Method for manufacturing semiconductor substrate, method for etching substrate, and composition for surface modification
Patent Information
- Application Number
- KR1020260031854
- Authority / Receiving Office
- KR · KR
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2025-02-25
- Filing Date
- 2026-02-20
- Publication Date
- 2026-09-01
Smart Images
Figure PAT00020_ABST
Abstract
Description
Technology Field
[0001] Cross-reference regarding related applications
[0002] The present invention claims priority to Japanese Patent Application No. 2025-027583, filed with the Japan Patent Office on February 25, 2025, and incorporates the entirety thereof into this specification by reference.
[0003] The present invention relates to a method for manufacturing a semiconductor substrate, a method for etching a substrate, and a composition for surface modification. Background Technology
[0004] Since semiconductor substrates used in integrated circuits and the like have recently been undergoing high integration due to miniaturization, signal delay in multilayer wiring is suppressed, and thus, ensuring reliability is required. For this reason, a Low-k film (Low-k material) with a low dielectric constant is used as an interlayer insulating film for semiconductor substrates. The Low-k film is patterned by dry etching. Subsequently, in order to prevent the wiring material, such as Cu, from diffusing into the Low-k film, a process of forming a barrier layer such as TaN is performed as a post-process after dry etching.
[0005] As a technology regarding the Low-k film described above, for example, Patent Document 1 discloses a method for treating a dielectric film, comprising a step of exposing at least one surface of the dielectric film to a treatment compound comprising an alkylsilane, an alkoxysilane, an alkylsiloxane, an alkoxysiloxane, an arylsilane, an acylsilane, a cyclosiloxane, a polysilsesquioxane (PSS), an arylsiloxane, an acylsiloxane, a halosiloxane, or a combination of any of these, wherein the dielectric film has a dielectric constant smaller than the dielectric constant of SiO2. Prior art literature
[0006] Japanese Patent Publication No. 2008-532268 The problem to be solved
[0007] However, since the Low-k film is damaged by dry etching, a problem arises in which the electrical properties of the semiconductor substrate deteriorate during the barrier layer deposition process performed after the dry etching, as the Low-k film is damaged. Therefore, regarding the semiconductor substrate manufacturing process and etching technology, there is a need to develop a technology that can repair the damage to the Low-k film and also facilitate the deposition of the barrier layer, which is a subsequent process.
[0008] The present invention is made in consideration of such problems and aims to provide a method for manufacturing a semiconductor substrate, a method for etching a substrate, and a composition for surface modification that can contribute to improving the dielectric constant of a Low-k film without causing defects in the formation of a barrier layer. means of solving the problem
[0009] The inventors, as a result of careful consideration to achieve the above-described objective, have obtained the insight that a method for manufacturing a semiconductor substrate comprises a process of dry-etching a substrate including a layer containing a Low-k material and a process of treating the dry-etched substrate with a surface modification composition, wherein the surface modification composition comprises (A) a silane coupling agent having a specific structure and / or a derivative thereof and (B) water, and thus have completed the present invention.
[0010] That is, the present invention is as follows.
[0011] <1>
[0012] A method for manufacturing a semiconductor substrate comprising a process of dry etching a substrate including a layer containing a low-k material and a process of treating the dry-etched substrate with a surface modification composition, wherein the surface modification composition comprises (A) a silane coupling agent represented by general formula (1) and / or a derivative thereof and (B) water.
[0013] [Chemical Formula 1]
[0014]
[0015] (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.)
[0016] <2>
[0017] The above surface modification composition further contains (C) a corrosion inhibitor, <1> This is a method for manufacturing a semiconductor substrate as described in [the document].
[0018] <3>
[0019] The above (C) inhibitor is a compound having an aromatic ring structure containing nitrogen atoms, <2> This is a method for manufacturing a semiconductor substrate as described in [the document].
[0020] <4>
[0021] The content of component (A) in the surface modification composition is 0.01 to 10 mass%, <1> ~ <3> It is a method for manufacturing a semiconductor substrate described in any one of the following.
[0022] <5>
[0023] The content of the (C) component in the above surface modification composition is 0.001 to 5 mass%, <2> or <3> This is a method for manufacturing a semiconductor substrate as described in [the document].
[0024] <6>
[0025] The pH of the surface modification composition is 6.0 to 12.0, <1> ~ <5> It is a method for manufacturing a semiconductor substrate described in any one of the following.
[0026] <7>
[0027] A method for etching a substrate comprising a process of dry-etching a substrate including a layer containing a low-k material and a process of treating the dry-etched substrate with a surface modification composition, wherein the surface modification composition comprises (A) a silane coupling agent represented by general formula (1) and / or a derivative thereof and (B) water.
[0028] [Chemical Formula 2]
[0029]
[0030] (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.)
[0031] <8>
[0032] The above surface modification composition further contains (C) a corrosion inhibitor, <7> This is an etching method for a substrate described in [the document].
[0033] <9>
[0034] The pH of the surface modification composition is 6.0 to 12.0, <7> or <8> This is an etching method for a substrate described in [the document].
[0035] <10>
[0036] A surface modification composition for a substrate comprising a layer containing a low-k material, wherein the composition comprises (A) a silane coupling agent represented by general formula (1) and / or a derivative thereof, and (B) water.
[0037] [Chemical Formula 3]
[0038]
[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] <11>
[0041] The above surface modification composition further contains (C) a corrosion inhibitor, <10> It is a surface modification composition described in
[0042] <12>
[0043] The above (C) inhibitor is a compound having an aromatic ring structure containing nitrogen atoms, <11> It is a surface modification composition described in
[0044] <13>
[0045] The content of component (A) in the surface modification composition is 0.01 to 10 mass%, <10> ~ <12> It is a surface modification composition described in any one of the following.
[0046] <14>
[0047] The content of the (C) component in the above surface modification composition is 0.001 to 5 mass%, <11> or <12> It is a surface modification composition described in
[0048] <15>
[0049] The pH of the surface modification composition is 6.0 to 12.0, <10> ~ <14> It is a surface modification composition described in any one of the following. Effects of the invention
[0050] According to the present invention, a method for manufacturing a semiconductor substrate, a method for etching a substrate, and a composition for surface modification can be provided, which can repair damage to a Low-k film and promote the formation of a barrier layer in a subsequent process. Specific details for implementing the invention
[0051] Hereinafter, forms for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The present embodiment below is an example for explaining the present invention and is not intended to limit the present invention to the following contents. The present invention may be carried out by appropriate modifications within the scope of its gist. Furthermore, each component and parameter disclosed in this specification may be any combination unless specifically mentioned otherwise. Additionally, the upper and lower limits of values disclosed in this specification may be any combination unless specifically mentioned otherwise.
[0052] In addition, in this specification, “comprise” may be changed as needed to “in,” “consist essentially of,” and “consist of.” Also, “A and / or B” means “A, B, or both” unless specifically stated otherwise.
[0053] In addition, in this specification, “doing or to do” such as “doing or to do” may be replaced with “process” or “step,” “process” may be replaced with “doing or to do” or “step,” and “step” may be replaced with “process” or “process.” In addition, in this specification, “process” such as “process” may be “a device or part configured to perform the process,” “device” may be “a mechanism or part,” and “part” may be “a part or device for being provided in a mechanism, device, or system, etc.”
[0054] Method for manufacturing a semiconductor substrate
[0055] A method for manufacturing a semiconductor substrate related to the present embodiment comprises a process of dry-etching a substrate including a layer containing a Low-k material and a process of treating the dry-etched substrate with a surface modification composition, wherein the surface modification composition comprises (A) a silane coupling agent represented by general formula (1) and / or a derivative thereof and (B) water. In addition, the substrate including a layer containing a Low-k material may be abbreviated as "laminated substrate" below.
[0056] [Chemical Formula 4]
[0057]
[0058] (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.)
[0059] The inventors noted that, as a problem with conventional semiconductor substrate manufacturing methods, the electrical characteristics deteriorate when the Low-k film is damaged during dry etching, and the film formation properties of the barrier layer are poor during the barrier layer formation process, which is a post-dry etching process. The inventors hypothesized that one of the causes of the above problems might be that the surface of the Low-k material is altered by the etching gas of the dry etching, and the polarity of the said surface changes. For example, it is thought that during dry etching, the polarity increases as hydroxyl groups (-OH) derived from water (H2O) are introduced to the surface of the Low-k film.
[0060] Based on the above considerations, the inventors of the present invention, after careful examination, unexpectedly discovered that the problem described above can be solved by treating the substrate with the surface modification composition described above after dry etching. The reason for this is not certain, but it is thought that (A) a silane coupling agent and / or its derivative contained in the surface modification composition can restore the surface of a Low-k film with changed polarity, and that the nitrogen atom in (A) the silane coupling agent and / or its derivative acts as a reaction site for barrier layer formation, thereby promoting the formation of the barrier layer in the subsequent process (however, the operation and effect of the present embodiment are not limited to these).
[0061] Furthermore, when metal wiring on a semiconductor substrate is miniaturized, the surface area of the exposed surface of the metal wiring naturally increases along with the miniaturization, and thus the contact area with the etching gas for dry etching also increases. In this regard, the surface area of the damaged Low-k film increases, and there is a tendency for the area with poor barrier layer deposition performance to increase. Consequently, semiconductor substrates having miniaturized metal wiring exhibit a significant degradation in electrical characteristics due to dry etching. However, according to the semiconductor substrate manufacturing method related to the present embodiment, since the deposition of the barrier layer in the subsequent process can be promoted while repairing damage to the Low-k film, it is possible to meet the demands for miniaturization of semiconductor substrates (however, the operation and effects of the present embodiment are not limited to these).
[0062] Hereinafter, each process of the method for manufacturing a semiconductor substrate related to the present embodiment and the composition of the surface modification composition, etc., will be explained in more detail.
[0063] (Dry etching process)
[0064] In the dry etching process, a substrate including a layer containing a Low-k material is dry etched. Specific examples of a substrate including a layer containing a Low-k material include, for instance, a laminated substrate having a metal wiring layer, an etch stop layer (etch stopper), and a Low-k film (interlayer insulating film) containing a Low-k material stacked on the substrate, and a hard mask layer (HM layer) on top thereof (substrate / metal wiring layer / etch stop layer / Low-k film (interlayer insulating film) / HM layer). In the method for manufacturing a semiconductor substrate related to the present embodiment, it goes without saying that various functional layers other than the layers described above may be additionally stacked as long as they are within the range where the desired effect is obtained, and the layer structure is not limited. For example, the type, size, shape, number of layers, and stacking order of each layer described above stacked on the substrate are not particularly limited, and any desired configuration can be adopted.
[0065] As a substrate, there are no particular limitations, but examples include a substrate containing at least one selected from the group consisting of silicon, amorphous silicon, and glass.
[0066] The metal wiring layer is not particularly limited and may include, for example, a metal wiring layer containing at least one selected from the group consisting of metals such as 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), 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), and their metal oxides, metal nitrides, metal chlorides, and metal fluorides.
[0067] The etching stop layer is not particularly limited and, for example, silicon-based materials such as SiN, SiON, 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, etc., may be used.
[0068] Low-k films (interlayer insulating films) containing low-k materials are not particularly limited and examples include SiOC, SiCOH, and SiOCN. Generally, materials with a dielectric constant lower than that of SiO2 (dielectric constant k = 4.1) are preferably used. Unnecessary parts of the low-k film are removed by dry etching to form a predetermined pattern shape. However, the surface exposed after removal is damaged by dry etching. The larger the area of the exposed surface, the greater the impact of damage caused by dry etching.
[0069] As for the hard mask layer (HM layer), it is sufficient to be a layer containing a material that functions as a protective film against dry etching; the material is not particularly limited, and an appropriately desirable material can be selected considering manufacturing conditions, etc. By forming a patterned HM layer, a Low-k film, etc., can be dry etched to correspond to the pattern. As for the HM layer, for example, TiO₂ x , TiN, ZrO x 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, SiN, SiO2, etc.) may be used.
[0070] The method of forming the various layers described above on a substrate is not particularly limited, but examples include the ALD (atomic layer deposition), sputtering, CVD (chemical vapor deposition), PVD (physical vapor deposition), spin-on method, etc. In addition, plasma treatment may be performed on a film formed by these methods, etc.
[0071] In addition, the substrate comprising a layer containing a Low-k material preferably has a Low-k film (interlayer insulating film) containing a Low-k material and a functional layer containing at least one type 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 additionally have an etching stop layer as needed, and may additionally have a hard mask layer (HM layer) on its outermost surface.
[0072] The method and conditions of dry etching are not particularly limited, and preferred methods and conditions may be adopted by considering the material or composition 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 Examples of etching methods include those using inorganic fluorine gases such as F2 and SF6 (where x, y, and z each represent numbers independently), or organic fluorine gases. Additionally, etching devices such as CCP (Capacitive Coupled Plasma) and ICP (Inductively Coupled Plasma) can be employed.
[0073] While dry etching has the characteristic of excellent anisotropy, it has the problem that the substrate to be etched is susceptible to damage, and in particular, the surface of the Low-k film is susceptible to damage. However, according to the manufacturing method related to the present embodiment, in the processing process described below, by using (A) a silane coupling agent and / or a derivative thereof represented by general formula (1) and (B) a surface modification composition containing water to treat the substrate, the damage to the Low-k film can be repaired while promoting the formation of the barrier layer in the subsequent process.
[0074] (Treatment process, composition for surface modification)
[0075] In a process (processing process) in which a substrate on which dry etching has been performed is treated with a surface modification composition, a surface modification composition containing (A) a silane coupling agent having a structure represented by general formula (1) and / or a derivative thereof, and (B) water is used. By using such a surface modification composition, damage to the Low-k film can be repaired, and the subsequent formation of the barrier layer can be promoted.
[0076] [Chemical Formula 5]
[0077]
[0078] (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.)
[0079] ((A) Component: Silane coupling agent and / or derivative thereof)
[0080] In general formula (1), 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.
[0081] As for the hydrocarbon group, it is preferable that it be 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 even more preferably 3 or more. In addition, the upper limit of the number of carbon atoms is more preferably 7 or less, and even more preferably 6 or less.
[0082] As for the organic group containing a nitrogen atom, it is preferable that it be a monovalent organic group containing only a nitrogen atom, a carbon atom, and a hydrogen atom; -(CH2) p -NH2(p represents a number from 1 to 5), and -(CH2) q -NH(CH2) r -(CH2) s It is more preferable that at least one type is selected from the group consisting of -NH2(q, r, and s each independently represent a number from 1 to 5); -(CH2) t -NH2(t represents a number from 1 to 3), and -(CH2) u -NH(CH2) v -(CH2) wIt is more preferable that at least one type is selected from the group consisting of -NH2 (u, v, and w each independently represent a number from 1 to 3).
[0083] X and Y in general formula (1) each independently represent an alkyl group, an alkoxy group, a hydrogen atom, a halogen atom, or a hydroxyl group. As for the alkyl group, it is preferable that it be an alkyl group having 1 to 5 carbon atoms, more preferable that it be an alkyl group having 1 to 3 carbon atoms, and even more preferable that it be an alkyl group having 1 or 2 carbon atoms. As for the alkoxy group, it is preferable that it be at least one selected from the group consisting of a methoxy group, an ethoxy group, an n-propoxy group, and an iso-propoxy group.
[0084] Z in general formula (1) represents an alkoxy group or a hydroxyl group. As for the alkoxy group, it is preferable to have at least one selected from the group consisting of a methoxy group, an ethoxy group, an n-propoxy group, and an iso-propoxy group.
[0085] n in general formula (1) represents a number. n is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.
[0086] Derivatives of the silane coupling agent represented by general formula (1) are not particularly limited and may be derivatives having a structure that the silane coupling agent can take. For example, some or all of the alkoxy groups are hydrolyzed to have silanol groups, or dehydration condensation products of the generated silanols (e.g., oligomers, dimers).
[0087] A specific example of a silane coupling agent represented by general formula (1) is 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-aminobutyltrimethoxysilane, and 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (AEAEAPTMS).
[0088] In addition, 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.
[0089] The content of component (A) in the surface modification composition is not particularly limited, but is preferably 0.01 to 10 mass%. The lower limit of this content is more preferably 0.05 mass% or more, more preferably 0.1 mass% or more, and more preferably 0.5 mass% or more. In addition, the upper limit of this content is more preferably 8 mass% or less, more preferably 6 mass% or less, and more preferably 5 mass% or less. By controlling the content within this range, the effect of modifying a damaged Low-k film while suppressing inhibition of barrier film formation can be further enhanced.
[0090] ((B) Ingredient: Water)
[0091] Water is not particularly limited, and, from the perspective of being suitable for manufacturing semiconductor substrates, for example, deionized water (DIW) can be used.
[0092] The content of component (B) in the surface modification composition is not particularly limited, but is preferably 45 to 99.99 mass%. The lower limit of the water content may be, for example, 60 mass% or more, 70 mass% or more, 80 mass% or more, or 85 mass% or more. When the water content is high, it can be preferably used as a so-called water-based surface modification composition, but the water content may be selected according to the application, taking into account the type of metal to be cleaned, etc. In addition, when preparing, the necessary components other than water may be added, and water may be added as the remainder.
[0093] ((C) Ingredient: Anti-corrosion agent)
[0094] The surface modification composition preferably further contains (C) a corrosion inhibitor. As for the corrosion inhibitor, it is more preferable that it be a compound having an aromatic ring structure containing a nitrogen atom.
[0095] Specific examples of the anti-corrosion agent are not particularly limited, but it is preferable to have 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, pyrazol 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 anti-corrosion properties of various layers (e.g., metal wiring layers, etching stop layers, interlayer insulating films, hard mask layers, etc.) containing copper atoms, cobalt atoms, tungsten atoms, and / or molybdenum atoms can be improved.
[0096] 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, 5-methylbenzimidazole, etc.
[0097] 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, 4-carboxyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazole methyl ester, 4-carboxyl-1H-benzotriazole butyl ester, and 4-carboxyl-1H-benzotriazole octyl ester. Examples include 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, 3-aminotriazole, etc. 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, 5-methyl-1H-benzotriazole (5M-BTA), etc. are preferred, and 1,2,4-triazole (TAZ), 3-amino-1H-1,2,4-triazole (3A-TAZ), 5-methyl-1H-benzotriazole (5M-BTA), etc. are more preferred.
[0098] Specific examples of carbazole ring-containing compounds include 9H-carbazole, 4-hydroxycarbazole, 1-methyl-carbazole, 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, 2,7-dibromocarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 2,3-benzcarbazole, and 9-acetyl-3,6-diiodocarbazole. Examples include 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, 7H-benzo[c]carbazole, etc.
[0099] 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-acetamidepyridine, 4-pyrrolidinopyridine, 2-cyanopyridine, 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, Examples include 4,4'-di-tert-butyl-2,2'-bipyridyl, 4,4'-dinonyl-2,2'-bipyridyl, etc.
[0100] 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-tetraaminopyrimidinesulfate, 2,4,5-trihydroxypyrimidine, 2,4,6-triaminopyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-trimethoxypyrimidine, 2,4,6-triphenylpyrimidine, 2,4-diamino6-hydroxypyrimidine, 2,4-diaminopyrimidine, Examples include 2-acetamidepyrimidine, 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, 4-aminopyrazolo[3,4-d]pyrimidine, etc.
[0101] Examples of tetrazole ring-containing compounds include 2,3,5-triphenyltetrazole, 2,3,5-triphenyltetrazole chloride, 2,3,5-triphenyltetrazole bromide, 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 1-(2-diaminoethyl)-5-mercaptotetrazole, etc.
[0102] 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, benzidamine hydrochloride, etc. Among these, 3-phenylpyrazole, indazole, 4-fluoroindazole, 5-nitroindazole, indazole-3-carboxylic acid, benzidamine hydrochloride, etc. are preferred.
[0103] Specific examples of purine ring-containing compounds include purines, etc.
[0104] Specific examples of phenanthroline ring-containing compounds include 1,10-phenanthroline.
[0105] Specific examples of benzothioazole ring-containing compounds include benzothiazole, 2,5-dimethylbenzothiazole, 2,6-dimethylbenzothiazole, etc.
[0106] In addition, the anti-corrosion agent may be a salt of the compound described above, and specific examples of the salt are not particularly limited, but examples include sodium salt, potassium salt, chloride salt, ammonium salt, alkylammonium salt (e.g., tetramethylammonium salt, etc.). In addition, it may be a hydrate of the compound described above.
[0107] The anti-corrosion agent may be used as a single type of the above-mentioned agent, or two or more types may be used in combination. The surface modification composition may contain two or more types of anti-corrosion agents from the perspective that it can impart an anti-corrosion effect to various types of metals. The anti-corrosion agent may be selected according to the type of various layers to be targeted (e.g., metal wiring layer, etching stop layer, interlayer insulating film, hard mask layer, etc.). When the surface modification composition contains two or more types of anti-corrosion agents, it is more preferable to include at least two types 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, pyrazol ring-containing compounds, purine ring-containing compounds, and phenanthroline ring-containing compounds as anti-corrosion agents. All of these may be those described above.
[0108] In the composition for surface modification, the content of component (C) is preferably 0.001 to 5 mass%. The lower limit of this content is more preferably 0.03 mass% or more, more preferably 0.05 mass% or more, and more preferably 0.1 mass% or more. In addition, the upper limit of this content is more preferably 3 mass% or less, more preferably 2 mass% or less, and more preferably 1 mass% or less. When two or more types of anti-corrosion agents are included as component (C), it is preferable that the sum of their contents falls within the range described above. In addition, when the hydrate described above is used as an anti-corrosion agent, it is preferable that the content of the pure flavor, excluding the hydrated water contained in the hydrate, falls within the range described above. By controlling the content of component (C) within this range, it is difficult to leave it on the substrate surface after chemical treatment, and further excellent anti-corrosion properties can be exhibited.
[0109] (Other ingredients)
[0110] The surface modification composition may additionally contain other components as necessary, in addition to the above components. Examples of other components include pH adjusters such as organic acids or amines. Specific examples of organic acids include acetic acid, citric acid, phosphoric acid, sulfuric acid, methanesulfonic acid, etc. Specific examples of amines include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), ammonia (NH3), ethylenediamine, diethylenetriamine, triethanolamine, monoethanolamine (MEA), etc. are more preferred.
[0111] (Organic solvent)
[0112] The surface modification composition may contain an organic solvent. Specific examples of organic solvents are not particularly limited, but it is preferable that at least one is 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 comprises only at least one organic solvent 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 organic solvents other than these.
[0113] 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; 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.
[0114] Specific examples of glycol ester-based solvents include, for example, ethylene-based 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, ethylene glycol-phenyl ether, etc.; Ethylene-based glycol ether acetates such as ethylene glycol monobutyl ether acetate and diethylene glycol monobutyl ether acetate; Propylene-based glycol ethers such as 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 glycol monobutyl ether, propylene glycol dibutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dibutyl ether, tripropylene glycol monobutyl ether, tripropylene glycol dibutyl ether, propylene glycol phenyl ether, etc.; Examples include propylene glycol ether acetates such as propylene glycol methyl ether acetate (PGMEA), dipropylene glycol methyl ether acetate, and propylene glycol diacetate.
[0115] Specific examples of sulfoxide-based solvents include, for instance, dimethyl sulfoxide (DMSO), diethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, thiophene, etc.
[0116] Specific examples of sulfone-based solvents include, for example, dimethylsulfone, diethylsulfone, tetramethylenesulfone, dipropylsulfone, sulfolane (alias: tetramethylenesulfone), 3-methylsulfolane, 2,4-dimethylsulfolane, 3,4-dimethylsulfolane, diphenylsulfolane, 3,4-diphenylmethylsulfolane, sulfolane, 3-methylsulfolane, 3-ethylsulfolane, etc.
[0117] Specific examples of amide-based solvents include, for instance, dimethylformamide (DMF), diethylformamide (DEF), dimethylacetamide (DMAc), N-methylpyrrolidine (MPD), hexamethylphosphate triamide (HMPA), etc.
[0118] Specific examples of lactone-based solvents include, for example, γ-butyrolactone, α-methyl-γ-butyrolactone, β-propiolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, γ-laurolactone, hexanolactone, etc.
[0119] 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, 1,3-diisopropyl-2-imidazolidinone, etc.
[0120] Specific examples of nitrile-based solvents include, for instance, acetonitrile, propionitrile, valeronitrile, butyronitrile, etc.
[0121] Specific examples of ketone-based 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, acetonyl acetone, phenylacetone, acetophenone, methyl naphthyl ketone, methylcyclohexanone, ionone, isophorone, propylene carbonate (propylene carbonate), diacetonyl alcohol, acetylcarbinol, etc.
[0122] 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, methylphenyl ether, etc.
[0123] Specific examples of ester-based solvents include, for example, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, propyl acetate, isopropyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate (2-methoxybutyl acetate), 3-methoxybutyl acetate (3-methoxybutyl acetate), 4-methoxybutyl acetate (4-methoxybutyl acetate), 3-methoxy-3-methylbutyl acetate (3-methoxy-3-methylbutyl acetate), 3-ethyl-3-methoxybutyl acetate (3-ethyl-3-methoxybutyl acetate), 4-methyl-4-methoxypentyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl lactate, ethyl lactate, propyl lactate. Examples include 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, 2-methyl hydroxypropionate, 2-ethyl hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc.
[0124] Specific examples of pyrrolidone-based solvents include, for example, N-methylpyrrolidone (NMP), 2-pyrrolidone, N-vinyl-2-pyrrolidone, etc.
[0125] 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, N,N-dimethylpropyleneurea, etc.
[0126] Among the above, the organic solvent, which is an optional component, is preferably a water-soluble organic solvent. Among the above specific examples, a preferred example of a water-soluble organic solvent is, for instance, at least one selected from the group consisting of alcohol-based solvents and glycol ester-based solvents; and 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).
[0127] Organic solvents are optional ingredients that may be added, but when added, one type may be used alone or two or more types may be used in combination.
[0128] Furthermore, it is expected that the surface modification composition will achieve the desired effect without using halogen-based solvents. In other words, it is possible to use it as an environmentally friendly, halogen-free surface modification composition. In this regard, preferred examples of surface modification compositions include those that substantially do not contain halogen atoms, or furthermore, those that do not contain them. In particular, when the composition substantially does not contain fluorine atoms such as fluorides, it is expected that unintended damage to the semiconductor substrate can be effectively suppressed.
[0129] In addition, "substantially not contained" means that the case in which the component is inevitably incorporated as an impurity is not excluded. For example, the content of the component in the surface modification composition is preferably 1 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.3 mass% or less, even more preferably 0.1 mass% or less, and even more preferably 0 mass%.
[0130] In addition, while it is expected that a surface modification composition can achieve sufficient effects even without containing an organic solvent, it is also expected that a sufficient effect can be achieved even if it contains an organic solvent. That is, the surface modification composition may contain an organic solvent. In this regard, the content of the organic solvent in the surface modification composition may be 0 to 95 mass%. Furthermore, the lower limit of the organic solvent content may be 0 mass%, or, depending on the components of the surface modification composition, it may be, for example, 5 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, 50 mass% or more, or 60 mass% or more. Also, the upper limit of the organic solvent content may be, for example, 90 mass% or less, 80 mass% or less, or 70 mass% or less.
[0131] When the surface modification composition contains water and an organic solvent, it is preferable that the content of the organic solvent relative to the sum of the water content and the organic solvent content be 0.05 to 50 mass%. The lower limit of this content ratio may be, for example, 0.1 mass% or more. In addition, the upper limit of this content ratio may be 30 mass% or less, 20 mass% or less, or 10 mass% or less. When water and an organic solvent are contained, by using the above ratios, a water-soluble mixed solvent can be used as the solvent, thereby imparting higher water solubility to the cleaning solution, and it is expected that the solubility of the components, reduction of the burden on the environment, and economic efficiency can be further improved.
[0132] (Impurities, etc. in the surface modification composition)
[0133] The surface modification composition used in the present embodiment may include, for example, a metal impurity comprising at least one metal atom selected from the group consisting of Fe atoms, Cr atoms, Ni atoms, Zn atoms, Ca atoms, and Pb atoms.
[0134] The total content of metal atoms in the surface modification composition used in the present embodiment is preferably 100 mass ppt or less with respect to the total mass of the surface modification composition. The lower limit of the total content of metal atoms is preferably lower, but, for example, 0.001 mass ppt or more may be used. The total content of metal atoms may be, for example, 0.001 to 100 mass ppt. It is believed that by keeping the total content of metal atoms below the above-mentioned preferred upper limit, the defect suppression and residue suppression properties of the surface modification composition are improved. It is believed that by keeping the total content of metal atoms above the above-mentioned preferred lower limit, it becomes difficult for metal atoms to exist freely in the system, thereby making it difficult to adversely affect the manufacturing yield of the entire object to be treated.
[0135] The content of metal impurities can be adjusted, for example, by purification treatment such as filtering. Purification treatment such as filtering may be performed on part or all of the raw materials before preparing the surface modification composition, or it may be performed after preparing the surface modification composition.
[0136] The surface modification composition used in the present embodiment may include, for example, impurities derived from organic matter (organic impurities). The total content of the above-mentioned organic impurities in the surface modification composition used in the present embodiment is preferably 5,000 mass ppm or less. The lower limit of the organic impurity content is preferably lower, but, for example, 0.1 mass ppm or more may be given. The total content of organic impurities may be, for example, 0.1 to 5,000 mass ppm.
[0137] The surface modification composition used in the present embodiment may include, for example, a sample to be counted of a size counted by a light scattering liquid particle counter. The size of the sample to be counted is, for example, 0.04 μm or larger. The number of samples to be counted in the surface modification composition used in the present embodiment is, for example, 1,000 or less per 1 mL of the surface modification composition, and the lower limit is, for example, 0.1 or larger. It is believed that by keeping the number of samples to be counted in the surface modification composition within the range described above, the metal corrosion inhibition effect or defect inhibition effect by the surface modification composition is improved (however, the operation and effect of the present embodiment are not limited to these).
[0138] The above-mentioned organic impurities and / or substances to be added to the surface modification composition, or they may be inevitably incorporated into the surface modification composition during the manufacturing process of the surface modification composition. Examples of cases where they are inevitably incorporated during the manufacturing process of the surface modification composition include, for instance, cases where organic impurities are included in the raw materials (e.g., organic solvents) used to manufacture the surface modification composition, and cases where they are incorporated from the external environment during the manufacturing process of the surface modification composition (e.g., contamination), but are not limited to the above.
[0139] When adding a substance to be modified to a surface modification composition, the abundance ratio may be adjusted for each specific size, taking into account the surface roughness of the object to be treated.
[0140] 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. In addition, 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 be within the range described above, the repair of damage to the Low-k film and the promotion of the subsequent process of forming a barrier layer can be further enhanced.
[0141] (Other post-processing)
[0142] The method for manufacturing a semiconductor substrate related to the present embodiment may additionally perform any process as needed after the processing process described above. The method for manufacturing a semiconductor substrate related to the present embodiment may additionally include a process of forming a barrier layer on a substrate that has undergone the dry etching process (surface treatment) after the process of treating (surface treatment) the substrate that has undergone the dry etching process with a surface modification composition (dry etching process). For example, a process of forming a barrier layer may be additionally performed after the processing process. Examples of the barrier layer described herein include a film intended to suppress the diffusion of wiring metal ions and to increase the adhesion of the wiring substrate. The barrier layer may be formed by a process of depositing a film on a Low-k film after the processing process using a CVD method, ALD method, or PVD method, including the presence or absence of plasma enhancement.
[0143] As for the barrier layer, for example, a layer containing at least one selected from the group consisting of tantalum atoms, titanium atoms, tungsten atoms, cobalt, and silicon is preferred. Furthermore, as for the material of the barrier layer, it is more preferable to be at least one selected from the group consisting of TaN, Ta, TiN, Ti, Co, TaSiN, W2N, and Si3N4. According to the present embodiment, such a barrier layer can exhibit even higher film-forming properties.
[0144] <Substrate Etching Method>
[0145] The etching method of a substrate related to the present embodiment comprises a process of dry-etching a substrate including a layer containing a Low-k material (etching process) and a process of treating the dry-etched substrate with a surface modification composition (treatment process), wherein the surface modification composition comprises (A) a silane coupling agent represented by the general formula (1) described above and / or a derivative thereof, and (B) water. For the etching process and the treatment process, the methods and conditions described in the semiconductor substrate manufacturing method described above may be appropriately adopted. Furthermore, regarding the composition and characteristics of the surface modification composition, matters described in the semiconductor substrate manufacturing method described above may also be appropriately adopted.
[0146] According to the etching method of a substrate related to the present embodiment, while etching a substrate including a layer containing a Low-k material and repairing damage to the Low-k film, the formation of a barrier layer in a subsequent process can be promoted.
[0147] Examples
[0148] The present invention will be explained in more detail by the following examples and comparative examples, but the present invention is not limited in any way by the following examples.
[0149] Ingredients
[0150] The abbreviations in this embodiment are as follows.
[0151] ·BDMADMS :
[0152] Bis(dimethylamino)dimethylsilane
[0153] [Chemical Formula 6]
[0154]
[0155] ·HMDS :
[0156] 1,1,1,3,3,3-Hexamethyldisilazane
[0157] [Chemical Formula 7]
[0158]
[0159] ·APTES :
[0160] 3-Aminopropyltriethoxysilane
[0161] [Chemical Formula 8]
[0162]
[0163] ·AEAPDMMS :
[0164] 3-(2-Aminoethylamino)propyldimethoxymethylsilane
[0165] [Chemical Formula 9]
[0166]
[0167] ·AEAEAPTMS :
[0168] 3-[2-(2-Aminoethylamino)ethylamino]propyltrimethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane
[0169] [Chemical Formula 10]
[0170]
[0171] ·AcOH :
[0172] Acetic acid
[0173] ·3A-TAZ :
[0174] 3-Amino-1H-1,2,4-triazole
[0175] [Chemical Formula 11]
[0176]
[0177] ·TAZ :
[0178] 1,2,4-Triazole
[0179] [Chemical Formula 12]
[0180]
[0181] ·5M-BTA :
[0182] 5-Methyl-1H-Benzotriazole
[0183] [Chemical Formula 13]
[0184]
[0185] ·PGMEA :
[0186] Propylene glycol methyl ether acetate
[0187] ·DIW :
[0188] water
[0189] ·EDG :
[0190] Diethylene glycol monoethyl ether
[0191] ·1,3-Propanediol :
[0192] 1,3-propanediol
[0193] <Preparation of a Composition for Surface Modification>
[0194] A surface modification composition was prepared to have the compositions shown in each table. For example, the surface modification composition of Example 1 is a surface modification composition containing 0.1 mass% of APTES, 0.017 mass% of AcOH, 0.1 mass% of 3A-TAZ, and the remainder being water (DIW), and has a pH of 9.5.
[0195] <TaN ALD 성막량의 평가>
[0196] (Quantity of the Tabernacle for reference)
[0197] A laminated substrate having a Low-k layer was prepared on a substrate (a 12-inch silicon substrate). This laminated substrate was subjected to dry etching under conditions containing CF gas (etching process). Subsequently, the substrate was heated at 350°C for 2 minutes, and a TaN film was deposited on the substrate (a 12-inch silicon substrate) by the ALD method (atomic layer deposition) under plasma-enhanced conditions using pentakis(dimethylamino)tantal (PDMAT) and NH3. The film thickness of this TaN film was measured by XRF. This was used as a reference example. That is, the reference example is a case in which only the dry etching process is performed and the processing process described below is not performed.
[0198] (Amount of membrane formation in the example and comparative example)
[0199] A laminated substrate having a Low-k layer was prepared on a substrate (a 12-inch silicon substrate). This laminated substrate was subjected to dry etching under conditions containing CF gas (etching process). Subsequently, the dry-etched laminated substrate was treated using the surface modification compositions of each example and each comparative example (treatment process). Specifically, the laminated substrate was immersed for 2 minutes in a beaker containing the surface modification composition kept constant at 25°C, after which the treatment solution was completely replaced using DIW or IPA, dried using an N2 blower, and then heated at 350°C for 2 minutes. Then, a TaN film was deposited on the substrate (a 12-inch silicon substrate) using pentakis(dimethylamino)tantalum (PDMAT) and NH3 under plasma-enhanced conditions by the ALD method (atomic layer deposition). The film thickness of the TaN film was then measured by XRF.
[0200] The evaluation of the film deposition amount (TaN ALD film deposition amount) of the examples and comparative examples was carried out by setting the thickness of the TaN film of the reference example to 100%, calculating the relative ratio to this, and based on the following criteria.
[0201] A: The amount of TaN ALD film formation was 100% or more.
[0202] B: The amount of TaN ALD film formation was 80% or more and less than 100%.
[0203] C: The amount of TaN ALD film formation was less than 80%.
[0204] <Evaluation of Permittivity Improvement Rate>
[0205] (Permittivity of the reference example)
[0206] A laminated substrate having a Low-k layer was prepared on a substrate (a 12-inch silicon substrate). This laminated substrate was subjected to dry etching under conditions containing CF gas (etching process). Subsequently, the substrate was heated at 350°C for 2 minutes, and the dielectric constant was measured by CV measurement using the mercury probe method. This was used as a reference example.
[0207] (Permittivity improvement rate of Examples and Comparative Examples)
[0208] A laminated substrate having a Low-k layer was prepared on a substrate (a 12-inch silicon substrate). This laminated substrate was subjected to dry etching under conditions containing CF gas (etching process). Subsequently, the dry-etched laminated substrate was treated using the surface modification compositions of each example and each comparative example (treatment process). Specifically, the laminated substrate was immersed for 2 minutes in a beaker containing the surface modification composition kept constant at 25°C, after which the treatment solution was completely replaced using DIW or IPA, dried using an N2 blower, and then heated at 350°C for 2 minutes. The prepared substrate was measured by CV measurement using the mercury probe method.
[0209] The evaluation of the dielectric constant improvement rate of the examples and comparative examples was carried out by calculating the relative dielectric constant using the accumulated capacitance (capacitance) and Low-k film thickness measured by CV measurement, setting the value of the reference example to 100%, determining the relative ratio (dielectric constant improvement rate) to this, and based on the following criteria.
[0210] A: The dielectric constant improvement rate was 3.0% or higher.
[0211] B: The dielectric constant improvement rate was 0.0% or more and less than 3.0%.
[0212] C: The dielectric constant improvement rate was less than 0%.
[0213] The composition, characteristics, and evaluation results of Reference Example, Examples 1 to 5, and Comparative Examples 1 and 2 are shown in Table 1. The composition, characteristics, and evaluation results of Examples 6 to 12 are shown in Table 2. The composition, characteristics, and evaluation results of Examples 13 to 18 are shown in Table 3.
[0214]
[0215]
[0216]
[0217] From the above, it has been confirmed that, according to the present embodiment, it is possible to repair damage to the Low-k film while promoting the formation of the barrier layer in the subsequent process.
Claims
Claim 1 A method for manufacturing a semiconductor substrate comprising a process of dry etching a substrate including a layer containing a low-k material, and a process of treating the substrate on which the dry etching has been performed with a surface modification composition, wherein the surface modification composition comprises (A) a silane coupling agent represented by general formula (1) and / or a derivative thereof, and (B) water. (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.) Claim 2 A method for manufacturing a semiconductor substrate, wherein the surface modification composition of claim 1 further comprises (C) a corrosion inhibitor. Claim 3 A method for manufacturing a semiconductor substrate according to claim 2, wherein the (C) inhibitor is a compound having an aromatic ring structure containing nitrogen atoms. Claim 4 A method for manufacturing a semiconductor substrate according to claim 1 or 2, wherein the content of component (A) in the surface modification composition is 0.01 to 10 mass%. Claim 5 A method for manufacturing a semiconductor substrate according to claim 2, wherein the content of the (C) component in the surface modification composition is 0.001 to 5 mass%. Claim 6 A method for manufacturing a semiconductor substrate according to claim 1 or 2, wherein the pH of the surface modification composition is 6.0 to 12.
0. Claim 7 A method for etching a substrate comprising a process of dry-etching a substrate including a layer containing a low-k material, and a process of treating the dry-etched substrate with a surface modification composition, wherein the surface modification composition comprises (A) a silane coupling agent represented by general formula (1) and / or a derivative thereof, and (B) water. (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.) Claim 8 In claim 7, the surface modification composition further comprises (C) a corrosion inhibitor, a method for etching a substrate. Claim 9 A method for etching a substrate according to claim 7 or 8, wherein the pH of the surface modification composition is 6.0 to 12.
0. Claim 10 A surface modification composition for a substrate comprising a layer containing a low-k material, comprising (A) a silane coupling agent represented by general formula (1) and / or a derivative thereof, and (B) water. (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.) Claim 11 In claim 10, the surface modification composition further comprises (C) a corrosion inhibitor, a surface modification composition. Claim 12 In claim 11, the surface modification composition, wherein the (C) inhibitor is a compound having an aromatic ring structure containing a nitrogen atom. Claim 13 A surface modification composition according to claim 10 or 11, wherein the content of component (A) in the surface modification composition is 0.01 to 10 mass%. Claim 14 A surface modification composition according to claim 11, wherein the content of the (C) component in the surface modification composition is 0.001 to 5 mass%. Claim 15 A surface modification composition according to claim 10 or 11, wherein the pH of the surface modification composition is 6.0 to 12.0.