Method for manufacturing a semiconductor substrate, method for etching a substrate, and composition for surface modification.

Abstract

The present invention provides a method for manufacturing a semiconductor substrate, a method for etching a substrate, and a surface modification composition that can repair damage to the low-k film while promoting the deposition of a barrier layer in a subsequent process. [Solution] A method for manufacturing a semiconductor substrate, comprising the steps of dry etching a substrate containing a layer containing a low-k material, and treating the dry-etched substrate with a surface modification composition, wherein the surface modification composition contains a silane coupling agent and / or a derivative thereof represented by general formula (1), and water. JPEG2026141170000020.jpg55170

Description

[Technical Field]

[0001] This invention relates to a method for manufacturing a semiconductor substrate, a method for etching a substrate, and a composition for surface modification. [Background technology]

[0002] In recent years, semiconductor substrates used in integrated circuits and other applications have become more highly integrated due to miniaturization, which requires suppressing signal delays in multilayer wiring and ensuring reliability. For this reason, low-k films (low-k materials) with low dielectric constants are used as interlayer insulating films in semiconductor substrates. The low-k films are then patterned by dry etching. Subsequently, to prevent the diffusion of wiring materials such as Cu into the low-k films, a barrier layer of TaN or similar material is deposited as a post-processing step after dry etching.

[0003] As a technology relating to the Low-k film mentioned above, for example, Patent Document 1 discloses a method for treating a dielectric film, comprising the step of exposing at least one surface of the dielectric film to a treatment compound containing alkylsilane, alkoxysilane, alkylsiloxane, alkoxysiloxane, arylsilane, acylsilane, cyclosiloxane, polysilsesquioxane (PSS), arylsiloxane, acylsiloxane, halosiloxane, or any combination thereof, wherein the dielectric film has a dielectric constant smaller than that of SiO2. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 2008-532268 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, dry etching damages the low-k film, leading to further damage to the low-k film during the subsequent barrier layer deposition process, resulting in a decrease in the electrical properties of the semiconductor substrate. Therefore, there is a need to develop semiconductor substrate manufacturing processes and etching technologies that can repair the damage to the low-k film and accelerate the subsequent barrier layer deposition process.

[0006] This invention has been made in view of the above problems, and aims to provide a method for manufacturing a semiconductor substrate, a method for etching a substrate, and a surface modification composition that can contribute to improving the dielectric constant of a low-k film without causing defects in the formation of the barrier layer. [Means for solving the problem]

[0007] As a result of diligent research to achieve the above-mentioned objectives, the present inventors have found that the present invention is a method for manufacturing a semiconductor substrate comprising the steps of dry etching a substrate containing a layer containing a low-k material, and treating the dry-etched substrate with a surface modification composition, wherein the surface modification composition comprises (A) a silane coupling agent and / or a derivative thereof having a specific structure, and (B) water, and has thus completed the present invention.

[0008] In other words, the present invention is as follows. <1> A method for manufacturing a semiconductor substrate, comprising the steps of: dry etching a substrate containing a layer containing a low-k material; and treating the dry-etched substrate with a surface modification composition, wherein the surface modification composition contains (A) a silane coupling agent and / or a derivative thereof represented by general formula (1), and (B) water.

[0009] [ka]

[0010] (In the formula, A and B each independently represent an organic group containing a hydrogen atom, a hydroxyl group, a hydrocarbon group, or a nitrogen atom, and at least one of A and B represents a hydrogen atom. X and Y each independently represent an alkyl group, an alkoxy group, a hydrogen atom, a halogen atom, or a hydroxyl group, and Z represents an alkoxy group or a hydroxyl group. n represents a number.) <2> The surface modification composition further contains (C) a corrosion inhibitor. <1> This is a method for manufacturing a semiconductor substrate as described above. <3> The aforementioned (C) corrosion inhibitor is a compound having an aromatic ring structure containing a nitrogen atom. <2> This is a method for manufacturing a semiconductor substrate as described above. <4> The content of component (A) in the surface modification composition is 0.01 to 10% by mass. <1> ~ <3> This is a method for manufacturing a semiconductor substrate as described in any of the above. <5> The content of component (C) in the surface modification composition is 0.001 to 5% by mass. <2> or <3> This is a method for manufacturing a semiconductor substrate as described above. <6> The pH of the surface modification composition is 6.0 to 12.0. <1> ~ <5> This is a method for manufacturing a semiconductor substrate as described in any of the above. <7> A method for etching a substrate, comprising the steps of: dry etching a substrate containing a layer containing a low-k material; and treating the dry-etched substrate with a surface modification composition, wherein the surface modification composition contains (A) a silane coupling agent and / or a derivative thereof represented by general formula (1), and (B) water.

[0011] [ka]

[0012] (wherein A and B each independently represent a hydrogen atom, a hydroxy group, a hydrocarbon group, or an organic group containing a nitrogen atom, and at least one of A and B represents a hydrogen atom; X and Y each independently represent an alkyl group, an alkoxy group, a hydrogen atom, a halogen atom, or a hydroxy group; Z represents an alkoxy group or a hydroxy group; and n represents a number.) <8> The substrate etching method according to <7>, wherein the surface modification composition further contains (C) a corrosion inhibitor. <9> The substrate etching method according to <7> or <8>, wherein the pH of the surface modification composition is 6.0 to 12.0. <10> A composition for surface modification of a substrate including a layer containing a low-k material, which is a surface modification composition containing (A) a silane coupling agent represented by general formula (1) and / or a derivative thereof and (B) water.

[0013]

Chemical Formula

[0014] (wherein A and B each independently represent a hydrogen atom, a hydroxy group, a hydrocarbon group, or an organic group containing a nitrogen atom, and at least one of A and B represents a hydrogen atom; X and Y each independently represent an alkyl group, an alkoxy group, a hydrogen atom, a halogen atom, or a hydroxy group; Z represents an alkoxy group or a hydroxy group; and n represents a number.) <11> The surface modification composition according to <10>, wherein the surface modification composition further contains (C) a corrosion inhibitor. <12> The surface modification composition according to <11>, wherein the (C) corrosion inhibitor is a compound having an aromatic ring structure containing a nitrogen atom. <13> The surface modification composition according to any one of <10> to <12>, wherein the content of the component (A) in the surface modification composition is 0.01 to 10% by mass. <14> The content of component (C) in the surface modification composition is 0.001 to 5% by mass. <11> or <12> This is a surface modification composition as described above. <15> The pH of the surface modification composition is 6.0 to 12.0. <10> ~ <14> It is a surface modification composition as described in any of the above. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a method for manufacturing a semiconductor substrate, a method for etching a substrate, and a surface modification composition that can repair damage to the low-k film while promoting the subsequent process of forming a barrier layer. [Modes for carrying out the invention]

[0016] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "these embodiments"). These embodiments are illustrative for explaining the present invention and are not intended to limit the present invention to the following. The present invention can be appropriately modified and implemented within the scope of its gist. Furthermore, the configurations and parameters disclosed herein can be any combination unless otherwise specified. Moreover, the upper and lower limits of the values ​​disclosed herein can be any combination unless otherwise specified.

[0017] <Manufacturing method for semiconductor substrates>

[0018] The semiconductor substrate manufacturing method according to this embodiment is a method for manufacturing a semiconductor substrate comprising the steps of dry etching a substrate including a layer containing a low-k material, and treating the dry-etched substrate with a surface modification composition, wherein the surface modification composition contains (A) a silane coupling agent and / or a derivative thereof represented by general formula (1), and (B) water. In the following, a substrate including a layer containing a low-k material may be abbreviated as "laminated substrate".

[0019] [ka]

[0020] (In the formula, A and B each independently represent an organic group containing a hydrogen atom, a hydroxyl group, a hydrocarbon group, or a nitrogen atom, and at least one of A and B represents a hydrogen atom. X and Y each independently represent an alkyl group, an alkoxy group, a hydrogen atom, a halogen atom, or a hydroxyl group, and Z represents an alkoxy group or a hydroxyl group. n represents a number.)

[0021] The inventors focused on two problems with conventional semiconductor substrate manufacturing methods: the deterioration of electrical properties due to damage to the Low-k film during dry etching, and the poor film formation of the barrier layer in the subsequent barrier layer deposition process after dry etching. The inventors considered that one of the causes of these problems might be that the surface of the Low-k material is altered by the etching gas during dry etching, causing a change in the polarity of the surface. For example, it is conceivable that the polarity increases when hydroxyl groups (-OH) derived from water (H2O) are introduced to the surface of the Low-k film during dry etching.

[0022] Based on the above considerations, the inventors conducted diligent studies and, unexpectedly, discovered that the above-mentioned problems could be solved by treating the substrate with the surface modification composition described above after dry etching. The reason for this is not entirely clear, but it is thought that the (A) silane coupling agent and / or its derivative contained in the surface modification composition can repair the surface of the Low-k film whose polarity has changed, and that the nitrogen atoms in the (A) silane coupling agent and / or its derivative act as reaction sites for barrier layer formation, thereby promoting the formation of the barrier layer in the subsequent process (however, the effects and benefits of this embodiment are not limited to these).

[0023] Furthermore, when metal wiring on a semiconductor substrate is miniaturized, the surface area of ​​the exposed surface of the metal wiring naturally increases with miniaturization, and therefore the contact area with the etching gas in dry etching also increases. As a result, the surface area of ​​the Low-k film that is damaged increases, and the area (area) where the barrier layer deposition is poor tends to increase. Therefore, semiconductor substrates with miniaturized metal wiring experience a significant decrease in electrical properties due to dry etching. However, the semiconductor substrate manufacturing method according to this embodiment can repair damage to the Low-k film while promoting the deposition of the barrier layer in the subsequent process, thus meeting the demand for miniaturization of semiconductor substrates (however, the operation and effects of this embodiment are not limited to these).

[0024] The following describes in more detail each step in the manufacturing method of the semiconductor substrate according to this embodiment, as well as the composition of the surface modification composition.

[0025] (Dry etching process)

[0026] In the dry etching process, a substrate containing a layer with a low-k material is dry-etched. A specific example of a substrate containing a layer with a low-k material is a laminated substrate in which a metal wiring layer, an etching stopper layer, and a low-k film (interlayer insulating film) containing a low-k material are laminated on the substrate, and a hard mask layer (HM layer) is placed on top of them (substrate / metal wiring layer / etching stopper layer / low-k film (interlayer insulating film) / HM layer). In the semiconductor substrate manufacturing method according to this embodiment, various functional layers other than those described above may be further laminated as long as the desired effect can be obtained, and it goes without saying that the layer structure is not limited. For example, the type, size, shape, number of layers, and stacking order of the above-mentioned layers laminated on the substrate are not particularly limited, and any desired configuration can be adopted.

[0027] The substrate is not particularly limited, and examples include a substrate containing at least one selected from the group consisting of silicon, amorphous silicon, and glass.

[0028] The metal wiring layer is not particularly limited and may include, for example, molybdenum (Mo), tungsten (W), ruthenium (Ru), copper (Cu), gold (Au), silver (Ag), iron (Fe), nickel (Ni), aluminum (Al), lead (Pb), zinc (Zn), tin (Sn), tantalum (Ta), magnesium (Mg), cobalt (Co), bismuth (Bi), cadmium (Cd), titanium (Ti), zirconium (Zr), and anticarbon. Examples of metal wiring layers include those containing metals such as mon (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 at least one selected from the group consisting of these metal oxides, metal nitrides, metal chlorides, and metal fluorides.

[0029] The etching stop layer is not particularly limited and may include, for example, silicon-based materials such as SiN, SiON, and SiOCN, metal nitrides such as AlN, and AlO x An etching stop layer containing at least one selected from the group consisting of metal oxides and the like is also mentioned.

[0030] The low-k film (interlayer insulating film) containing the low-k material is not particularly limited and includes materials such as SiOC, SiCOH, and SiOCN. Generally, materials with a dielectric constant lower than SiO2 (dielectric constant k=4.1) are preferred. The low-k film is etched by dry etching to remove unwanted portions so that it forms a predetermined pattern shape. However, the surface exposed after etching is damaged by the dry etching. The larger the surface area of ​​the exposed surface, the greater the impact of the damage caused by dry etching.

[0031] The hard mask layer (HM layer) can be any layer containing a material that functions as a protective film against dry etching, and the material is not particularly limited; a suitable material can be selected as appropriate considering the manufacturing conditions, etc. By providing a patterned HM layer, a low-k film or the like can be dry-etched to correspond to the pattern. Examples of HM layers include TiO x ,TiN,ZrO x Examples include a hard mask layer containing at least one selected from the group consisting of WDC (tungsten-doped carbon), CHM (carbon hard mask), and SiHM (silicon hard mask, such as SiN or SiO2).

[0032] The method for forming the various layers described above on the substrate is not particularly limited, but examples include ALD (atomic layer deposition), sputtering, CVD (chemical vapor deposition), PVD (physical vapor deposition), and spin-on deposition. Alternatively, the film formed by these methods may be subjected to plasma treatment.

[0033] Furthermore, the substrate containing the layer containing the Low-k material preferably has a Low-k film (interlayer insulating film) containing the Low-k material and a functional layer containing at least one selected from the group consisting of copper atoms, cobalt atoms, tungsten atoms, and molybdenum atoms. The functional layer is not particularly limited, but examples include the metal wiring layer described above. The substrate may further have an etching stop layer as needed, or a hard mask layer (HM layer) on the outermost surface.

[0034] The dry etching method and conditions are not particularly limited, and suitable methods and conditions can be adopted considering the material and structure of the laminated substrate to be processed. Examples include plasma etching, sputter etching, and reactive ion etching. For example, C x H y F z(x, y, and z each represent numbers independently.) Examples of etching methods include using inorganic fluorine gases such as F2 and SF6, or organic fluorine gases. Furthermore, etching equipment such as CCP (capacitively coupled plasma) and ICP (inductively coupled plasma) can be used.

[0035] While dry etching has the advantage of excellent anisotropy, it has the problem that the substrate being etched is susceptible to damage, and in particular, the surface of the Low-k film is easily damaged. However, according to the manufacturing method of this embodiment, by treating the substrate with a surface modification composition containing (A) a silane coupling agent and / or a derivative thereof represented by general formula (1) and (B) water in the processing step described later, it is possible to repair damage to the Low-k film while promoting the formation of the barrier layer in the subsequent step.

[0036] (Processing steps, surface modification compositions)

[0037] In the process of treating a dry-etched substrate with a surface modification composition (processing step), a surface modification composition containing (A) a silane coupling agent and / or a derivative thereof having a structure represented by general formula (1), and (B) water is used. By using such a surface modification composition, it is possible to repair damage to the low-k film while promoting the formation of the barrier layer in the subsequent process.

[0038] [ka]

[0039] (In the formula, A and B each independently represent an organic group containing a hydrogen atom, a hydroxyl group, a hydrocarbon group, or a nitrogen atom, and at least one of A and B represents a hydrogen atom. X and Y each independently represent an alkyl group, an alkoxy group, a hydrogen atom, a halogen atom, or a hydroxyl group, and Z represents an alkoxy group or a hydroxyl group. n represents a number.)

[0040] (Component (A): a silane coupling agent and / or a derivative thereof)

[0041] A and B in General Formula (1) each independently represent a hydrogen atom, a hydroxy group, a hydrocarbon group, or an organic group containing a nitrogen atom, and at least one of A and B represents a hydrogen atom.

[0042] The hydrocarbon group is preferably an alkyl group having 1 to 8 carbon atoms. The lower limit of the number of carbon atoms is more preferably 2 or more, and still more preferably 3 or more. Further, the upper limit of the number of carbon atoms is more preferably 7 or less, and still more preferably 6 or less.

[0043] The organic group containing a nitrogen atom is preferably a monovalent organic group containing only a nitrogen atom, a carbon atom, and a hydrogen atom; -(CH2) p -NH2 (p represents a number of 1 to 5), and -(CH2) q -NH(CH2) r -(CH2) s -NH2 (q, r, and s each independently represent a number of 1 to 5), more preferably at least one selected from the group consisting of; -(CH2) t -NH2 (t represents a number of 1 to 3), and -(CH2) u -NH(CH2) v -(CH2) w -NH2 (u, v, and w each independently represent a number of 1 to 3), still more preferably at least one selected from the group consisting of.

[0044] X and Y in General Formula (1) each independently represent an alkyl group, an alkoxy group, a hydrogen atom, a halogen atom, or a hydroxy group. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably an alkyl group having 1 or 2 carbon atoms. The alkoxy group is preferably at least one selected from the group consisting of a methoxy group, an ethoxy group, an n-propyl group, and an iso-propyl group.

[0045] In general formula (1), Z represents an alkoxy group or a hydroxyl group. The alkoxy group is preferably at least one selected from the group consisting of a methoxy group, an ethoxy group, an n-propyl group, and an iso-propyl group.

[0046] In general formula (1), n ​​represents a number. n is preferably between 1 and 5, more preferably between 1 and 4, and even more preferably between 1 and 3.

[0047] The derivatives of the silane coupling agent represented by general formula (1) are not particularly limited, and any derivative having a structure that the silane coupling agent can take is acceptable. For example, some or all of the alkoxy groups are hydrolyzed to have silanol groups, or the resulting dehydration condensates of silanols (e.g., oligomers, dimers) are examples.

[0048] Specific examples of the silane coupling agent represented by general formula (1) are preferably at least one selected from the group consisting of 3-aminopropyltriethoxysilane (APTES), 3-aminopropyltrimethoxysilane (APTMS), 4-aminobutyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane (AEAPDMMS), 3-(2-aminoethylamino)propyldiethoxymethylsilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 4-aminobutyltriethoxymerane, and 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (AEAEAPTMS).

[0049] Furthermore, specific examples of derivatives of the silane coupling agent represented by general formula (1) are preferably at least one selected from the group consisting of 3-aminopropylsilanol, 4-aminobutylsilanol, N-(2-aminoethyl)-3-aminopropylsilanol, 3-(2-aminoethylamino)propylmethylsilanol, and 3-[2-(2-aminoethylamino)ethylamino]propylsilanol.

[0050] The content of component (A) in the surface modification composition is not particularly limited, but is preferably 0.01 to 10% by mass. The lower limit of this content is more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. The upper limit of this content is more preferably 8% by mass or less, even more preferably 6% by mass or less, and even more preferably 5% by mass or less. By controlling the content within this range, it is possible to further improve the effect of modifying damaged low-k films while suppressing inhibition of barrier film formation.

[0051] ((B) component: water)

[0052] The type of water used is not particularly limited, and from the perspective of being suitable for the manufacture of semiconductor substrates, for example, deionized water (DIW) can be used.

[0053] The content of component (B) in the surface modification composition is not particularly limited, but is preferably 45 to 99.99% by mass. The lower limit of the water content may be, for example, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 85% by mass or more. When the water content is high, it can be suitably used as a so-called aqueous surface modification composition, but the water content can also be selected according to the application, taking into consideration the type of metal to be cleaned, etc. When preparing the composition, other necessary components may be added, and water may be added as the remainder.

[0054] ((C) component: corrosion inhibitor)

[0055] The surface modification composition preferably further contains (C) a corrosion inhibitor. The corrosion inhibitor is more preferably a compound having an aromatic ring structure containing a nitrogen atom.

[0056] While not particularly limited, specific examples of corrosion inhibitors are preferably at least one selected from the group consisting of imidazole ring-containing compounds, triazole ring-containing compounds, carbazole ring-containing compounds, pyridine ring-containing compounds, pyrimidine ring-containing compounds, tetrazole ring-containing compounds, pyrazole ring-containing compounds, purine ring-containing compounds, phenanthroline ring-containing compounds, and benzothioazole ring-containing compounds. Among these, triazole ring-containing compounds and tetrazole ring-containing compounds are more preferred. By using these, the corrosion resistance of various layers containing copper atoms, cobalt atoms, tungsten atoms, and / or molybdenum atoms (e.g., metal wiring layers, etching stop layers, interlayer insulating films, hard mask layers, etc.) can be improved.

[0057] Specific examples of imidazole ring-containing compounds include 1-decyl-3-methylimidazolium chloride, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-propylimidazole, 2-butylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-aminoimidazole, 2,2'-biimidazole, and 5-methylbenzimidazole.

[0058] Specific examples of triazole ring-containing compounds include 1,2,4-triazole (TAZ), 1,2,3-benzotriazole (BTA), 1,2,3-triazole, 3-amino-1H-1,2,4-triazole (3A-TAZ), 1-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole (5M-BTA), 1-hydroxybenzotriazole, 1-hydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, and 4-carboxyl-1 Examples include H-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. Among these, 1,2,4-triazole (TAZ), 1,2,3-benzotriazole (BTA), 1,2,3-triazole, 3-amino-1H-1,2,4-triazole (3A-TAZ), 1-methyl-1H-benzotriazole, and 5-methyl-1H-benzotriazole (5M-BTA) are preferred, and 1,2,4-triazole (TAZ), 3-amino-1H-1,2,4-triazole (3A-TAZ), and 5-methyl-1H-benzotriazole (5M-BTA) are more preferred.

[0059] Specific examples of carbazole ring-containing compounds include 9H-carbazole, 4-hydroxycarbazole, 1-methylcarbazole, 3-methyl-9H-carbazole, 9-methyl-1H-carbazole, 2-methoxycarbazole, 1-bromocarbazole, 2-bromocarbazole, 3-bromocarbazole, 4-bromocarbazole, 2-chlorocarbazole, 3-chlorocarbazole, 2-fluorocarbazole, 3-fluorocarbazole, 2-iodocarbazole, 3-iodocarbazole, 9-acetylcarbazole, 2 Examples include 7-dibromocarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 2,3-benzcarbazole, 9-acetyl-3,6-diiodocarbazole, 2-bromo-7-methoxy-9H-carbazole, 3,6-dimethylcarbazole, 2,7-dimethylcarbazole, 3,6-diaminocarbazole, 3-amino-ethylcarbazole, 3,6-dimethoxy-9H-carbazole, 2,7-dimethoxy-9H-carbazole, 3,3'-bicarbazole, and 7H-benzo[c]carbazole.

[0060] Specific examples of pyridine ring-containing compounds include 1H-1,2,3-triazolo[4,5-b]pyridine, 1,2,4-triazolo[4,3-a]pyridine-3(2H)-one, 3H-1,2,3-triazolo[4,5-b]pyridine-3-ol, 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, 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 4,4'-di-tert-butyl-2,2'-bipyridyl, and 4,4'-dinonyl-2,2'-bipyridyl.

[0061] Specific examples of pyrimidine ring-containing compounds include pyrimidine, 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, and 2,4,6-tri Examples include phenylpyrimidine, 2,4-diamino-6-hydroxylpyrimidine, 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.

[0062] Examples of tetrazole ring-containing compounds include 2,3,5-triphenyltetrazole, 2,3,5-triphenyltetrazolium chloride, 2,3,5-triphenyltetrazolium bromide, 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, and 1-(2-diaminoethyl)-5-mercaptotetrazole.

[0063] Examples of pyrazole ring-containing compounds include 3,5-dimethylpyrazole, 3-amino-5-methylpyrazole, 4-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-phenylpyrazole, indazole, 4-fluoroindazole, 5-nitroindazole, indazole-3-carboxylic acid, and benzydamine hydrochloride. Among these, 3-phenylpyrazole, indazole, 4-fluoroindazole, 5-nitroindazole, indazole-3-carboxylic acid, and benzydamine hydrochloride are preferred.

[0064] Specific examples of purine ring-containing compounds include purines.

[0065] Specific examples of phenanthroline ring-containing compounds include 1,10-phenanthroline.

[0066] Specific examples of benzothioazole ring-containing compounds include benzothiazole, 2,5-dimethylbenzothiazole, and 2,6-dimethylbenzothiazole.

[0067] Furthermore, the corrosion inhibitor may be a salt of the compound described above. Specific examples of salts are not limited to sodium salts, potassium salts, chloride salts, ammonium salts, alkylammonium salts (e.g., tetramethylammonium salt), etc. Alternatively, the compound may be a hydrate.

[0068] The corrosion inhibitors may be used individually or in combination of two or more. The surface modification composition may contain two or more corrosion inhibitors from the viewpoint of providing corrosion protection to various metals. The corrosion inhibitors can be selected according to the type of target layer (e.g., metal wiring layer, etching stop layer, interlayer insulating film, hard mask layer, etc.). When the surface modification composition contains two or more corrosion inhibitors, it is more preferable that the corrosion inhibitors include at least two selected from the group consisting of imidazole ring-containing compounds, triazole ring-containing compounds, carbazole ring-containing compounds, pyridine ring-containing compounds, pyrimidine ring-containing compounds, tetrazole ring-containing compounds, pyrazole ring-containing compounds, purine ring-containing compounds, and phenanthroline ring-containing compounds. Any of these can be those described above.

[0069] The content of component (C) in the surface modification composition is preferably 0.001 to 5% 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, and even more preferably 0.1% by mass or more. The upper limit of this content is more preferably 3% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less. If the composition contains two or more corrosion inhibitors as component (C), it is preferable that the sum of their contents is within the above range. Furthermore, if the above-mentioned hydrate is used as a corrosion inhibitor, it is preferable that the net content, excluding the water of hydration contained in the hydrate, is within the above range. By controlling the content of component (C) within this range, it is possible to make it less likely to remain on the substrate surface after chemical treatment and to exhibit even better corrosion resistance.

[0070] (Other ingredients)

[0071] The surface modification composition may further contain other components as needed, in addition to the components mentioned above. Examples of other components include pH adjusters such as organic acids and amines. Preferred organic acids include acetic acid, citric acid, phosphoric acid, sulfuric acid, and methanesulfonic acid. More preferred amines include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), ammonia (NH3), ethylenediamine, diethylenetriamine, triethanolamine, and monoethanolamine (MEA).

[0072] (Organic solvents)

[0073] The surface modification composition may contain an organic solvent. Specific examples of the organic solvent are not particularly limited, but it is preferable that it be at least one selected from the group consisting of alcohol-based solvents, glycol ester-based solvents, sulfoxide-based solvents, sulfone-based solvents, amide-based solvents, lactone-based solvents, imidazolidinone-based solvents, nitrile-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, pyrrolidone-based solvents, and urea-based solvents. Furthermore, it is more preferable that the surface modification composition contains only at least one selected from the group consisting of alcohol-based solvents, glycol ester-based solvents, sulfoxide-based solvents, sulfone-based solvents, amide-based solvents, lactone-based solvents, imidazolidinone-based solvents, nitrile-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, pyrrolidone-based solvents, and urea-based solvents, and does not contain any other organic solvents.

[0074] Specific examples of alcohol-based solvents include, for example, aliphatic alcohols such as methanol, ethanol, denatured ethanol, isopropanol, n-propanol, n-butanol, and 3-methoxy-3-methyl-1-butanol; and glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, furfuryl alcohol, and hexylene glycol.

[0075] Specific examples of glycol ester solvents include, for example, ethylene glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monoethyl ether (EDG), diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, triethylene glycol monobutyl ether, triethylene glycol dibutyl ether, ethylene glycol monohexyl ether, ethylene glycol dihexyl ether, diethylene glycol monohexyl ether, diethylene glycol dihexyl ether, and ethylene glycol-phenyl ether; and ethylene glycol ether acetates such as ethylene glycol monobutyl ether acetate and diethylene glycol monobutyl ether acetate.Propylene glycol monomethyl ether (PGME), propylene glycol dimethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, propylene glycol monoethyl ether, propylene glycol diethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol diethyl ether, propylene glycol monopropyl ether, propylene glycol dipropyl ether, dipropylene Examples include propylene glycol ethers such as propylene glycol monopropyl ether, dipropylene glycol dipropyl ether, propylene glycol monobutyl ether, propylene glycol dibutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dibutyl ether, tripropylene glycol monobutyl ether, tripropylene glycol dibutyl ether, and propylene glycol phenyl ether; and propylene glycol ether acetates such as propylene glycol methyl ether acetate (PGMEA), dipropylene glycol methyl ether acetate, and propylene glycol diacetate.

[0076] Specific examples of sulfoxide solvents include dimethyl sulfoxide (DMSO), diethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, and thiophene.

[0077] Specific examples of sulfone-based solvents include, for example, dimethyl sulfone, diethyl sulfone, tetramethylene sulfone, dipropyl sulfone, sulfolane (also known as tetramethylene sulfone), 3-methyl sulfolane, 2,4-dimethyl sulfolane, 3,4-dimethyl sulfolane, diphenyl sulfolane, 3,4-diphenylmethyl sulfolane, sulfolene, 3-methyl sulfolene, and 3-ethyl sulfolene.

[0078] Specific examples of amide solvents include dimethylformamide (DMF), diethylformamide (DEF), dimethylacetamide (DMAc), N-methylpyrrolidine (MPD), and hexamethyltriamide (HMPA).

[0079] Specific examples of lactone-based solvents include, for example, γ-butyllactone, α-methyl-γ-butyrolactone, β-propiolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, γ-laurolactone, and hexanolactone.

[0080] Specific examples of imidazolidinone-based solvents include, for example, 2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone.

[0081] Specific examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0082] Specific examples of ketone solvents include, for example, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisobutyl ketone, cyclohexanone, diacetone alcohol, 1-hexanone, 2-hexanone, 4-heptanone, 2-heptanone (methyl amyl ketone), 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetylacetone, acetonylacetone, phenylacetone, acetophenone, methyl naphthyl ketone, methylcyclohexanone, ionone, isophorone, propylene carbonate (propylene carbonate), diacetonyl alcohol, and acetylcarbinol.

[0083] Specific examples of ether-based solvents include, for example, diisopropyl ether, 1,4-dioxane, methyl-tert-butyl ether (MTBE), dimethyl ether, diethyl ether, dipropyl ether, and methylphenyl ether.

[0084] Specific examples of ester solvents include, for example, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, propyl acetate, isopropyl acetate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 3-ethyl-3-methoxybutyl acetate, 4-methyl-4-methoxypentyl acetate, methyl formate, and formic acid. Examples include ethyl ethyl, propyl formate, butyl formate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc.

[0085] Specific examples of pyrrolidone-based solvents include, for example, N-methylpyrrolidone (NMP), 2-pyrrolidone, and N-vinyl-2-pyrrolidone.

[0086] Specific examples of urea-based solvents include, for example, 1,3-dimethylurea, 1,3-diethylurea, 1,3-dipropylurea, 1,3-diisopropylurea, tetramethylurea, tetraethylurea, tetrapropylurea, tetraisopropylurea, and N,N-dimethylpropyleneurea.

[0087] Among the above, the optional organic solvent is preferably a water-soluble organic solvent. Among the above specific examples, preferred water-soluble organic solvents are, for example, at least one selected from the group consisting of alcohol-based solvents and glycol ester-based solvents; more preferably at least one selected from the group consisting of 1,3-propanediol, glycerin, ethylene glycol, propylene glycol, hexylene glycol, diethylene glycol monoethyl ether (EDG), diethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether (DPM).

[0088] Organic solvents are optional components that may be added, and when added, one type may be used alone, or two or more types may be used in combination.

[0089] Furthermore, the surface modification composition is expected to achieve the desired effect without the use of halogen-based solvents. In other words, it can be used as an environmentally friendly, halogen-free surface modification composition. From this viewpoint, preferred examples of surface modification compositions include those that substantially do not contain halogen atoms, and even those that do not contain halogen atoms at all. In particular, if the composition substantially does not contain fluorine atoms such as fluorides, it can be expected that unintended damage to semiconductor substrates can be effectively suppressed.

[0090] Furthermore, "substantially absent" means that cases where the component is inevitably included as an impurity are not excluded. For example, the content of the component in the surface modification composition is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.3% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0% by mass.

[0091] Furthermore, while a surface modification composition can be expected to provide sufficient effects even without containing organic solvents, it can also be expected to provide sufficient effects even with organic solvents. In other words, a surface modification composition may contain organic solvents. From this perspective, the content of organic solvents in a surface modification composition can be 0 to 95% by mass. The lower limit of the organic solvent content may be 0% by mass, or it may be 5% or more by mass, 10% or more by mass, 20% or more by mass, 30% or more by mass, 40% or more by mass, 50% or more by mass, or 60% or more by mass, depending on the components of the surface modification composition. The upper limit of the organic solvent content may be 90% or less by mass, 80% or less by mass, or 70% or less by mass, for example.

[0092] If the surface modification composition contains water and an organic solvent, the content of the organic solvent relative to the total content of water and the organic solvent is preferably 0.05 to 50% by mass. The lower limit of this content ratio may be, for example, 0.1% by mass or more. The upper limit of this content ratio may be 30% by mass or less, 20% by mass or less, or 10% by mass or less. When water and an organic solvent are included, by setting the above ratio, a water-soluble mixed solvent can be made as the solvent, thereby imparting high water solubility to the cleaning solution, and it is expected that the solubility of the components, reduction of environmental impact, and economic efficiency will be further improved.

[0093] (Impurities, etc., in surface modification compositions)

[0094] The surface modification composition used in this embodiment may contain a metallic impurity, for example, one metal atom selected from the group consisting of Fe atoms, Cr atoms, Ni atoms, Zn atoms, Ca atoms, and Pb atoms.

[0095] The total content of metal atoms in the surface modification composition used in this embodiment is preferably 100 ppt by mass or less, relative to the total mass of the surface modification composition. The lower limit of the total content of metal atoms is preferable as it is lower, but for example, 0.001 ppt by mass or more is acceptable. For example, the total content of metal atoms can range from 0.001 to 100 ppt by mass. By setting the total content of metal atoms to or below the above-mentioned preferred upper limit, it is believed that the defect suppression and residue suppression properties of the surface modification composition will be improved. By setting the total content of metal atoms to or above the above-mentioned preferred lower limit, it is believed that metal atoms will be less likely to be released and exist in the system, thus reducing the likelihood of adverse effects on the overall manufacturing yield of the processed product.

[0096] The content of metal impurities can be adjusted, for example, by purification treatment such as filtering. This purification treatment may be performed on some or all of the raw materials before preparing the surface modification composition, or it may be performed after preparing the surface modification composition.

[0097] The surface modification composition used in this embodiment may contain, for example, organic impurities (organic impurities). The total content of the above-mentioned organic impurities in the surface modification composition used in this embodiment is preferably 5000 ppm by mass or less. The lower limit of the organic impurity content is preferable as it is lower, but for example, 0.1 ppm by mass or more is acceptable. The total content of organic impurities can range from 0.1 to 5000 ppm by mass, for example.

[0098] The surface modification composition used in this embodiment may contain countable particles of a size that can be counted by, for example, a light scattering type liquid particle counter. The size of the countable particles is, for example, 0.04 μm or larger. The number of countable particles in the surface modification composition used in this embodiment is, for example, 1000 or less per 1 mL of surface modification composition, with a lower limit of, for example, 0.1 or more. It is believed that the metal corrosion suppression effect and defect suppression effect of the surface modification composition are improved by the number of countable particles in the surface modification composition being within the above range (however, the effects and benefits of this embodiment are not limited to these).

[0099] The organic impurities and / or substances to be counted described above may be added to the surface modification composition, or they may be inevitably introduced into the surface modification composition during the manufacturing process of the surface modification composition. Examples of cases in which organic impurities are inevitably introduced during the manufacturing process of the surface modification composition include, but are not limited to, cases in which organic impurities are contained in the raw materials (e.g., organic solvents) used in the manufacture of the surface modification composition, and cases in which they are introduced from the external environment during the manufacturing process of the surface modification composition (e.g., contamination).

[0100] When adding the substance to be measured to a surface modification composition, the ratio of each specific size may be adjusted considering the surface roughness of the object to be treated.

[0101] The pH of the surface modification composition is preferably 6.0 to 12.0. The lower limit of this pH is more preferably 7.0 or higher, and even more preferably 7.5 or higher. The upper limit of this pH is more preferably 11.5 or lower, and even more preferably 11.0 or lower. By controlling the pH of the surface modification composition to fall within the above range, the repair of damage to the low-k film and the acceleration of subsequent barrier layer formation can be further improved.

[0102] (Other post-processing steps)

[0103] The semiconductor substrate manufacturing method according to this embodiment may further include any additional steps after the processing steps described above, as needed. The semiconductor substrate manufacturing method according to this embodiment may further include a step of forming a barrier layer on the substrate that has been subjected to the dry etching process, after the step of treating (surface treatment) the dry-etched substrate with a surface modification composition (dry etching step). For example, a step of forming a barrier layer may be added after the processing step. Examples of barrier layers described herein include films intended to suppress the diffusion of wiring metal ions and improve the adhesion of the wiring substrate. The barrier layer can be formed by a step of forming a film on a low-k film after a processing step using a CVD method, ALD method, or PVD method, including or excluding plasma enhancement.

[0104] As the barrier layer, a layer containing at least one selected from the group consisting of tantalum atoms, titanium atoms, tungsten atoms, cobalt, and silicon is preferred. More preferably, the material of the barrier layer is at least one selected from the group consisting of TaN, Ta, TiN, Ti, Co, TaSiN, W2N, and Si3N4. According to this embodiment, such a barrier layer can exhibit even higher film-forming properties.

[0105] <Method for etching substrates>

[0106] The substrate etching method according to this embodiment is a substrate etching method comprising: a step of dry etching a substrate containing a layer containing a low-k material (etching step); and a step of treating the dry-etched substrate with a surface modification composition (treatment step), wherein the surface modification composition contains (A) a silane coupling agent and / or a derivative thereof represented by the general formula (1) described above, and (B) water. For the etching step and the treatment step, the methods and conditions described in the semiconductor substrate manufacturing method described above can be appropriately adopted. Furthermore, for the composition and properties of the surface modification composition, the matters described in the semiconductor substrate manufacturing method described above can also be appropriately adopted.

[0107] According to the substrate etching method of this embodiment, it is possible to etch a substrate containing a layer of low-k material while repairing damage to the low-k film and promoting the subsequent process of forming a barrier layer. [Examples]

[0108] The present invention will be described in more detail by the following examples and comparative examples, but the present invention is not limited in any way by the following examples.

[0109] <Ingredients>

[0110] The abbreviations used in this embodiment are as follows: BDMADMS: Bis(dimethylamino)dimethylsilane

[0111] [ka]

[0112] HMDS: 1,1,1,3,3,3-Hexamethyldisilazane

[0113] [ka]

[0114] ·APTES: 3-Aminopropyltriethoxysilane, 3-Aminopropyltriethoxysilane

[0115] [ka]

[0116] ·AEAPDMMS: 3-(2-Aminoethylamino)propyldimethoxymethylsilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane

[0117] [ka]

[0118] ·AEAEAPT MS: 3-[2-(2-Aminoethylamino)ethylamino]propyltrimethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane

[0119] [ka]

[0120] ·AcOH: Acetic acid, acetic acid ·3A-TAZ: 3-Amino-1H-1,2,4-triazole

[0121] [ka]

[0122] ·TAZ: 1,2,4-Triazole

[0123] [ka]

[0124] · 5M BTA: 5-Methyl-1H-Benzotriazole, 5-methyl-1H-benzotriazole

[0125]

Chem.

[0126] ·PGMEA: Propylene glycol methyl ether acetate, Propylene glycol methyl ether acetate ·DIW: Water ·EDG: Diethylene glycol monoethyl ether, Diethylene glycol monoethyl ether ·1,3-Propanediol: 1,3-Propanediol

[0127] <Preparation of Composition for Surface Modification>

[0128] Compositions for surface modification were prepared so as to have the compositions shown in each table. For example, the composition for surface modification of Example 1 is a composition for surface modification containing 0.1% by mass of APTES, 0.017% by mass of AcOH, 0.1% by mass of 3A-TAZ, and the balance water (DIW), and having a pH of 9.5.

[0129] <Evaluation of TaN ALD Deposition Amount>

[0130] (Deposition Amount of Reference Example) A laminated substrate having a Low-k layer on a substrate (12-inch silicon substrate) was prepared. This laminated substrate was subjected to dry etching under conditions containing CF gas (etching step). Subsequently, after heating the substrate at 350° C. for 2 minutes, a TaN film was formed on the substrate (12-inch silicon substrate) by an ALD method (atomic layer deposition method) under plasma-enhanced conditions using pentakis(dimethylamino)tantalum (PDMAT) and NH3. Then, the film thickness of the TaN film was measured by XRF. This was taken as a reference example. That is, the reference example is a case where only the dry etching step is performed and the treatment step described later is not performed.

[0131] (Film deposition amount in the examples and comparative examples) A laminated substrate having a low-k layer was prepared on a substrate (12-inch silicon substrate). This laminated substrate was dry-etched under conditions containing CF gas (etching step). Subsequently, the dry-etched laminated substrate was treated with the surface modification compositions for each example and comparative example (treatment step). Specifically, the laminated substrate was immersed for 2 minutes in a beaker containing the surface modification composition, which was kept at a constant temperature of 25°C. Then, the treatment solution was completely replaced using DIW or IPA, and after drying using N2 blow, the substrate was heated at 350°C for 2 minutes. Then, a TaN film was deposited on the substrate (12-inch silicon substrate) using the ALD method (atomic layer deposition) under plasma-enhanced conditions with pentakis(dimethylamino)tantalum (PDMAT) and NH3. The thickness of this TaN film was then measured by XRF.

[0132] The evaluation of the film deposition amount (TaN ALD film deposition amount) for the examples and comparative examples was performed by setting the thickness of the TaN film in the reference example to 100%, calculating the relative ratio to this, and based on the following criteria. A: The amount of TaN ALD film deposited was 100% or more. B: The amount of TaN ALD film deposited was between 80% and 100%. The amount of C:TaN ALD film deposited was less than 80%.

[0133] <Evaluation of dielectric constant improvement rate>

[0134] (Dielectric constant of the example) A laminated substrate having a low-k layer was prepared on a substrate (12-inch silicon substrate). This laminated substrate was dry-etched under conditions containing CF gas (etching process). Subsequently, the dielectric constant was measured by CV measurement using the mercury probe method with the substrate heated at 350°C for 2 minutes. This was used as a reference example.

[0135] (Dielectric constant improvement rate of the examples and comparative examples) A laminated substrate having a low-k layer was prepared on a substrate (12-inch silicon substrate). This laminated substrate was dry-etched under conditions containing CF gas (etching step). Subsequently, the dry-etched laminated substrate was treated with the surface modification composition for each example and comparative example (treatment step). Specifically, the laminated substrate was immersed for 2 minutes in a beaker containing the surface modification composition kept at a constant temperature of 25°C, then the treatment solution was completely replaced using DIW or IPA, dried using N2 blow, and then heated at 350°C for 2 minutes. The fabricated substrates were measured by CV measurement using the mercury probe method.

[0136] The dielectric constant improvement rate of the examples and comparative examples was evaluated by calculating the relative dielectric constant using the storage capacitance and low-k film thickness measured by CV measurement. The value of the reference example was set to 100%, and the relative ratio (dielectric constant improvement rate) was determined based on the following criteria. A: The dielectric constant improvement rate was 3.0% or higher. B: The dielectric constant improvement rate was between 0.0% and less than 3.0%. C: The dielectric constant improvement rate was less than 0%.

[0137] Table 1 shows the composition, properties, and evaluation results of Reference Examples, Examples 1-5, and Comparative Examples 1 and 2. Table 2 shows the composition, properties, and evaluation results of Examples 6-15. Table 3 shows the composition, properties, and evaluation results of Examples 16-21.

[0138] [Table 1]

[0139] [Table 2]

[0140] [Table 3]

[0141] Based on the above, it has been confirmed that this embodiment can repair damage to the low-k film while promoting the subsequent process of forming the barrier layer.

Claims

1. A process of dry etching a substrate containing a layer of Low-k material, A method for manufacturing a semiconductor substrate, comprising the step of treating the substrate that has undergone the dry etching with a surface modification composition, A method for manufacturing a semiconductor substrate, wherein the surface modification composition contains (A) a silane coupling agent represented by general formula (1) and / or a derivative thereof, and (B) water. 【Chemistry 1】 (In the formula, A and B each independently represent an organic group containing a hydrogen atom, a hydroxyl group, a hydrocarbon group, or a nitrogen atom, and at least one of A and B represents a hydrogen atom. X and Y each independently represent an alkyl group, an alkoxy group, a hydrogen atom, a halogen atom, or a hydroxyl group, and Z represents an alkoxy group or a hydroxyl group. n represents a number.)

2. The surface modification composition further contains (C) a corrosion inhibitor. A method for manufacturing a semiconductor substrate according to claim 1.

3. The aforementioned (C) corrosion inhibitor is a compound having an aromatic ring structure containing a nitrogen atom. A method for manufacturing a semiconductor substrate according to claim 2.

4. The content of component (A) in the surface modification composition is 0.01 to 10% by mass. A method for manufacturing a semiconductor substrate according to claim 1 or 2.

5. The content of component (C) in the surface modification composition is 0.001 to 5% by mass. A method for manufacturing a semiconductor substrate according to claim 2.

6. The pH of the surface modification composition is 6.0 to 12.

0. A method for manufacturing a semiconductor substrate according to claim 1 or 2.

7. A process of dry etching a substrate containing a layer of Low-k material, A method for etching a substrate, comprising the step of treating the substrate that has undergone the dry etching with a surface modification composition, A method for etching a substrate, wherein the surface modification composition contains (A) a silane coupling agent and / or a derivative thereof represented by general formula (1), and (B) water. 【Chemistry 2】 (In the formula, A and B each independently represent an organic group containing a hydrogen atom, a hydroxyl group, a hydrocarbon group, or a nitrogen atom, and at least one of A and B represents a hydrogen atom. X and Y each independently represent an alkyl group, an alkoxy group, a hydrogen atom, a halogen atom, or a hydroxyl group, and Z represents an alkoxy group or a hydroxyl group. n represents a number.)

8. The surface modification composition further contains (C) a corrosion inhibitor. The method for etching a substrate according to claim 7.

9. The pH of the surface modification composition is 6.0 to 12.

0. The method for etching a substrate according to claim 7 or 8.

10. A surface modification composition for a substrate comprising a layer containing a Low-k material, A surface modification composition comprising (A) a silane coupling agent represented by general formula (1) and / or a derivative thereof, and (B) water. 【Transformation 3】 (In the formula, A and B each independently represent an organic group containing a hydrogen atom, a hydroxyl group, a hydrocarbon group, or a nitrogen atom, and at least one of A and B represents a hydrogen atom. X and Y each independently represent an alkyl group, an alkoxy group, a hydrogen atom, a halogen atom, or a hydroxyl group, and Z represents an alkoxy group or a hydroxyl group. n represents a number.)

11. The surface modification composition further contains (C) a corrosion inhibitor. The surface modification composition according to claim 10.

12. The aforementioned (C) corrosion inhibitor is a compound having an aromatic ring structure containing a nitrogen atom. The surface modification composition according to claim 11.

13. The content of component (A) in the surface modification composition is 0.01 to 10% by mass. The surface modification composition according to claim 10 or 11.

14. The content of component (C) in the surface modification composition is 0.001 to 5% by mass. The surface modification composition according to claim 11.

15. The pH of the surface modification composition is 6.0 to 12.

0. The surface modification composition according to claim 10 or 11.

Images