a second filtering.

<Impurity and coarse particles>
The treatment liquid of the present invention is preferably low in impurities, such as metals, etc., in the liquid in view of its use. In particular, the concentration of Na, K, and Ca ions in the solution is preferably in the range of 5 ppm (mass basis) or less.
Moreover, it is preferable that the treatment liquid contains substantially no coarse particles.
The coarse particles contained in the treatment liquid are particles such as dust, dust, organic solid matter, inorganic solid matter, etc. contained as impurities in the raw material, and dusts and dust carried as contaminants during the preparation of the treatment liquid. And organic solid matter and particles such as inorganic solid matter and the like which are not dissolved in the treatment liquid and are present as particles. The number of coarse particles present in the treatment liquid can be measured in the liquid phase using a commercially available measuring device in a light scattering type liquid-in-liquid measurement method using a laser as a light source.

<Metal concentration>
In the treatment liquid of the present invention, the ion concentration of a metal (a metal element of Na, K, Ca, Cu, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn) excluding Fe contained as impurities in the liquid is It is preferable that all are 5 ppm or less (preferably 1 ppm or less). In particular, since it is assumed that a processing solution with higher purity is required in the manufacture of the most advanced semiconductor device, the metal concentration is lower than the ppm order, ie, less than the ppb order. More preferably, it is further preferred that the order is ppt (the above-mentioned concentrations are all based on mass), and it is particularly preferred that it is substantially not contained.

(Storage container and storage conditions)
The material of the storage container for containing the treatment liquid (i.e., the portion in contact with the treatment liquid) is preferably a resin from the viewpoint of no metal elution. In the storage container for storing the treatment liquid, in particular, it is preferable that the material of the inner wall of the storage unit for storing the treatment liquid of the storage container is resin.
Specific examples of the resin include high density polyethylene (HDPE), high density polypropylene (PP), 6,6-nylon, tetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA) ), Polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), ethylene / tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene / hexafluoropropylene copolymer (FEP) and the like. Among them, a fluorine-based resin containing a fluorine atom in the molecule is preferable as the material of the inner wall of the housing portion.
As a specific example of the container whose material of the inner wall of the housing portion is a fluorine-based resin, for example, a FluoroPure PFA composite drum manufactured by Entegris can be mentioned. Also, the containers described on page 4 of JP-A-3-5026, page 3 of WO 2004/016526 and pages 9 and 16 of WO 99/46309, etc. It can be used.

  In the storage container, the pressure in the storage container is preferably near atmospheric pressure, more preferably from 96000 to 106000 Pa, and still more preferably from 9900 to 103300 Pa.

In addition, in order to facilitate control of the porosity, the storage container preferably has a plurality of openings that can be sealed by a lid, a valve, and the like at the top of the container. That is, by removing the lid, the valve and the like, it is possible to exchange the gas in the storage container with the atmosphere through the opening.
Further, at least one of the plurality of openings described above is preferably a gas vent provided with a gas vent function, and it is more preferable to have a gas vent valve at the gas vent. . The degassing valve may be in a form (method) integrated with the opening of the container, or may be a form (method) separate from the opening and attachable at the time of use.

Compounds selected from hydroxylamine and its salts, which are contained in the treatment liquid of the present invention, may decompose in storage conditions to produce a gas containing nitrogen oxides and the like. This decomposition is more likely to occur in the presence of carbon dioxide or in a high temperature environment.
Therefore, from the viewpoint of maintaining the effects of the present invention, storage at a storage temperature described later is preferable.
The treatment liquid of the present invention may be stored under an atmosphere of an inert gas such as nitrogen gas. In this case, the storage container is preferably in an aspect provided with a mechanism for filling the space in the storage container with an inert gas.
Furthermore, a preferred embodiment is a storage container having a function of releasing a gas containing nitrogen oxide or the like generated by the decomposition of a compound selected from hydroxylamine and a salt thereof from the container, as described above. It is more preferable that the mode having the above-described aspect and the mode in which at least one opening is a gas vent provided with a gas vent function, and in particular, it is preferable to have a gas vent valve in the gas vent.

As described above, the porosity in the storage container when the processing liquid is stored in the storage container is 0.01 to 30% by volume, and the deterioration of the residue removal performance of the processing liquid is further suppressed, 1-25 volume% is more preferable, and 12-20 volume% is further more preferable.
The effect of the present invention is remarkable when the porosity is 0.01 to 30% by volume.
In addition, the porosity is calculated | required by the following formula (1).
Formula (1): porosity = {1-(volume of processing solution for semiconductor device in storage container / container volume of storage container)} × 100
In the above formula, “container volume of storage container” means the volume of the storage container that contains the treatment liquid. Also, "the volume of the treatment liquid in the storage container" means the volume of the treatment liquid stored in the storage container. The space not filled with the treatment liquid in the storage container contains air containing oxygen.
In addition, the liquid temperature of the processing liquid in the storage container is, as described above, from room temperature standing (approximately 25 ° C., preferably 23 to 27 ° C.) to refrigerated storage (5 ° C.) from the viewpoint of achieving the effects of the present invention. The temperature range may be in the vicinity, preferably between 0 and 7 ° C., and more preferably between 0 and 5 ° C. The treatment liquid of the present invention is unlikely to cause the deterioration of the residue removal performance even when stored under the thermocycle environment in the room temperature standing condition and the cold storage.

  Moreover, it is preferable that the temperature at the time of enclosing a process liquid in a storage container is 20-25 degreeC.

[Treatment liquid container]
The treatment liquid container of the present invention comprises: a storage container; and a processing solution for a semiconductor device containing at least one selected from hydroxylamine and a hydroxylamine salt, contained in the storage container, and water. The void ratio in the storage container is 0.01 to 30% by volume. That is, the treatment liquid container is intended to be the one in which the above-mentioned treatment liquid for semiconductor device is accommodated in the storage container. In addition, the porosity is calculated | required by the above-mentioned Formula (1).
About the suitable aspect of a process liquid container and its effect, it is the same as that of the aspect demonstrated in the storage method of the above-mentioned process liquid.

(Application of treatment liquid for semiconductor device)
The processing liquid for semiconductor devices is suitably used in each process at the time of manufacturing a semiconductor device. For example, as described above, it can be used as a cleaning solution for removing residues after the dry etching process, and as a stripping solution for stripping a resist film, a permanent film (for example, a color filter), etc. . Among them, it can be suitably used as a cleaning solution.
The semiconductor device processing solution can also be suitably applied as a cleaning solution after a dry etching process using a metal hard mask as a mask. As a material which comprises a metal hard mask, it is preferable to contain any one or more of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx, for example. Here, x and y are numbers represented by x = 1 to 3 and y = 1 to 2, respectively.
Moreover, it can use suitably also for the dry ashing residue removal by having passed through the dry etching process (for example, dry ashing process) optionally performed after the dry etching process using a metal hard mask.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the following examples.

(Examples A1 to A7, B1 to B7, C1 to C7, D1 to D7, E1 to E7, F1 to F7, G1 to G7, H1 to H7, I1 to I7, J1 to J7, K1 to K7, L1 to L7 , M1 to M7, Comparative Examples A1, A2, B1, B2, C1, C2, D1, D2, E1, E2, F1, F2, G1, G2, H1, H2, I1, I2, J1, J2, K1, K2 , L1, L2, M1, M2)

(1) Preparation of treatment solution <Purification of water>
The water used for preparation of the following process liquids was prepared using the method as described in Unexamined-Japanese-Patent No.2011-110515 stage-to [0084]. In addition, this method includes a metal ion removal step.
The obtained water had an Fe ion content and a Co ion content of 1 ppt mass or less, respectively. In addition, each content of Fe ion and Co ion was measured by inductively coupled plasma mass spectrometry (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).

Next, treatment solutions A to M shown below were prepared (each at a pH of 7 to 11). Next, the obtained treatment liquid was passed through an ion exchange membrane for purification to remove Fe ions in the treatment liquid.
In each treatment, the contents (% by mass) of various components to be used are as described in the table, and the balance is the water obtained above.

The various components used for the process liquid are shown below.
<Reductant>
HA: hydroxylamine (manufactured by BASF)
HAS: hydroxyl ammonium sulfate (manufactured by BASF)

<Corrosion inhibitor>
1-thioglycerol (corresponding to formula (A), manufactured by Wako Pure Chemical Industries, Ltd.)
5-methyl-1H-benzotriazole (5 MBTA: equivalent to the formula (C), manufactured by Tokyo Chemical Industry Co., Ltd.)
Catechol (equivalent to formula (B), manufactured by Kanto Chemical Co., Ltd.)

Chelating agent
DPTA: Diethylenetriaminepentaacetic acid (manufactured by Chubu Kyrest Co., Ltd.)

<Water-soluble organic solvent>
EGBE: ethylene glycol monobutyl ether (manufactured by Wako Pure Chemical Industries, Ltd.)
<PH adjuster>
DBU: 1,8-Diazabicyclo [5.4.0] undec-7-ene (San-Apro)
NH ₄ OH: ammonium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.)
<Aquatic ammonium hydroxides>
Colin: Seichem's <Fluoride>
NH ₄ F: ammonium fluoride (manufactured by Wako Pure Chemical Industries, Ltd.)

<Alkanolamines>
Monoethanolamine (made by Tokyo Chemical Industry Co., Ltd.)
Diglycolamine (alias: 2- (2-aminoethoxy) ethanol, manufactured by Tokyo Chemical Industry Co., Ltd.)
TEA: Triethanolamine (made by Tokyo Chemical Industry Co., Ltd.)

(2) Evaluation The evaluation shown below was performed about each process liquid prepared above. In the following evaluation, a model film made of TiO, which is 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, the residue removal performance is excellent, and when the etching rate is low, the residue removal performance is inferior.
(A) Etching rate at fresh time (ER _Fr )
A model film in which a TiO film was laminated on the substrate surface was prepared. For each of the treatment solutions A to M, each treatment solution is brought into contact with the TiO film immediately after preparation of the treatment solution (immediately after composition of the treatment solution), etching treatment of the TiO film is performed, and the etching rate is calculated It was ER _Fr.
(B) Etching rate after thermo cycle test (ER _Age )
Porosity (porosity (volume%) = {1- (volume of processing solution for semiconductor device in storage container / container volume of storage container) shown in Tables 1 to 13 at 25 ° C. and atmospheric pressure, respectively} × 100 Each of the treatment solutions A to M was sealed in a resin container so as to be the above. The resin container was a clean bottle manufactured by Icero Chemical Co., Ltd., and the total volume of the container was 500 ml.
Then, for each treatment solution sealed in the container, 8 hours at 5 ° C. which is a normal cold storage temperature → 4 hours at 25 ° C. which is a room temperature → 8 hours at 5 ° C. which is a normal cold storage temperature → A thermocycling test was performed at a constant temperature of 25.degree. C. for 4 hours in a cycle of 180 days. Next, the TiO film was etched using the processing solution after the thermocycle test, and the etching rate (etching rate) was defined as ER _Age .

(C) Calculation and evaluation of etching rate maintenance rate Based on the obtained etching rates ER _Fr and ER _Age , the etching rate maintenance rate (etching rate maintenance rate (%) = ER _Age / ER _Fr x 100) is calculated, Evaluation was performed according to the following evaluation criteria.
<Etching rate maintenance rate (%)>
"1": 60% or less "2": 60% to 70% or less "3": 70% to 80% or less "4": 80% to 90% or less "5": 90% to 95% Less than "6": more than 95% to 100%

(Treatment solution A)
HA 4 mass%
Water 96% by mass

(Treatment solution B)
HAS 4 mass%
Amount needed to adjust to NH ₄ OH pH 7.8

(Treatment solution C)
HA 15% by mass
Water 84 mass%
1-thioglycerol 1% by mass

(Treatment solution D)
HA 20 mass%
Water 72.5 mass%
TEA 7.5 mass%

(Treatment solution E)
HA 20 mass%
Water 72.5 mass%
Choline 7.5 mass%

(Treatment solution F)
HA 20 mass%
79% water
NH ₄ F 0.5 mass%
NH ₄ OH 0.5 mass%

(Treatment solution G)
HA 4 mass%
Water 89.4% by mass
EGBE 5 mass%
DBU 0.85 mass%
DTPA 0.5 mass%
5MBTA 0.25 mass%

(Treatment solution H)
HA 15% by mass
Water 83.5% by mass
1-thioglycerol 1% by mass
5MBTA 0.5 mass%

(Treatment solution I)
HA 20 mass%
Water 72% by mass
TEA 7.5 mass%
5MBTA 0.5 mass%

(Treatment solution J)
HA 20 mass%
Water 72% by mass
Choline 7.5 mass%
5MBTA 0.5 mass%

(Treatment solution K)
HA 20 mass%
Water 78.5 mass%
NH ₄ F 0.5 mass%
NH ₄ OH 0.5 mass%
5MBTA 0.5 mass%

(Processing solution L)
HA 20 mass%
Water 20% by mass
Diglycolamine 55% by mass
Catechol 5% by mass

(Treatment solution M)
HA 20 mass%
Water 20% by mass
55% by mass of monoethanolamine
Catechol 5% by mass

From the results shown in Tables 1 to 13, even when any treatment liquid is used, the porosity is set to 0.01 to 30% by volume (preferably 1 to 25% by volume, more preferably 12 to 20% by volume). It has been confirmed that when the etching rate is reduced (in other words, the etching rate is well maintained). From these results, it is understood that the deterioration of the residue removal performance is suppressed if the porosity is a predetermined value.
On the other hand, when the porosity was out of the numerical range of 0.01 to 30% by volume, a decrease in the etching rate was confirmed.

Examples A11 to 17
Next, in the formulation of treatment solution A, treatment solutions 2A to 7A were prepared in which the amount of hydroxylamine was changed as shown in Table 14, and the method was the same as in Example A1 with the porosity in the container being 15% by volume. The thermocycle test was carried out according to Based on the obtained etching rates ER _Fr and ER _Age , the etching rate maintenance rate was calculated and evaluated.
The results are shown in Table 14.

(Examples B11 to B17)
Next, in the formulation of the treatment solution B, treatment solutions 2B to 7B were prepared in which the amount of hydroxylamine salt was changed as shown in Table 15, and in each case the porosity in the container was 15% by volume as in Example B1. The thermocycle test was carried out according to the method. Based on the obtained etching rates ER _Fr and ER _Age , the etching rate maintenance rate was calculated and evaluated.
The results are shown in Table 15.

  From the results in Table 14 and Table 15, the content of at least one compound selected from hydroxylamine and hydroxyamine salt was 4 to 25% by mass (preferably 12 to 18% by mass) based on the total mass of the treatment liquid. In the case, it was confirmed that the reduction of the etching rate is more suppressed (in other words, the etching rate is well maintained).

(Example A21 to Example A27)
Next, in the formulation of treatment solution A, when purifying the treatment solution through an ion exchange membrane, the treatment was performed such that the content of Fe ions in the treatment solution (the amount relative to the total mass of treatment solution) was prepared as shown in Table 16. Solutions 12A to 17A were prepared, and the thermocycle test was carried out in the same manner as in Example A1, with the void ratio in the container being 15% by volume. Based on the obtained etching rates ER _Fr and ER _Age , the etching rate maintenance rate was calculated and evaluated.
In addition, content of Fe ion with respect to the process liquid total mass in a process liquid was measured by the inductive coupling plasma mass spectrometer (Yokogawa Analytical Systems make, Agilent 7500cs type | mold).
The results are shown in Table 16.

Example A28
The treatment liquid 28A prepared so that the Fe concentration was 12 mass ppm was prepared for the treatment liquid A prepared above, and the evaluation was 5 under the same conditions as in Example A21 except the above. .

  From the results of Table 16 and Example A28, 10 mass ppt to 10 mass ppm (preferably 1 mass ppb to 1 mass ppm, more preferably 1 mass ppb to 50 mass ppb, more preferably 1) of Fe ions in the treatment liquid It was confirmed that the decrease of the etching rate is further suppressed (in other words, the etching rate is well maintained) by being present in a small amount such as mass ppb to 5 mass ppb).

(Examples C11, D11, E11, F11, G11)
Next, in the formulations of treatment solutions C to G, when purifying the treatment solution through an ion exchange membrane, the content (amount relative to the total mass of treatment solution) of Fe ions in the treatment solution is 5 as shown in Table 17 respectively. The thermocycling test was implemented by the method similar to Example A1, all prepared the processing liquids 2C-2G adjusted to mass ppb, and made the porosity in a container 15 volume% in all. Based on the obtained etching rates ER _Fr and ER _Age , the etching rate maintenance rate was calculated and evaluated.
In addition, content of Fe ion with respect to the process liquid total mass in a process liquid was measured by the inductive coupling plasma mass spectrometer (Yokogawa Analytical Systems make, Agilent 7500cs type | mold).
The results are shown in Table 17.

  From the results in Table 17, also in the formulations of treatment liquids C to G, 10 mass ppt to 10 mass ppm (preferably 1 mass ppb to 1 mass ppm, more preferably 1 mass ppb to 50 mass) of Fe ions in the treatment liquid It was confirmed that lowering the etching rate is further suppressed (in other words, the etching rate is well maintained) by being present in a small amount of ppb, more preferably 1 mass ppb to 5 mass ppb).

(Application to semiconductor substrate)
(1) Preparation of a Laminate Having a Co Film First, a laminate having a Co film, a SiN film, an SiO ₂ film, and a metal hard mask (TiN) having a predetermined opening in this order on a substrate (Si) Formed.
Next, using this laminate, plasma etching was performed using a metal hard mask as a mask to etch the SiN film and the SiO ₂ film until the surface of the Co film was exposed, thereby forming holes. When the cross section of the laminate in which the hole was formed was confirmed by a scanning electron microscope (SEM: Scanning Electron Microscope), plasma etching residues were observed on the wall of the hole.
(2) Cleaning of Semiconductor Substrate The treatment solutions A prepared above were subjected to the above-mentioned thermocycle test under predetermined porosity conditions (each treatment solution prepared in Examples A1 to A7 and Comparative Examples A1 and A2) A processing solution (corresponding to a processing solution) was prepared, and the processing speed of the plasma etching residue deposited on the obtained semiconductor substrate was evaluated.

The evaluation of the processing rate of the plasma etching residue was also performed by the same method as the etching rate maintenance rate described above.
Specifically, based on the processing speed (processing speed _Fr ) at the Fresh time and the processing speed (processing speed _age ) after the thermocycle test, the maintenance rate of the processing speed (processing speed maintenance rate (%) = processing speed _age / The processing rate _Fr × 100) was calculated, and the evaluation was performed according to the same evaluation criteria as the etching rate maintenance rate described above.
As a result, even when the processing solution A is applied as a cleaning liquid for a semiconductor substrate, the same results as those of Examples A1 to A7 and Comparative Examples A1 and A2 are obtained. The reduction of the processing speed of the plasma etching residue is suppressed when it is set to 01 to 30% by volume (preferably 1 to 25% by volume, more preferably 12 to 20% by volume) (the processing rate of the plasma etching residue is It is confirmed that it is maintained well.
Moreover, it replaced with the process liquid A and the same result was confirmed also about process liquid BM.

  Moreover, about the process liquid CM, when the process liquid which substituted HA to HAS was produced and the same experiment was done, the same result was obtained in all.

In the treatment solution J, the pH was adjusted by adjusting the amount of choline. In addition, when setting it as acidic pH, oxalic acid dihydrate (Wako Pure Chemical Industries Ltd. make) was added and adjusted. Thus, treatment solutions N1 to N5 of pH 5.0, 6.0, 7.0, 7.5, and 11.0 were prepared. A thermocycle test was carried out in the same manner as in Example A1 except that the porosity in the container was 15% by volume. Based on the obtained etching rates ER _Fr and ER _Age , the etching rate maintenance rate was calculated and evaluated.
As a result of evaluation, the treatment liquid N1 (pH 5.0) was 3, the treatment liquid N2 was 4, and the treatment liquids N3 to N5 were 5.

In the same manner as in Example A1, except that the processing solution N3 was sealed in a container provided with a degassing valve and stored for 2 days at 70 ° C. with a porosity of 15% by volume, the calculation of the etching rate retention rate was performed. It evaluated.
In the container provided with the degassing valve, there was no influence of changes in internal pressure and the like, and no change in residue removal performance was observed before and after storage.
From this result, even in a storage environment at high temperature, such as outdoors in summer, it is expected that the container having the degassing valve does not have the influence of the internal pressure change and the effect of the present invention can be stably obtained. Be done.

Claims (21)

A storage method of a processing solution for semiconductor device, which stores the processing solution for semiconductor device containing at least one selected from hydroxylamine and hydroxylamine salt and water in a storage container,
In the treatment liquid, the total content of at least one selected from the hydroxylamine and the hydroxylamine salt is 4 to 25% by mass with respect to the total mass of the treatment liquid, and the content of Fe ions is 10 mass ppt to 10 mass ppm,
The storage method of the processing liquid for semiconductor devices which sets the porosity in the said storage container as 0.01-30 volume%.
In addition, the porosity is calculated | required by the following formula (1).
Formula (1): porosity = {1-(volume of the processing solution for semiconductor devices in the storage container / container volume of the storage container)} × 100 A storage method of a processing solution for semiconductor device, which stores the processing solution for semiconductor device containing at least one selected from hydroxylamine and hydroxylamine salt and water in a storage container,
The treatment liquid is sealed in the storage container so that the porosity in the storage container is 0.01 to 30% by volume, and the treatment liquid is stored in the storage container,
A storage method of a processing solution for a semiconductor device, wherein a space not filled with the processing solution in the storage container contains air.
In addition, the porosity is calculated | required by the following formula (1).
Formula (1): porosity = {1-(volume of the processing solution for semiconductor devices in the storage container / container volume of the storage container)} × 100   The semiconductor device according to claim 2, wherein the total content of at least one selected from the hydroxylamine and the hydroxylamine salt in the treatment liquid is 1 to 30% by mass with respect to the total mass of the treatment liquid. Storage method of treatment solution.   The storage method of the processing liquid for semiconductor devices according to claim 2 or 3 whose content of Fe ion is 10 mass ppt-10 mass ppm in said processing liquid.   The storage method of the process liquid for semiconductor devices of any one of Claims 1-4 whose porosity in the said storage container is 1-25 volume%.   The storage method of the process liquid for semiconductor devices of any one of Claims 1-5 whose porosity in the said storage container is 12-20 volume%.   The storage method of a semiconductor device processing solution according to any one of claims 1 to 6, wherein the semiconductor device processing solution further contains a corrosion inhibitor.   The method for storing a semiconductor device processing solution according to any one of claims 1 to 7, wherein the semiconductor device processing solution further contains at least one of a water-soluble organic solvent and an alkanolamine.   The storage method of a semiconductor device processing solution according to any one of claims 1 to 8, wherein the semiconductor device processing solution further contains quaternary ammonium hydroxides.   The storage method of a semiconductor device processing solution according to any one of claims 1 to 9, wherein the semiconductor device processing solution further contains a fluoride.   The method for storing a semiconductor device processing solution according to any one of claims 1 to 10, wherein the semiconductor device processing solution further contains a chelating agent. The processing solution for a semiconductor device according to any one of claims 7 to 11, wherein the corrosion inhibitor is at least one selected from the group consisting of compounds represented by the following formulas (A) to (C). Storage method.

In Formula (A), each of R ^{1A to} R ^5A independently represents a hydrogen atom, a hydrocarbon group, a hydroxyl group, a carboxy group, or an amino group. However, the structure contains at least one group selected from a hydroxyl group, a carboxy group and an amino group.
In Formula (B), R ^{1B to} R ^4B each independently represent a hydrogen atom or a hydrocarbon group.
In Formula (C), R ^1C , R ^2C and R ^N each independently represent a hydrogen atom or a hydrocarbon group. Also, R ^1C and R ^2C may combine to form a ring.   The pH of the said processing liquid for semiconductor devices is 6-11, The storage method of the processing liquid for semiconductor devices of any one of Claims 1-12. A treatment liquid container comprising: a storage container; and a processing solution for semiconductor device containing at least one selected from hydroxylamine and hydroxylamine salt, and water, contained in the storage container. ,
In the treatment liquid, the total content of at least one selected from the hydroxylamine and the hydroxylamine salt is 4 to 25% by mass with respect to the total mass of the treatment liquid, and the content of Fe ions is 10 mass ppt to 10 mass ppm,
The process liquid container whose porosity in the said storage container is 0.01-30 volume%.
In addition, the porosity is calculated | required by the following formula (1).
Formula (1): porosity = {1-(volume of the processing solution for semiconductor devices in the storage container / container volume of the storage container)} × 100 A treatment liquid container comprising: a storage container; and a processing solution for semiconductor device containing at least one selected from hydroxylamine and hydroxylamine salt, and water, contained in the storage container. ,
The treatment liquid is enclosed in the storage container so that the porosity in the storage container is 0.01 to 30% by volume, and the treatment liquid is stored in the storage container,
A treatment liquid container, wherein a space not filled with the treatment liquid in the storage container contains air.
In addition, the porosity is calculated | required by the following formula (1).
Formula (1): porosity = {1-(volume of the processing solution for semiconductor devices in the storage container / container volume of the storage container)} × 100 The treatment liquid container according to claim 14 or 15, wherein the porosity in the storage container is 1 to 25% by volume. The processing liquid container according to any one of claims 14 to 16, wherein the porosity in the storage container is 12 to 20% by volume.   The processing liquid container according to any one of claims 14 to 17, wherein a material of an inner wall of the storage container is a resin.   The material of the inner wall of the storage container is high density polyethylene, high density polypropylene, 6,6-nylon, tetrafluoroethylene, copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, polychlorotrifluoroethylene, ethylene / chlorotrile The resin according to any one of claims 14 to 18, which is at least one resin selected from a fluoroethylene copolymer, an ethylene / tetrafluoroethylene copolymer, and a tetrafluoroethylene / hexafluoropropylene copolymer. The treatment liquid container described in.   The treatment liquid container according to any one of claims 14 to 19, wherein the material of the inner wall of the storage container is a fluorine-based resin containing a fluorine atom in the molecule.   The processing liquid container according to any one of claims 14 to 20, wherein the storage container has a plurality of openings.