Treatment liquid for semiconductor device

Abstract

To provide a treatment liquid for a semiconductor device which is excellent in corrosion resistance of a cobalt atom-containing layer and a tungsten atom-containing layer and excellent in removability of fluorine-based residues.SOLUTION: A treatment liquid for a semiconductor device contains a fluorine-containing compound, a cyclic ether compound, diaminoalkane, and water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a processing liquid for semiconductor devices. [Background technology]

[0002] In the manufacturing process of semiconductor devices such as semiconductor elements and various substrates, a dry etching process is usually employed when forming semiconductor integrated circuits. This dry etching process generates dry etching residues such as fluorine-based residues, which must be removed. Some semiconductor devices to be processed contain metal wiring materials (e.g., cobalt, tungsten, etc.).

[0003] As an example of such a treatment liquid, Patent Document 1 describes a treatment liquid for semiconductor devices that contains a fluorine-containing compound and a water-soluble aromatic compound that has a benzene ring but no heterocyclic group, and has a pH of 5 or less. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2018 / 61582 Summary of the Invention [Problem to be solved by the invention]

[0005] There are various metal materials for wiring used in semiconductor devices and masking materials used during dry etching, and the combinations of these materials are also varied. Therefore, from the viewpoint of corrosion prevention and the like for various metal materials used in wiring and the like for semiconductor devices, the development of a new semiconductor device treatment solution is desired. An example of such a semiconductor device is a substrate having a layer containing cobalt atoms (cobalt atom-containing layer) or a layer containing tungsten atoms (tungsten atom-containing layer). In this regard, there is a demand for a treatment solution that has excellent corrosion prevention properties for the cobalt atom-containing layer and the tungsten atom-containing layer, as well as excellent removability of dry etching residues such as fluorine-based residues. However, there is still room for improvement.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a semiconductor device treatment liquid that has excellent corrosion prevention properties for a cobalt atom-containing layer and a tungsten atom-containing layer, and is also excellent in removing fluorine-based residues. [Means for solving the problem]

[0007] As a result of intensive investigations to achieve the above-mentioned object, the present inventors have discovered that a semiconductor device treatment liquid contains a fluorine-containing compound, a cyclic ether compound, a diaminoalkane, and water, and have thus completed the present invention.

[0008] That is, the present invention is as follows. <1> The semiconductor device treatment liquid contains a fluorine-containing compound, a cyclic ether compound, a diaminoalkane, and water. <2> the fluorine-containing compound is at least one selected from the group consisting of hydrogen fluoride, ammonium fluoride, tetrafluoroboric acid, tetramethylammonium fluoride, and triethanolamine hydrofluoride; <1> 1. The semiconductor device treatment liquid according to claim 1, <3> In the cyclic ether compound, the number of carbon atoms forming the ring is 2 to 4, and the number of oxygen atoms forming the ring is 1 to 2. <1> 1. The semiconductor device treatment liquid according to claim 1, <4> The content of the cyclic ether compound is 0.000001% by mass to 0.01% by mass. <1> 1. The semiconductor device treatment liquid according to claim 1, <5> The diaminoalkane is a compound represented by the following formula (1): <1> 1. The semiconductor device treatment liquid according to claim 1,

[0009] [ka]

[0010] (In the formula, n represents a number from 1 to 15.) <6> the semiconductor device includes a substrate having a metal layer containing cobalt atoms, and the semiconductor device treatment solution is used to treat the metal layer. <1> 1. The semiconductor device treatment liquid according to claim 1, <7> the semiconductor device includes a substrate having a metal layer containing tungsten atoms, and the semiconductor device treatment solution is used to treat the metal layer. <1> 1. The semiconductor device treatment liquid according to claim 1, <8> It is used to remove residues generated after etching a substrate having a metal layer, which is used in the manufacture of the semiconductor device. <1> 1. The semiconductor device treatment liquid according to claim 1, [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a semiconductor device treating liquid that has excellent corrosion prevention properties for a cobalt atom-containing layer and a tungsten atom-containing layer, and is also excellent in removing fluorine-based residues. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The following present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be practiced by appropriately modifying it within the scope of its gist. Furthermore, unless otherwise specified, the configurations and parameters disclosed in this specification can be arbitrarily combined. Furthermore, unless otherwise specified, the upper and lower limits of the values ​​disclosed in this specification can be arbitrarily combined.

[0013] <Semiconductor device processing solution>

[0014] The semiconductor device processing solution according to the present embodiment (hereinafter, sometimes simply referred to as the "processing solution") contains a fluorine-containing compound, a cyclic ether compound, a diaminoalkane, and water. Conventional processing solutions have been formulated with acidic components such as hydrogen fluoride to improve residue removability. However, this tends to reduce corrosion resistance, leaving room for improvement in achieving both residue removability and corrosion resistance at a practical level. For example, cobalt and tungsten are promising semiconductor materials, both now and in the future. Therefore, increased demand for these substrate processing processes is expected. Furthermore, in the development of cleaning solutions for removing residues after dry etching in semiconductor manufacturing processes, the corrosiveness (damage) of cleaning solutions containing fluorine-containing compounds such as hydrogen fluoride to tungsten is not negligible, limiting their use.

[0015] In this regard, the treatment liquid according to this embodiment is surprisingly excellent in corrosion prevention of cobalt atom-containing layers and tungsten atom-containing layers, and is also excellent in removing fluorine-based residues, and therefore can be suitably used as a treatment liquid for semiconductor devices having a cobalt atom-containing layer and / or a tungsten atom-containing layer. The reason for this is unclear, but it is presumed that the treatment liquid using a fluorine-containing compound in combination with a cyclic ether compound and a diaminoalkane can prevent corrosion of cobalt and tungsten while maintaining the residues (however, the function of this embodiment is not limited to this). Each component will be described below.

[0016] ((a) Fluorine-containing compound)

[0017] The treatment solution according to this embodiment contains a fluorine-containing compound. Specific examples of the (a) fluorine-containing compound include, but are not limited to, hydrogen fluoride, ammonium fluoride, tetrafluoroboric acid, ammonium tetrafluoroborate, tetramethylammonium fluoride, and triethanolamine hydrofluoride. These compounds also include isomers of ammonium bifluoride and tetraalkylammonium bifluoride. Among these, at least one compound selected from the group consisting of hydrogen fluoride, ammonium fluoride, tetrafluoroboric acid, tetramethylammonium fluoride, and triethanolamine hydrofluoride is preferred, with hydrogen fluoride and / or ammonium fluoride being more preferred, and hydrogen fluoride being even more preferred. These fluorine-containing compounds may be salts. Furthermore, the fluorine-containing compound is preferably a compound that does not contain metal ions. These compounds may be used alone or in combination. The use of such fluorine-containing compounds can achieve both corrosion resistance of the cobalt atom-containing layer and the tungsten atom-containing layer and the ability to remove fluorine-based residues at a higher level.

[0018] The content of the fluorine-containing compound is not particularly limited, but is preferably 0.01 to 10% by mass. The lower limit of this content is more preferably 0.03% by mass or more, even more preferably 0.05% by mass or more, even more preferably 0.07% by mass or more, and even more preferably 0.1% by mass or more. The upper limit of this content is more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. By setting the content of the fluorine-containing compound within the above range, it is possible to achieve both corrosion resistance of the cobalt atom-containing layer and the tungsten atom-containing layer and removability of fluorine-based residues at an even higher level.

[0019] The content of each component in the semiconductor device treatment solution may be adjusted to the desired concentration in advance, or the solution may be a concentrated product distributed or supplied and diluted to the desired concentration when used to treat semiconductor devices (including electronic devices, etc.).

[0020] ((b) Cyclic ether compounds)

[0021] The treatment liquid according to this embodiment contains a cyclic ether compound. (b) The cyclic ether compound preferably contains one ring containing an oxygen atom in the molecule. The number of carbon atoms forming the ring in the cyclic ether compound is preferably 2 to 4. The number of carbon atoms forming the ring here refers to the number of carbon atoms forming one ring. The number of oxygen atoms forming the ring in the cyclic ether compound is preferably 1 to 2.

[0022] The molecular weight of the cyclic ether compound is not particularly limited, but is preferably 200 or less, more preferably 150 or less, even more preferably 105 or less, even more preferably 90 or less, and still more preferably 50 or less. The lower limit of this molecular weight is preferably 40 or more.

[0023] Specific examples of cyclic ether compounds include ethylene oxide (ethylene oxide, oxirane; molecular weight 44.5), 1,4-dioxane (molecular weight 88.1), tetrahydrofuran (THF, molecular weight 72.1), and 4-methyltetrahydropyran (MTHP, molecular weight 100). Among these, ethylene oxide (EO) and 1,4-dioxane (DO) are preferred, with ethylene oxide being more preferred. These compounds may be used alone or in combination of two or more. Use of such cyclic ether compounds can achieve both higher levels of corrosion resistance for the cobalt atom-containing layer and the tungsten atom-containing layer and higher levels of removability of fluorine-based residues.

[0024] The cyclic ether compound preferably contains ethylene oxide and 1,4-dioxane, and more preferably contains only ethylene oxide and / or 1,4-dioxane. When ethylene oxide and 1,4-dioxane are used in combination, the mass ratio (ethylene oxide:1,4-dioxane) is, for example, preferably 10:90 to 90:10, more preferably 15:85 to 85:15, even more preferably 30:70 to 70:30, and even more preferably 40:60 to 60:40.

[0025] The content of the cyclic ether compound is preferably 0.000001% by mass to 0.01% by mass. The lower limit of this content is more preferably 0.000005% by mass or more, even more preferably 0.000008% by mass or more, and even more preferably 0.00001% by mass or more. The upper limit of this content is more preferably 0.005% by mass or less, even more preferably 0.003% by mass or less, even more preferably 0.001% by mass or less, even more preferably 0.0001% by mass or less, and even more preferably 0.00007% by mass or less. When two or more cyclic ether compounds are used in combination, the total content of each component is preferably within the above-mentioned numerical range. By setting the content of the cyclic ether compound within the above-mentioned range, it is possible to achieve both corrosion resistance of the cobalt atom-containing layer and the tungsten atom-containing layer and removability of fluorine-based residues at an even higher level.

[0026] ((c) Diaminoalkane)

[0027] The treatment liquid according to this embodiment contains a diaminoalkane. (c) The structure of the diaminoalkane is not particularly limited and may be either linear or branched, but linear is preferred. Furthermore, the diaminoalkane contains a linear alkylene group (-(CH2) n -, where n represents a number.) The number of carbon atoms in the diaminoalkane is not particularly limited, but is preferably 1 to 15. The lower limit of the number of carbon atoms is more preferably 3 or more, even more preferably 4 or more, still more preferably 5 or more, and even more preferably 6 or more. The upper limit of the number of carbon atoms is more preferably 13 or less, even more preferably 12 or less, still more preferably 11 or less, and even more preferably 10 or less. By using such a diaminoalkane, it is possible to achieve both corrosion resistance of the cobalt atom-containing layer and the tungsten atom-containing layer and removability of fluorine-based residues at an even higher level.

[0028] The diaminoalkane is preferably a compound represented by the following formula (1).

[0029] [ka]

[0030] (In the formula, n represents a number from 1 to 15.)

[0031] In formula (1), n ​​is 1 to 15, and the lower limit of n is more preferably 3 or more, even more preferably 4 or more, still more preferably 5 or more, and even more preferably 6 or more. The upper limit of n is more preferably 13 or less, even more preferably 12 or less, still more preferably 11 or less, and even more preferably 10 or less. When the number of carbon atoms is within this numerical range, it is possible to achieve both corrosion resistance of the cobalt atom-containing layer and the tungsten atom-containing layer and removability of fluorine-based residues at an even higher level.

[0032] A specific example of the diaminoalkane is preferably at least one selected from the group consisting of 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, and 1,10-diaminodecane. The diaminoalkane may be used alone or in combination of two or more.

[0033] The content of the diaminoalkane is preferably 50 ppm by mass to 3000 ppm by mass. The lower limit of this content is more preferably 60 ppm by mass or more, even more preferably 70 ppm by mass or more, and even more preferably 80 ppm by mass or more. The upper limit of this content is more preferably 2500 ppm by mass or less, even more preferably 2000 ppm by mass or less, even more preferably 1500 ppm by mass or less, and even more preferably 1300 ppm by mass or less. Note that "ppm" is by mass (ppm by mass) unless otherwise specified. Furthermore, when two or more diaminoalkanes are used in combination, it is preferable that the total content of each component is in the above-mentioned numerical range. By setting the content of the diaminoalkane within the above-mentioned range, it is possible to achieve both the corrosion prevention properties of the cobalt atom-containing layer and the tungsten atom-containing layer and the removability of fluorine-based residues at an even higher level.

[0034] ((d)Wed)

[0035] The treatment liquid according to this embodiment contains water. Although the type of water is not particularly limited, it is preferable that the water has been subjected to distillation, ion exchange treatment, filtering, various adsorption treatments, or the like to remove or reduce metal ions, organic impurities, particle particles, and the like. Examples of the water that is preferable include pure water, ultrapure water, and deionized water.

[0036] The content of water is not particularly limited, but it is used as a solvent. As the solvent, it may be used in combination with an organic solvent described later. Water may be contained as the balance of the components described above and the components described later, and is typically 40 to 99.999 mass% based on the total amount of the semiconductor device treatment liquid. The lower limit may be, for example, 80 mass% or more, 90 mass% or more, or 95 mass% or more. The upper limit may be, for example, 99.998 mass% or less, or 99.99 mass% or less.

[0037] (e) Organic Solvent

[0038] The treatment liquid according to this embodiment may further contain an organic solvent. The (e) organic solvent may be, for example, a water-soluble organic solvent. The (e) organic solvent may be any organic solvent that is miscible with the above-described components (a), (b), (c), and (d), and an appropriate organic solvent may be selected taking into consideration the type and content of the other components used. Preferably, the organic solvent is an organic solvent other than the compounds corresponding to components (a), (b), and (c). Furthermore, when an (e) organic solvent is used, it is preferably a water-soluble organic solvent other than the above-described (b) cyclic ether compound.

[0039] Specific examples of the water-soluble organic solvent include alcohols such as isopropanol, ethanol, ethylene glycol, propylene glycol, glycerin, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, furfuryl alcohol, and 2-methyl-2,4-pentanediol; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; and dimethyl sulfoxide (DMSO). sulfoxides such as dimethyl sulfone, diethyl sulfone, bis(2-hydroxyethyl) sulfone, tetramethylene sulfone, and the like; sulfones such as N,N-dimethylformamide (DMF), N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-diethylacetamide, and the like; lactams such as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone, and the like; imidazolidinones such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone, and the like; lactones such as γ-butyrolactone and δ-valerolactone, and derivatives thereof. These may be used alone or in combination of two or more.

[0040] The content of the organic solvent relative to the total content of water and organic solvent is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less. The lower limit of the content of the organic solvent relative to the total content of water and organic solvent is not particularly limited, but may be 0.01% by mass or more, or 0.1% by mass or more.

[0041] The treatment liquid according to this embodiment is preferably a water-based treatment liquid (sometimes referred to as an aqueous treatment liquid, etc.) from the viewpoints of component solubility, environmental load reduction, cost efficiency, etc. A water-based treatment liquid is a treatment liquid that does not contain an organic solvent, or a treatment liquid that contains water and an organic solvent and in which the content of the organic solvent is lower than the content of water. From this viewpoint, a more preferred embodiment is one in which the content of the organic solvent in the treatment liquid according to this embodiment is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 0% by mass or less (i.e., containing only water as the solvent).

[0042] ((f) Other ingredients)

[0043] The treatment solution according to this embodiment may further contain optional components other than the components described above, as long as the effects of this embodiment can be obtained. Such optional components can be appropriately selected in consideration of the composition of the treatment solution, the intended use, and the material composition of the semiconductor device to be treated. Examples of such optional components include anticorrosive agents, surfactants, pH adjusters, buffers, etc.

[0044] (corrosion inhibitor) The semiconductor device treatment liquid according to this embodiment may contain an anticorrosive agent, such as a compound containing a nitrogen-containing heterocycle, such as a triazole ring, an imidazole ring, a pyridine ring, a phenanthroline ring, a tetrazole ring, a pyrazole ring, a pyrimidine ring, or a purine ring.

[0045] Examples of compounds containing a triazole ring include triazoles such as 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, 1-acetyl-1H-1,2,3-triazolo[4,5-b]pyridine, 1H-1,2,3-triazolo[4,5-b]pyridine, 1,2,4-triazolo[4,3-a]pyridin-3(2H)-one, and 3H-1,2,3-triazolo[4,5-b]pyridin-3-ol; 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole, 1-hydroxybenzotriazole, 1-hydroxypropylbenzotriazole, and 2,3-dicarboxypropylbenzotriazole. and benzotriazoles such as 1,2,3-benzotriazole, 4-hydroxybenzotriazole, 4-carboxyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazole methyl ester, 4-carboxyl-1H-benzotriazole butyl ester, 4-carboxyl-1H-benzotriazole octyl ester, 5-hexylbenzotriazole, [1,2,3-benzotriazolyl-1-methyl][1,2,4-triazolyl-1-methyl][2-ethylhexyl]amine, tolyltriazole, naphthotriazole, bis[(1-benzotriazolyl)methyl]phosphonic acid, and 3-aminotriazole.

[0046] Examples of compounds containing an imidazole ring include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-propylimidazole, 2-butylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-aminoimidazole, and benzimidazole; and biimidazoles such as 2,2'-biimidazole.

[0047] Examples of compounds containing a pyridine ring include pyridines such as 1H-1,2,3-triazolo[4,5-b]pyridine, 1-acetyl-1H-1,2,3-triazolo[4,5-b]pyridine, 3-aminopyridine, 4-aminopyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-acetamidopyridine, 4-pyrrolidinopyridine, 2-cyanopyridine, 2,6-pyridinecarboxylic acid, and 2,4,6-trimethylpyridine; and bipyridyls such as 2,2′-bipyridyl, 4,4′-dimethyl-2,2′-bipyridyl, 4,4′-di-tert-butyl-2,2′-bipyridyl, 4,4′-dinonyl-2,2′-bipyridyl, 2,2″-bipyridine-6,6′-dicarboxylic acid, and 4,4′-dimethoxy-2,2′-bipyridyl.

[0048] An example of a compound containing a phenanthroline ring is 1,10-phenanthroline.

[0049] Examples of compounds containing a tetrazole ring include 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, and 1-(2-diaminoethyl)-5-mercaptotetrazole.

[0050] Examples of compounds containing a pyrazole ring include 3,5-dimethylpyrazole, 3-amino-5-methylpyrazole, 4-methylpyrazole, and 3-amino-5-hydroxypyrazole.

[0051] Examples of compounds containing a pyrimidine ring include pyrimidine, 4-methylpyrimidine, 1,2,4-triazolo[1,5-a]pyrimidine, 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine, 1,3-diphenyl-pyrimidine-2,4,6-trione, 1,4,5,6-tetrahydropyrimidine, 2,4,5,6-tetraaminopyrimidine sulfate, 2,4,5-trihydroxypyrimidine, 2,4,6-triaminopyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-trimethoxypyrimidine, 2, Examples include 4,6-triphenylpyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4-diaminopyrimidine, 2-acetamidopyrimidine, 2-aminopyrimidine, 2-methyl-5,7-diphenyl-(1,2,4)triazolo(1,5-a)pyrimidine, 2-methylsulfanyl-5,7-diphenyl-(1,2,4)triazolo(1,5-a)pyrimidine, 2-methylsulfanyl-5,7-diphenyl-4,7-dihydro-(1,2,4)triazolo(1,5-a)pyrimidine, and 4-aminopyrazolo[3,4-d]pyrimidine.

[0052] Compounds containing a purine ring include adenine, guanine, hypoxanthine, xanthine, uric acid, theophylline, and the like.

[0053] The anticorrosive agent may be used alone or in combination of two or more kinds.

[0054] When the semiconductor device treatment liquid of this embodiment contains an anticorrosive, the content of the anticorrosive is not particularly limited, but is preferably 0.0001 to 1.0 mass % (1 to 10,000 mass ppm) relative to the total mass of the semiconductor device treatment liquid.

[0055] The semiconductor device treatment liquid of this embodiment may not contain one or more compounds selected from the group consisting of compounds containing a triazole ring, compounds containing an imidazole ring, compounds containing a pyridine ring, compounds containing a phenanthroline ring, compounds containing a tetrazole ring, compounds containing a pyrazole ring, compounds containing a pyrimidine ring, and compounds containing a purine ring, and may not contain one or more of the compounds listed above as specific examples of anticorrosive agents. The semiconductor device treatment liquid of this embodiment may not contain an anticorrosive agent.

[0056] (surfactant)

[0057] The semiconductor device treatment liquid of this embodiment may contain a surfactant for the purposes of preventing foaming, adjusting the wettability of the cleaning liquid to the substrate, etc. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

[0058] Examples of nonionic surfactants include polyalkylene oxide alkyl phenyl ether surfactants, polyalkylene oxide alkyl ether surfactants, block polymer surfactants consisting of polyethylene oxide and polypropylene oxide, polyoxyalkylene distyrene-substituted phenyl ether surfactants, polyalkylene tribenzyl phenyl ether surfactants, and acetylene polyalkylene oxide surfactants.

[0059] Examples of anionic surfactants include alkyl sulfonic acids, alkyl benzene sulfonic acids, alkyl naphthalene sulfonic acids, alkyl diphenyl ether sulfonic acids, fatty acid amide sulfonic acids, polyoxyethylene alkyl ether carboxylic acids, polyoxyethylene alkyl ether acetic acids, polyoxyethylene alkyl ether propionic acids, alkyl phosphonic acids, and salts of fatty acids. Examples of "salts" include ammonium salts, sodium salts, potassium salts, and tetramethylammonium salts.

[0060] Examples of cationic surfactants include alkylpyridium surfactants.

[0061] Examples of amphoteric surfactants include betaine surfactants, amino acid surfactants, imidazoline surfactants, and amine oxide surfactants.

[0062] These surfactants are generally commercially available. One type of surfactant may be used alone, or two or more types may be used in combination.

[0063] When the semiconductor device treatment liquid of the present embodiment contains a surfactant, the content of the surfactant is not particularly limited, but is preferably, for example, 0.0001 to 5 mass % relative to the total mass of the semiconductor device treatment liquid. When the surfactant content is within this range, the bubbles generated by the foaming agent tend to be dense.

[0064] The semiconductor device treatment liquid of this embodiment may not contain one or more surfactants selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and may not contain one or more of the compounds exemplified above as these surfactants. The semiconductor device treatment liquid of this embodiment may not contain a surfactant.

[0065] (pH adjuster)

[0066] The semiconductor device treatment liquid of this embodiment may contain a pH adjuster. Examples of pH adjusters include acidic compounds and basic compounds. The basic compound may be an organic basic compound or an inorganic basic compound. The semiconductor device treatment liquid of this embodiment may not contain a pH adjuster.

[0067] (buffering agent)

[0068] The semiconductor device treatment liquid of this embodiment may contain a buffer. The buffer is a compound that has the effect of suppressing changes in the pH of the semiconductor device treatment liquid. As the buffer, a compound having pH buffering ability can be used as appropriate.

[0069] The buffering agent may be used alone or in combination of two or more. When the semiconductor device treatment liquid of the present embodiment contains a buffering agent, the content of the buffering agent is not particularly limited, but may be 0.001 to 10 mass % relative to the total mass of the semiconductor device treatment liquid.

[0070] The semiconductor device treating liquid of this embodiment does not need to contain a buffering agent.

[0071] (Impurities, etc.)

[0072] The semiconductor device treating liquid of this embodiment may contain metal impurities including metal atoms such as Fe atoms, Cr atoms, Ni atoms, Zn atoms, Ca atoms, or Pb atoms. The total content of the metal atoms in the semiconductor device treating liquid of this embodiment is preferably 100 mass ppt or less, based on the total mass of the semiconductor device treating liquid. The lower the lower limit of the total metal atom content, the more preferable it is, and for example, 0.001 mass ppt or more. The total metal atom content may be, for example, 0.001 mass ppt to 100 mass ppt. By setting the total metal atom content to the above-mentioned preferred upper limit or less, the defect suppression and residue suppression properties of the cleaning liquid are improved. By setting the total metal atom content to the above-mentioned preferred lower limit or more, it is thought that metal atoms are less likely to be free and present in the system, and therefore are less likely to adversely affect the overall production yield of the objects to be cleaned.

[0073] The content of metal impurities can be adjusted by, for example, a purification treatment such as filtering, etc. The purification treatment such as filtering may be performed on some or all of the raw materials before preparing the cleaning liquid, or may be performed after preparing the semiconductor device treatment liquid.

[0074] The semiconductor device treatment liquid of this embodiment may contain, for example, impurities derived from organic substances (organic impurities). The total content of the organic impurities in the semiconductor device treatment liquid of this embodiment is preferably 5000 ppm by mass or less. The lower limit of the organic impurity content is preferably as low as possible, and may be, for example, 1 ppq by mass or more. The total content of the organic impurities may be, for example, 1 ppq by mass to 5000 ppm by mass.

[0075] The semiconductor device processing liquid of this embodiment may contain countable entities of a size that can be counted by, for example, a light-scattering liquid-borne particle counter. The size of the countable entities is, for example, 0.04 μm or more. The number of countable entities in the semiconductor device processing liquid of this embodiment is, for example, 1,000 or less per mL of semiconductor device processing liquid, with the lower limit being, for example, 0.1 or more. By keeping the number of countable entities in the semiconductor device processing liquid within the above-mentioned range, it is believed that the metal corrosion suppression effect and defect suppression effect of the semiconductor device processing liquid will be improved (however, the effects of this embodiment are not limited to these).

[0076] The size of the objects to be counted may be a size that can be detected by a light scattering liquid particle counter, for example, 0.001 μm or more.

[0077] The organic impurities and / or the entities to be counted may be added to the cleaning solution, or may be inevitably mixed into the cleaning solution during the manufacturing process of the semiconductor device processing solution. Examples of cases where the organic impurities are inevitably mixed into the cleaning solution during the manufacturing process of the semiconductor device processing solution include, but are not limited to, cases where the organic impurities are contained in raw materials (e.g., organic solvents) used in the manufacturing of the semiconductor device processing solution, and cases where the organic impurities are mixed in from the external environment during the manufacturing process of the semiconductor device processing solution (e.g., contamination).

[0078] When the counted elements are added to the semiconductor device treatment solution, the abundance ratio may be adjusted for each specific size, taking into consideration the surface roughness of the object to be cleaned, etc.

[0079] (pH)

[0080] The pH of the semiconductor device treatment liquid of this embodiment is not particularly limited, but is preferably 1 to 8. The lower limit of the pH is more preferably 2 or higher, and even more preferably 3 or higher. The upper limit of the pH is more preferably 7 or lower, and even more preferably 6 or lower. When the pH is in this range, both corrosion resistance and cleaning properties can be easily achieved.

[0081] <Storage method for semiconductor device processing solutions>

[0082] The method for storing the treatment solution according to this embodiment is not particularly limited, and a conventionally known storage container can be used. The void ratio within the container and / or the type of gas to fill the voids when storing the treatment solution in the container may be appropriately determined so as to ensure the stability of the treatment solution. For example, the void ratio within the storage container may be approximately 0.01 to 30% by volume.

[0083] The treatment liquid according to this embodiment may be concentrated and stored as a highly concentrated solution before use (hereinafter, sometimes referred to as a "concentrated solution"). When in use, the concentrated solution may be diluted 2 to 2000 times to form a treatment liquid having the desired content described above, which may be used for treating semiconductor devices. Water, for example, may be used as a diluting solvent for the concentrated solution. In this regard, the aqueous treatment liquid described above is preferred because such concentration and dilution can be easily performed. When concentrating and diluting, an appropriate purification treatment may be performed, if necessary. A known purification method may be used depending on the type and content of the components.

[0084] <Methods of using semiconductor device treatment solutions, methods of treating semiconductor devices, etc.>

[0085] The semiconductor device treatment liquid according to this embodiment has excellent corrosion resistance for at least a cobalt atom-containing layer and a tungsten atom-containing layer, and is also excellent in removing fluorine-based residues, and therefore can be suitably used as a treatment liquid for treating a substrate having a cobalt atom-containing layer and / or a tungsten atom-containing layer. The configuration of the substrate to be treated is not particularly limited, but an example is shown below.

[0086] An example of the configuration of a laminated substrate for a semiconductor device is a laminated substrate in which functional layers such as metal wiring, a metal layer, an etching stop layer, an insulating layer, and an interlayer dielectric (ILD), as well as a protective film (hard mask layer, HM layer) are laminated on a substrate.

[0087] Examples of the substrate material include silicon, amorphous silicon, polysilicon, and glass.

[0088] Examples of metals used in the metal wiring and metal layers include metals such as cobalt (Co), tungsten (W), molybdenum (Mo), ruthenium (Ru), copper (Cu), iron (Fe), nickel (Ni), silicon (Si), aluminum (Al), lead (Pb), zinc (Zn), tin (Sn), tantalum (Ta), magnesium (Mg), bismuth (Bi), cadmium (Cd), zirconium (Zr), antimony (Sb), manganese (Mn), beryllium (Be), chromium (Cr), germanium (Ge), vanadium (V), gallium (Ga), hafnium (Hf), indium (In), niobium (Nb), rhenium (Re), and thallium (Tl), as well as metal oxides, metal nitrides, metal chlorides, metal fluorides, and the like of these metals. From the viewpoint of effectively utilizing the advantages of this embodiment, it is preferable that the material contains cobalt and / or tungsten. These may be cobalt alloys or tungsten alloys. In addition, for example, silicon-based materials include SiN, SiO2, low-k films (SiOC films, SiCOH films, etc.), ILDs, etc.

[0089] Examples of materials for the etching stop layer include aluminum oxide, SiN, SiON, and SiOCN.

[0090] Examples of materials for the interlayer dielectric (ILD) include silicon-based materials such as SiO2, SiN, SiOC, SiOCN, etc. The interlayer dielectric can be used as a functional layer that insulates wiring between multilayer wirings composed of multiple layers.

[0091] The material for the protective film (hard mask layer, HM layer) is not particularly limited as long as it functions as a protective film against etching, and a suitable material can be selected in consideration of manufacturing conditions, etc. Examples of protective film materials include silicon-based materials such as SiN, SiO, SiON, and SiCN, titanium-based materials such as Ti and TiN, and combinations thereof.

[0092] The treatment method using the semiconductor device treatment liquid according to this embodiment includes a step of contacting the semiconductor device treatment liquid with a semiconductor device (e.g., various semiconductor elements, various substrates, etc.). For example, by contacting the semiconductor device with the semiconductor device treatment liquid in an etching step (or a step before or after the etching step), etching residues can be removed. Furthermore, it is expected that protective films such as hard mask layers can also be removed. The etching method is not particularly limited, and may be wet etching or dry etching, but dry etching is preferred. Dry etching is advantageous in that it enables metal wiring at the nano-level and allows control of the gas used. Furthermore, dry etching has the drawback of causing relatively large damage to the substrate, etc. However, the use of the treatment liquid according to this embodiment is desirable in that such damage can be effectively suppressed, thereby more effectively utilizing the advantages of this embodiment.

[0093] As a method of contacting the treatment liquid with a semiconductor device (e.g., various semiconductor elements, various substrates, etc.), for example, the treatment liquid can be placed in a container and the semiconductor device to be cleaned can be immersed in the treatment liquid to remove dry etching residues and process the semiconductor device. Alternatively, the dry etching residues can be removed and the semiconductor device can be processed by processing the semiconductor device using a single-wafer cleaning method. The treatment liquid can be suitably used as an etching liquid as well as a dry etching residue removal liquid (cleaning liquid). The treatment liquid according to this embodiment can also be used as a cleaning liquid for cleaning semiconductor devices after a chemical mechanical polishing (CMP) process. Before and after a process using this treatment liquid, a rinsing process using an organic solvent, water, carbonated water, ammonia water, etc. may be performed.

[0094] The treatment temperature using the semiconductor device treatment liquid can be appropriately selected taking into consideration the configuration of the semiconductor device to be treated, the composition of the treatment liquid, and the like. The treatment temperature is usually 10 to 80°C. The lower limit is preferably 15°C or higher, and more preferably 20°C or higher. The upper limit is preferably 70°C or lower, more preferably 65°C or lower, even more preferably 60°C or lower, and even more preferably 50°C or lower.

[0095] The treatment time using the semiconductor device treatment liquid can be appropriately selected in consideration of the configuration of the semiconductor device to be treated, the composition of the treatment liquid, etc. The treatment time is usually 10 seconds to 60 minutes.

[0096] As described above, the treatment liquid according to this embodiment can be used, for example, as a treatment liquid for removing residues generated during a semiconductor etching process or the like. In particular, the treatment liquid according to this embodiment can suppress damage to various metal layers, such as cobalt-atom-containing layers and tungsten-atom-containing layers, and can effectively remove residues generated by dry etching, such as fluorine-based residues. From this perspective, the treatment liquid according to this embodiment is preferably used in a semiconductor device including a substrate having a metal layer containing cobalt atoms, and the treatment liquid is a semiconductor device treatment liquid used to treat the metal layer. Alternatively, the treatment liquid according to this embodiment is preferably used in a semiconductor device including a substrate having a metal layer containing tungsten atoms, and the treatment liquid is a semiconductor device treatment liquid used to treat the metal layer. Furthermore, the treatment liquid according to this embodiment is preferably used in a semiconductor device including a substrate having a metal layer used in the manufacture of semiconductor devices, and is used to remove residues generated after the substrate is subjected to an etching process. [Example]

[0097] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0098] (Preparation of semiconductor device treatment solution)

[0099] The components were mixed to obtain the compositions shown in Tables 1 to 3 to prepare semiconductor device treatment solutions (treatment solutions). Water was used as the balance of each treatment solution. The components used in the examples and listed in each table are as follows:

[0100] HF: Hydrogen fluoride 1,6-Diaminohexane 1,7-Diaminoheptane 1,8-Diaminooctane 1,10-Diaminodecane: 1,10-Diaminodecane Octylamine: Octylamine 8-Amino-1-Octanol 12-Amino-1-Dodecanol: 12-amino-1-dodecanol 7-Aminoheptanoic acid Dipropylamine: Dipropylamine 2-Methyl-1,5-diaminopentane 1,3-Diaminopentane 1,2-Cyclohexanediamine Bis(hexamethylene)triamine Tetraethylenepentamine: Tetraethylenepentamine Triethylenetetramine: Triethylenetetramine Diethylenetriamine: Diethylenetriamine EO: Ethylene oxide (ethylene oxide, 3-membered ring, 2 carbon atoms, 1 oxygen atom) DO: 1,4-dioxane (6-membered ring, 4 carbon atoms, 2 oxygen atoms) EO and DO mixture: A mixed solvent of ethylene oxide and 1,4-dioxane in a 1:1 mass ratio (EO:DO = 1:1, mass ratio)

[0101] (Evaluation of the corrosion protection properties of cobalt)

[0102] A cobalt film was prepared as a model film, and the etching property was evaluated based on the amount of etching. The film thickness of this model film was 150 Å. The model film was then etched using the treatment liquid of each example and comparative example. The etching conditions were as follows: the model film was immersed in the treatment liquid (25°C) for 15 minutes, rinsed with ultrapure water (25°C) for 3 seconds, then washed with isopropyl alcohol (25°C) for 30 seconds, and dried by nitrogen blowing. The etching property was then evaluated based on the difference in film thickness of the model film before and after immersion in the treatment liquid.

[0103] The thickness of the model film before and after the treatment was measured by fluorescent X-ray analysis using a "ZSX Primus IV" (manufactured by RIGAKU Corporation). The etching amount (amount of film loss) was judged and evaluated according to the following criteria. A: The film loss was less than 10 Å. B: The film loss was 10 Å or more and less than 20 Å. C: The film loss was 20 Å or more.

[0104] (Evaluation of the corrosion resistance of tungsten)

[0105] A tungsten film was prepared as a model film, and the etching property was evaluated based on the amount of etching. The film thickness of this model film was 80 Å. The model film was then etched using the treatment liquid of each example and comparative example. The etching conditions were as follows: the model film was immersed in the treatment liquid (25°C) for 30 minutes, rinsed with ultrapure water (25°C) for 3 seconds, then washed with isopropyl alcohol (25°C) for 30 seconds, and dried by nitrogen blowing. The etching property was then evaluated based on the difference in film thickness of the model film before and after immersion in the treatment liquid.

[0106] The thickness of the model film before and after the treatment was measured by fluorescent X-ray analysis using a "ZSX Primus IV" (manufactured by RIGAKU Corporation). The etching amount (amount of film loss) was judged and evaluated according to the following criteria. A: The film loss was less than 10 Å. B: The film loss was 10 Å or more and less than 50 Å. C: The film loss was 50 Å or more.

[0107] (Evaluation of fluorine-based residue removal ability)

[0108] Evaluation was performed using TiN substrates after dry etching using fluorine-based gas. First, the treatment solution for each example and comparative example was placed in a beaker. The TiN substrate was then immersed in the treatment solution at 25°C for 3 minutes, rinsed with ultrapure water (25°C) for 3 seconds, washed with isopropyl alcohol (25°C) for 30 seconds, and dried by nitrogen blowing. The amount of fluorine-based residue remaining on the TiN substrate was then measured by X-ray photoelectron spectroscopy (XPS) using an X-ray photoelectron spectrometer "K-ALPHA+" (manufactured by Thermo Fisher Scientific).

[0109] The remaining amount of fluorine-based residue was determined by the extent to which it varied from the control, Comparative Example 1, which was set as 100% (reference value). Specifically, the determination and evaluation were made according to the following criteria. A: The amount of fluorine-based residue remaining was equal to (within the range of 100±5%) or lower (less than 105%) than the amount of fluorine-based residue remaining in the control (100%). B: The amount of fluorine-based residue remaining was greater (greater than 105%) than the amount of fluorine-based residue remaining in the control (100%).

[0110] The compositions of the examples and comparative examples are shown in Tables 1 to 3, and the evaluation results of the examples and comparative examples are shown in Tables 4 and 5.

[0111] [Table 1]

[0112] [Table 2]

[0113] [Table 3]

[0114] [Table 4]

[0115] [Table 5]

[0116] From the above, it should be at least confirmed that the semiconductor device treating solution according to this example is excellent in corrosion prevention properties for the cobalt atom-containing layer and the tungsten atom-containing layer, and in removal properties for fluorine-based residues.

[0117] This application is based on U.S. Provisional Application No. 63 / 682,008, filed with the U.S. Patent and Trademark Office on August 12, 2024, the contents of which are incorporated herein by reference.

Claims

1. a fluorine-containing compound; a cyclic ether compound; a diaminoalkane, Water and A semiconductor device treatment solution comprising:

2. the fluorine-containing compound is at least one selected from the group consisting of hydrogen fluoride, ammonium fluoride, tetrafluoroboric acid, tetramethylammonium fluoride, and triethanolamine hydrofluoride; The semiconductor device treatment liquid according to claim 1 .

3. In the cyclic ether compound, the number of carbon atoms forming the ring is 2 to 4, and the number of oxygen atoms forming the ring is 1 to 2. The semiconductor device treatment liquid according to claim 1 .

4. The content of the cyclic ether compound is 0.000001% by mass to 0.01% by mass. The semiconductor device treatment liquid according to claim 1 .

5. The diaminoalkane is a compound represented by the following formula (1): The semiconductor device treatment liquid according to claim 1 . 【Chemistry 1】 (In the formula, n represents a number from 1 to 15.)

6. the semiconductor device includes a substrate having a metal layer containing cobalt atoms; The semiconductor device treatment solution is used to treat the metal layer. The semiconductor device treatment liquid according to claim 1 .

7. the semiconductor device includes a substrate having a metal layer containing tungsten atoms; The semiconductor device treatment solution is used to treat the metal layer. The semiconductor device treatment liquid according to claim 1 .

8. For a substrate provided with a metal layer used in the manufacture of the semiconductor device, It is used to remove residues generated after etching treatment of the substrate. The semiconductor device treatment liquid according to claim 1 .

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