Composition, method for treating a metal-containing film using the same, and method for manufacturing a semiconductor device using the same.

Abstract

The present invention provides a composition, a method for processing a metal-containing film using the same, and a method for manufacturing a semiconductor device using the same. [Solution] A composition comprising an oxidizing agent, an ammonium-based buffer, and an etching modifier, wherein the etching modifier comprises a compound represented by chemical formula 1; a method for treating a metal-containing film using the same; and a method for manufacturing a semiconductor device using the same. A description of chemical formula 1 is provided in this specification.

Description

[Technical Field]

[0001] The present invention relates to a composition, a method for treating a metal-containing film using the same, and a method for manufacturing a semiconductor device using the same. [Background technology]

[0002] To meet consumer demands for superior performance and low cost, there is a need for increased integration density and improved reliability of semiconductor devices. As the integration density of semiconductor devices increases, damage to the components of the semiconductor device during the manufacturing process has a greater impact on the reliability and electrical characteristics of the semiconductor memory device. In particular, various processing steps, such as etching and cleaning, are performed on a predetermined film (e.g., a metal-containing film) during the manufacturing process of semiconductor devices. There is a persistent need for compositions with appropriate etching rates and excellent cleaning capabilities to effectively perform metal-containing film processing steps. [Overview of the project] [Problems that the invention aims to solve]

[0003] The problem that this invention aims to solve is to provide a composition having an excellent etching selectivity ratio and excellent cleaning ability, a method for processing a metal-containing film using the same, and a method for manufacturing a semiconductor device using the same. [Means for solving the problem]

[0004] According to one aspect, It comprises an oxidizing agent, an ammonium-based buffer, and an etching controller. The content of the oxidizing agent is 16 wt% to 50 wt% per 100 wt% of the composition. The etching modifier is provided as a composition comprising a compound represented by chemical formula 1: [ka]

[0005] In the above Chemical Formula 1, R1 is a C 30 ,

[0006] , , ,

[0008] , , - , , , , 30 , , , ,

[0007] , , , -C 50 alkyl group or a C 12 -C 50 alkenyl group, R2 is hydrogen, a C1-C 50 alkyl group, or a C2-C<00000​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ During the contact step between the metal-containing film and the composition, a portion or more of the metal-containing film may be etched and cleaned.

[0009] The metal-containing film comprises a first region and a second region. The second etching rate at which the composition etches the second region is greater than the first etching rate at which the composition etches the first region.

[0010] The first region comprises at least one of cobalt and copper, and the second region comprises titanium nitride.

[0011] During the contact step between the metal-containing film and the composition, residues on the surface of the metal-containing film are removed, thereby cleaning a portion or more of the metal-containing film. The aforementioned residues include etching gas residues, polymer residues, metal-containing residues, or any combination thereof.

[0012] In other embodiments, The steps include preparing a substrate to which a metal-containing film is provided, A step of bringing the metal-containing film and the composition into contact, A method for manufacturing a semiconductor device is provided, which includes the step of carrying out subsequent manufacturing processes to produce a semiconductor device. [Effects of the Invention]

[0013] The aforementioned composition has an excellent etching selectivity ratio and excellent cleaning ability, and can be effectively used in various processing steps for diverse metal-containing films, such as etching and cleaning steps. Therefore, high-quality semiconductor devices can be manufactured by processing metal-containing films using the aforementioned composition. [Brief explanation of the drawing]

[0014] [Figure 1]This is a flowchart of one embodiment of a method for fabricating semiconductor devices. [Figure 2] This diagram briefly illustrates one embodiment of a method for treating metal-containing films. [Figure 3] This diagram briefly illustrates one embodiment of a method for treating metal-containing films. [Figure 4A] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4B] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4C] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4D] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4E] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4F] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4G] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4H] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4I] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Figure 4J] This is a cross-sectional view illustrating one embodiment of the trench and via hole pattern formation process for forming bit line electrodes. [Modes for carrying out the invention]

[0015] metal-containing film The metals contained in the aforementioned metal-containing film include alkali metals (e.g., sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.), alkaline earth metals (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.), lanthanide metals (e.g., lanthanum (La), europium (Eu), terbium (Tb), ytterbium (Yb), etc.), and transition metals (e.g., scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr)). This may include, for example, hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), nickel (Ni), copper (Cu), silver (Ag), zinc (Zn), etc., transition metals (e.g., aluminum (Al), gallium (Ga), indium (In), thallium (Tl), tin (Sn), bismuth (Bi), etc.), or any combination thereof.

[0016] According to one embodiment, the metal contained in the metal-containing film includes titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0017] According to another embodiment, the metal-containing film contains two or more different metals.

[0018] According to another embodiment, the metal contained in the metal-containing film is i) Titanium (Ti), and ii) containing indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0019] For example, the metal-containing film may include aluminum, titanium, lanthanum, cobalt, copper, or any combination thereof.

[0020] According to one embodiment, the metal-containing film contains titanium.

[0021] According to another embodiment, the metal-containing film contains cobalt.

[0022] In another embodiment, the metal-containing film contains copper.

[0023] In another embodiment, the metal-containing film includes titanium and cobalt.

[0024] In another embodiment, the metal-containing film includes titanium and copper.

[0025] The metal-containing film may include a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0026] According to one embodiment, the metal-containing film comprises a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, wherein each of the metal, the metal of the metal nitride, the metal of the metal oxide, and the metal of the metal oxynitride comprises titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0027] According to other embodiments, the metal-containing film includes the metal nitride described above.

[0028] In yet another embodiment, the metal-containing film includes the aforementioned metals (for example, at least one of cobalt and copper).

[0029] In yet another embodiment, the metal-containing film comprises a metal nitride and a metal (for example, at least one of cobalt and copper). For example, the metal contained in the metal nitride and the metal are different from each other.

[0030] In yet another embodiment, the metal-containing film comprises a metal nitride and a metal (for example, at least one of cobalt and copper), wherein the metal contained in the metal nitride includes indium, titanium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof.

[0031] In yet another embodiment, the metal-containing film comprises a titanium nitride and a metal (for example, at least one of cobalt and copper), wherein the titanium nitride may further optionally further comprise indium, aluminum, lanthanum, scandium, gallium, hafnium, zinc, tungsten, silicon, or any combination thereof.

[0032] In further embodiments, the metal-containing film includes titanium nitride (TiN), titanium nitride further containing aluminum (e.g., titanium / aluminum nitride (TiAlN)), titanium nitride further containing lanthanum, and the like.

[0033] As yet another example, the metal-containing film includes a metal oxide. The metals included in the metal oxide include titanium, aluminum, lanthanum, scandium, gallium, hafnium, or any combination thereof. For example, the metal-containing film includes aluminum oxide (e.g., Al2O3), IGZO (indium gallium zinc oxide), and the like.

[0034] As yet another example, the metal-containing film includes the metal nitride and the metal oxide.

[0035] As yet another example, the metal-containing film may further contain, in addition to metals, metalloids (e.g., boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), etc.), nonmetals (e.g., nitrogen (N), phosphorus (P), oxygen (O), sulfur (S), selenium (Se), etc.), and any combination thereof.

[0036] For example, the metal-containing film may further contain silicon oxide.

[0037] According to one embodiment, the metal-containing film is a)i) Titanium nitride, or ii) Titanium nitride further comprising indium, aluminum, lanthanum, scandium, gallium, hafnium, zinc, tungsten, silicon, or any combination thereof, and b) Contains at least one of cobalt and copper.

[0038] The metal-containing film is a single-layer structure containing one or more substances, or a multilayer structure containing different substances. The multiple films included in the multilayer structure may be stacked vertically or arranged horizontally. The single-layer and multilayer structures can have a variety of three-dimensional patterns (e.g., via holes, trenches, etc.).

[0039] According to one embodiment, the metal-containing film includes a first region and a second region, and the second etching rate at which the composition etches the second region is greater than the first etching rate at which the composition etches the first region. In a processing step for the metal-containing film (e.g., etching, cleaning, etc.), at least a portion of the first region and at least a portion of the second region are in contact with the composition, and since the second etching rate is greater than the first etching rate, the second region may be etched faster than the first region. According to one embodiment, the first etching rate is 0, and the first region is not etched.

[0040] For example, the first region includes a metal, a metal oxide (e.g., aluminum oxide), a silicon oxide, or any combination thereof.

[0041] According to one embodiment, the first region includes at least one of cobalt and copper.

[0042] As another example, the second region includes metal nitrides (e.g., titanium nitrides).

[0043] As yet another example, the second region includes i) titanium nitride (TiN), ii) titanium nitride (e.g., TiAlN) further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) combinations thereof.

[0044] As yet another example, each of the first and second regions includes i) titanium nitride, ii) titanium nitride further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0045] As yet another example, the first region contains at least one of cobalt and copper, while the second region does not contain cobalt or copper.

[0046] As yet another example, the first region comprises at least one of cobalt and copper, and the second region comprises i) titanium nitride (TiN), ii) titanium nitride (e.g., TiAlN) further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0047] As yet another example, the first region comprises at least one of cobalt and copper, and the second region comprises titanium nitride (TiN), titanium nitride further comprising aluminum (TiAlN), or any combination thereof.

[0048] As yet another example, the first region includes at least one of a cobalt film and a copper film, and the second region includes a titanium nitride film (TiN film), a titanium nitride film further containing aluminum (e.g., a titanium / aluminum nitride film (TiAlN film)), or any combination thereof.

[0049] As yet another example, the first region is a cobalt film, a copper film, or a combination thereof, and the second region is a titanium nitride film (TiN film), or a titanium nitride film further containing aluminum (e.g., a titanium / aluminum nitride film (TiAlN film)).

[0050] In this specification, etching of any film means that some or more of the material constituting the film is removed.

[0051] composition The aforementioned composition may include an oxidizing agent, an ammonium-based buffer, and an etching modifier.

[0052] The above composition can be used in a variety of processing steps for metal-containing films as described herein, such as etching and cleaning steps.

[0053] The aforementioned composition may further contain water.

[0054] According to one embodiment, the composition does not contain an abrasive.

[0055] According to other embodiments, the composition does not contain fluorine (F).

[0056] Oxidizing agent The oxidizing agent plays a role in etching a portion or more of the metal in the metal-containing film by oxidizing a portion or more of the metal to form a water-soluble complex, and may include, for example, at least one of hydrogen peroxide, nitric acid, and ammonium sulfate.

[0057] According to one embodiment, the oxidizing agent includes hydrogen peroxide.

[0058] In other embodiments, the oxidizing agent is hydrogen peroxide.

[0059] The content (weight) of the oxidizing agent is, for example, 16 wt% to 50 wt%, 18 wt% to 50 wt%, 20 wt% to 50 wt%, 22 wt% to 50 wt%, 25 wt% to 50 wt%, 16 wt% to 45 wt%, 18 wt% to 45 wt%, 20 wt% to 45 wt%, 22 wt% to 45 wt%, 25 wt% to 45 wt%, 16 wt% to 40 wt%, 18 wt% to 40 wt%, 20 wt% to 40 wt%, and 22 wt% to 40 wt% per 100 wt% of the composition. The values ​​are 25wt%~40wt%, 16wt%~35wt%, 18wt%~35wt%, 20wt%~35wt%, 22wt%~35wt%, 25wt%~35wt%, 16wt%~30wt%, 18wt%~30wt%, 20wt%~30wt%, 22wt%~30wt%, 25wt%~30wt%, 16wt%~27wt%, 18wt%~27wt%, 20wt%~27wt%, 22wt%~27wt%, or 25wt%~27wt%.

[0060] When the content range of the oxidizing agent satisfies the range described above, the composition can simultaneously have an excellent etching selectivity ratio and excellent cleaning ability.

[0061] Ammonium-based buffer The ammonium-based buffer can play a role in maintaining a high concentration of negative ions generated from the oxidizing agent, and in stabilizing the water-soluble composite formed when the negative ions oxidize a portion or more of the metal in the metal-containing film. By using such an ammonium-based buffer, a portion or more of the metal-containing film can be effectively etched.

[0062] The ammonium-based buffer contains an ammonium group.

[0063] According to one embodiment, the ammonium buffer is N(A 11 )(A 12 )(A 13 )(A 14 It includes a group represented by the A 11 ~A 14 These are, independently of each other, hydrogen, C1-C 30 Alkyl alkyl group, C2-C 30 Alkenyl group, C3-C 30 Carbon ring group, or C1-C 30 It is a heterocyclic group.

[0064] For example, A 11 ~A 14 These are, independently of each other, hydrogen or C1-C 10 It is an alkyl group.

[0065] According to another embodiment, the ammonium-based buffer does not contain fluorine (F). When the ammonium-based buffer does not contain fluorine, the acceleration of surface corrosion of the metal-containing film can be substantially prevented, and the metal-containing film treatment process using the composition can be carried out in a safe and environmentally friendly atmosphere.

[0066] In further embodiments, the ammonium buffer may be a hydroxide, acetate, bicarbonate, benzoate, carbonate, formate, nitrate, hydrogensulfate, carbamate, sulfamate, citrate, phosphate, or sulfide. This includes sulfite, sulfobenzoate, oxalate, lactate, tartrate, dihydrogencitrate, glutamate, salicylate, bioxalate, octanoate, propionate, glycolate, or gluconate. In this specification, the term "phosphate" includes tribasic phosphate, monohydrogen phosphate, dihydrogen phosphate, or a combination thereof.

[0067] In yet another embodiment, the ammonium buffer comprises a phosphate or a hydroxide.

[0068] In another embodiment, the ammonium buffer comprises at least one of the compounds represented by chemical formula 11-1, chemical formula 11-2, chemical formula 11-3, and chemical formula 11-4: [Chemical formula 11-1] [N(A 11 )(A 12 )(A 13 )(A 14 )3PO4 [Chemical formula 11-2] [N(A 11 )(A 12 )(A 13 )(A 14 )]2HPO4 [Chemical formula 11-3] [N(A 11 )(A 12 )(A 13 )(A 14 )]H2PO4 [Chemical formula 11-4] [N(A 11 )(A 12 )(A 13 )(A 14 )]OH In the above chemical formulas 11-1 to 11-4, A 11 ~A 14 The explanations relating to each are the same as those provided in this specification.

[0069] In further embodiments, the ammonium buffer comprises at least one of the following: tribasic ammonium phosphate ((NH4)3PO4), diammonium monohydrogen phosphate ((NH4)2HPO4), ammonium dihydrogen phosphate ((NH4)H2PO4), [N(CH3)4]3PO4, bis(tetramethylammonium) monohydrogen phosphate ([N(CH3)4]2HPO4), tetramethylammonium dihydrogen phosphate ([N(CH3)4]H2PO4), and ammonium hydroxide.

[0070] The content (weight) of the ammonium-based buffer is, for example, per 100 wt% of the composition: 0.01 wt% to 10 wt%, 0.05 wt% to 10 wt%, 0.1 wt% to 10 wt%, 0.3 wt% to 10 wt%, 0.5 wt% to 10 wt%, 0.01 wt% to 7 wt%, 0.05 wt% to 7 wt%, 0.1 wt% to 7 wt%, 0.3 wt% to 7 wt%, 0.5 wt% to 7 wt%, 0.01 wt% to 4 wt%, 0.05 wt% to 4 wt%, 0.1 wt% to 4 wt%, 0.3 wt% to 4 wt%, 0.5 wt% to 4 wt%, 0.01 wt% to 2 wt%, 0. The values ​​are 0.5wt%~2wt%, 0.1wt%~2wt%, 0.3wt%~2wt%, 0.5wt%~2wt%, 0.01wt%~1wt%, 0.05wt%~1wt%, 0.1wt%~1wt%, 0.3wt%~1wt%, 0.5wt%~1wt%, 0.01wt%~0.7wt%, 0.05wt%~0.7wt%, 0.1wt%~0.7wt%, 0.3wt%~0.7wt%, 0.5wt%~0.7wt%, 0.01wt%~0.5wt%, 0.05wt%~0.5wt%, 0.1wt%~0.5wt%, or 0.3wt%~0.5wt%.

[0071] When the content range of the ammonium buffer satisfies the range described above, the composition can simultaneously have an excellent etching selectivity ratio and excellent cleaning ability.

[0072] Etching modifier The etching modifier can interact with various metal atoms in the metal-containing film being processed, thereby regulating the etching rate and other parameters. Furthermore, the etching modifier can remove residues generated during the metal-containing film deposition process and / or patterning process.

[0073] The etching modifier includes a compound represented by the following chemical formula 1: [ka]

[0074] In the aforementioned chemical formula 1, R1 is C12 -C 50 Alkyl or C 12 -C 50 It is an alkenyl group, R2 is hydrogen, C1-C 50 Alkyl group, or C2-C 50 It is an alkenyl group, L1 is C1-C 20 It is an alkylene group, T1 is a linking group represented by one of the chemical formulas 2(1) to 2(3), [ka]

[0075] The aforementioned X is hydrogen, an alkali metal, or an ammonium group. At least one of the methylene groups in R1 and R2 is optionally substituted with O or S. At least one of the hydrogen atoms contained in R1, R2, and L1 is selectively a halogen atom, C1-C 30 Alkoxy group, or C1-C 30 Substituted with alkylthio groups, In the above chemical formulas 2(1) to 2(3), * is the binding site with L1, and *' is, In chemical formula 1, O - This is the bonding site with . In chemical formula 2(3), O - This refers to monovalent cations present in the composition, for example, H + It can be combined with this.

[0076] In the above chemical formula 1, O -Since the nitrogen (N) of the amide can form a strong bond (see "2a" in chemical formula 1') with the metal M (e.g., cobalt, copper, etc.) contained in the metal-containing film 2, the compound represented by chemical formula 1 can be effectively fixed to the surface of the metal-containing film 2. Furthermore, since R1 as defined above (see "2b" in chemical formula 1') is a hydrophobic group with a relatively long chain, the compound represented by chemical formula 1 can provide a hydrophobic protective film on the surface of the metal-containing film 2. Therefore, by using a composition containing the compound represented by chemical formula 1, the etching rate can be selectively adjusted by the metal of the metal-containing film, and at the same time, residues generated during the metal-containing film deposition process and / or patterning process can be effectively removed.

[0077] [ka]

[0078] According to one embodiment, in the chemical formula 1, R1 is 1) C 12 -C 30 Alkyl or C 12 -C 30 Is it an alkenyl group? 2) C 12 -C 20 Alkyl or C 12 -C 20 Is it an alkenyl group? 3) C 12 -C 17 Alkyl or C 12 -C 17 Is it an alkenyl group? 4) C 13 -C 50 Alkyl or C 13 -C 50 Is it an alkenyl group? 5) C 13 -C 30 Alkyl or C 13 -C 30 Is it an alkenyl group? 6) C 13 -C20 an alkyl group or C 13 -C 20 is an alkenyl group, or 7)C 13 -C 17 an alkyl group or C 13 -C 17 is an alkenyl group, or 8)C 15 -C 50 an alkyl group or C 15 -C 50 is an alkenyl group, or 9)C 15 -C 30 an alkyl group or C 15 -C 30 is an alkenyl group, or[[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ iv) It is a C1 alkylene group (methylene group).

[0081] In another embodiment, in chemical formula 1, T1 is a linking group represented by chemical formula 2(1).

[0082] In another embodiment, in the chemical formula 1, X is hydrogen, Na, K, or N(A1)(A2)(A3)(A4), and A1 to A4 are independently hydrogen, C1-C 30 Alkyl alkyl group, C2-C 30 Alkenyl group, C3-C 30 Carbon ring group, or C1-C 30 It is a heterocyclic group. For example, A1 to A4 are independently of each other, either hydrogen or C1-C 10 It is an alkyl group.

[0083] In another embodiment, in the chemical formula 1, at least one of the methylene groups contained in R1 and R2 (for example, one or two methylene groups) is optionally substituted with O or S.

[0084] In further embodiments, in the chemical formula 1, at least one of the hydrogen atoms contained in R1, R2, and L1 is selectively a halogen atom (e.g., -F, -Cl, -Br, etc.), C1-C 30 Alkoxy groups (e.g., C1-C 10 Alkoxy group), or C1-C 30 Alkylthio group (e.g., C1-C 10 It is substituted with an alkylthio group.

[0085] In another embodiment, the etching modifier comprises at least one of the following compounds 1 to 4: [ka]

[0086] Furthermore, according to other embodiments, the content of the etching modifier is, per 100 wt% of the composition, 0.001 wt% to 10 wt%, 0.01 wt% to 10 wt%, 0.1 wt% to 10 wt%, 0.2 wt% to 10 wt%, 0.001 wt% to 5 wt%, 0.01 wt% to 5 wt%, 0.1 wt% to 5 wt%, 0.2 wt% to 5 wt%, and 0.001 wt%~1wt%, 0.01wt%~1wt%, 0.1wt%~1wt%, 0.2wt%~1wt%, 0.001wt%~0.5wt%, 0.01wt%~0.5wt%, 0.1wt%~0.5wt%, 0.2wt%~0.5wt%, 0.001wt%~0.2wt%, 0.01wt%~0.2wt%, or 0.1wt%~0.2wt%.

[0087] The pH of the compositions described above is 1.0-10.0, 3.0-10.0, 5.0-10.0, 7.0-10.0, 3.0-8.0, 5.0-8.0, or 7.0-8.0. Having a pH within the above range allows for smoother interaction between the etching modifier and the metal atoms in the metal-containing film, as described later.

[0088] According to one embodiment, the composition can be used in metal-containing film processing steps, such as etching and cleaning steps for metal-containing films. A description of the metal-containing film is provided herein.

[0089] Alternatively, the composition can be used as an etching by-product remover, a post-etch by-product remover, an ashing by-product remover, a cleaning composition, a photoresist (PR) remover, an etching composition for the packaging process, a cleaning agent for the packaging process, a wafer adhesive remover, an etchant, a post-etch residue stripper, an ashing residue cleaner, a photoresist residue stripper, or a post-CMP cleaner.

[0090] Method for processing metal-containing films and method for manufacturing semiconductor devices Metal-containing films can be effectively treated using the compositions described above.

[0091] Referring to Figure 1, one embodiment of the method for processing the metal-containing film includes the steps of preparing a substrate to which the metal-containing film is provided (S100) and bringing the metal-containing film into contact with a composition as described herein (S110).

[0092] For a description of the aforementioned metal-containing film, please refer to the one provided in this specification.

[0093] For example, the metals contained in the metal-containing film include titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0094] As yet another example, the metal-containing film includes a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof.

[0095] As yet another example, the metal-containing film comprises a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof, wherein each of the metal, the metal of the metal nitride, the metal of the metal oxide, and the metal of the metal oxynitride includes titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

[0096] As yet another example, the metal-containing film includes titanium nitride.

[0097] As yet another example, the metal-containing film includes at least one of cobalt and copper.

[0098] According to one embodiment, a portion or more of the metal-containing film may be etched and cleaned during the contact step between the metal-containing film and the composition.

[0099] In the above composition, i) the oxidizing agent plays the role of etching a portion or more of the metal-containing film by oxidizing a portion or more of the metal in the metal-containing film to form a water-soluble composite, ii) the ammonium buffer plays the role of maintaining a high concentration of negative ions generated from the oxidizing agent and stabilizing the water-soluble composite formed by the oxidation of a portion or more of the metal in the metal-containing film by the negative ions, thereby effectively etching a portion or more of the metal-containing film, iii) O - An etching modifier containing a compound represented by chemical formula 1, in which the nitrogen (N) of the amide can strongly bond with the metal contained in the metal-containing film (e.g., cobalt, copper, etc.), and which has a relatively long-chain hydrophobic group R1, can selectively adjust the etching rate depending on the metal of the metal-containing film, and at the same time, can effectively remove residues generated during the metal-containing film deposition process and / or patterning process. Therefore, such compositions can be usefully used in a variety of processing steps for the metal-containing film.

[0100] Figures 2 and 3 are diagrams that briefly illustrate one embodiment of a method for treating a metal-containing film.

[0101] Referring to Figure 2, a substrate 10 is provided on which a metal-containing film 20 is provided. An intermediate layer 11 is placed between the substrate 10 and the metal-containing film 20. Although not shown in Figure 2, circuit elements (e.g., transistor gates, metal lines, impurity regions, semiconductor layers) may be placed inside the substrate 10, on top of the substrate 10, and / or between the substrate 10 and the intermediate layer 11. In one embodiment, the metal-containing film 20 is placed directly on the substrate 10, and the intermediate layer 11 may be omitted.

[0102] The metal-containing film 20 includes a first region 21 and a second region 22. The first region 21 and the second region 22 may be spaced apart from each other, or some or more of them may be in contact with each other, and the metal-containing film 20 can have a variety of three-dimensional patterns. The second etching rate at which the composition etches the second region 22 is greater than the first etching rate at which the composition etches the first region 21. For example, the first etching rate is 0, and the first region 21 is not etched.

[0103] Referring to Figure 3, the composition can be used to etch the metal-containing film 20 to etch a portion or more of the second region 22 and form a metal-containing film pattern (a pattern of the metal-containing layer) 25. This step is carried out by bringing a portion or more of the first region 21 and a portion or more of the second region 22 into contact with the composition.

[0104] The composition etches only a portion or more of the second region 22 without etching the first region 21. Alternatively, the composition etches a portion or more of the first region 21 and a portion or more of the second region 22, respectively. In Figure 3, the metal-containing film pattern 25 formed after etching includes a portion or more of the second region 22, but various modifications are possible, such as performing the etching process to completely remove the second region 22 in the metal-containing film pattern 25 when necessary.

[0105] According to another embodiment, the first region 21 includes at least one of cobalt and copper.

[0106] In yet another embodiment, the second region 22 includes a metal nitride (for example, titanium nitride).

[0107] In further embodiments, the second region 22 includes i) titanium nitride (TiN), ii) titanium nitride (e.g., TiAlN) further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0108] In further embodiments, each of the first region 21 and the second region 22 comprises i) titanium nitride, ii) titanium nitride further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0109] As yet another example, the first region 21 contains at least one of cobalt and copper, while the second region 22 does not contain cobalt or copper.

[0110] As yet another example, the first region 21 comprises at least one of cobalt and copper, and the second region 22 comprises i) titanium nitride (TiN), ii) titanium nitride (e.g., TiAlN) further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof.

[0111] As yet another example, the first region 21 includes at least one of cobalt and copper, and the second region 22 includes titanium nitride (TiN), titanium nitride further containing aluminum (TiAlN), or any combination thereof.

[0112] As yet another example, the first region 21 includes at least one of a cobalt film and a copper film, and the second region 22 includes a titanium nitride film (TiN film), a titanium nitride film further containing aluminum (e.g., a titanium / aluminum nitride film (TiAlN film)), or any combination thereof.

[0113] As yet another example, the first region 21 is a cobalt film, and the second region 22 is a titanium nitride film (TiN film), or a titanium nitride film further containing aluminum (e.g., a titanium / aluminum nitride film (TiAlN film)).

[0114] As yet another example, the first region 21 is a copper film, and the second region 22 is a titanium nitride film (TiN film), or a titanium nitride film further containing aluminum (e.g., a titanium / aluminum nitride film (TiAlN film)).

[0115] As yet another example, the contact step between the metal-containing film 20 and the composition removes the residue R on the surface of the metal-containing film 20, thereby cleaning a portion or more of the metal-containing film 20 and forming a metal-containing film pattern 25 without any residue R remaining, as shown in Figure 3.

[0116] The residue R is a by-product generated during the deposition and / or patterning of the metal-containing film 20, and is a substance that remains on the surface of the metal-containing film 20 and / or the metal-containing film pattern 25, causing increased electrical resistance and / or electrical short circuits between electrical wiring. The residue R is also an etching residue generated as a result of etching, and includes, for example, etching gas residue, polymer residue, metal-containing residue, or any combination thereof.

[0117] The etching gas residue is a residue derived from the etching gas used in dry etching. The etching gas is, for example, carbon fluoride gas. For example, the etching gas includes CHF3, C2F6, CF4, C4F8, C2HF5, etc. The etching gas residue may include the etching gas itself and / or the reaction products of any substance that came into contact with the etching gas during the etching process using the etching gas.

[0118] The polymer residue is a polymer derived from various organic materials contained in the photoresist, dielectric layer, buffer layer, diffusion barrier layer, etc., used during the fabrication and / or patterning of the metal-containing film 20. For example, the polymer residue is a polymer containing carbon, silicon, fluorine, or any combination thereof.

[0119] The metal-containing residue is any residue containing metal that is separated from the metal-containing film during the production and / or patterning of the metal-containing film 20.

[0120] Referring to Figure 1, a method for manufacturing a semiconductor device according to one embodiment includes the steps of: preparing a substrate provided with a metal-containing film (S100); bringing the metal-containing film into contact with the composition (S110); and carrying out subsequent steps to manufacture a semiconductor device (S120).

[0121] For example, the steps of preparing a substrate to which the metal-containing film is provided (S100) and bringing the metal-containing film into contact with the composition (S110) are used in the trench and via hole pattern formation steps for forming bit line electrodes in the semiconductor device manufacturing method.

[0122] Hereinafter, with reference to Figures 4A to 4J, an embodiment of the trench and via hole pattern formation process for forming bit line electrodes using the above composition will be described.

[0123] Figure 4A shows a portion of a semiconductor substrate (transistors and the like are not shown) including a first dielectric layer 103 and a metal layer 101. The metal layer 101 includes, for example, at least one of copper and cobalt. A first diffusion barrier layer 105 is disposed between the first dielectric layer 103 and the metal layer 101. The first diffusion barrier layer 105 includes, for example, tantalum, titanium, tungsten, tantalum nitride, titanium nitride, tungsten nitride, or any combination thereof.

[0124] A second diffusion barrier layer 107 is placed on the first dielectric layer 103 and the metal layer 101 in Figure 4A. The second diffusion barrier layer 107 includes, for example, silicon nitride, nitrogen-doped silicon carbide, or aluminum oxide.

[0125] A second dielectric layer 109 is placed on the second diffusion barrier layer 107 in Figure 4A. The second dielectric layer 109 includes, for example, an ULK (ultra-low K) dielectric or a silicon oxide.

[0126] On the second dielectric layer 109 in Figure 4A, a mechanically robust buffer layer 111 is placed to prevent damage to the second dielectric layer 109 during the deposition of the hard mask layer 113. The buffer layer 111 includes, for example, tetraethyl orthosilicate (TEOS) or carbon-doped silicon oxide (SiCOH).

[0127] A hard mask layer 113 is placed on the buffer layer 111 in Figure 4A. The hard mask layer 113 comprises i) titanium nitride (TiN), ii) titanium nitride (e.g., TiAlN) further comprising indium, aluminum, lanthanum, scandium, gallium, zinc, hafnium, or any combination thereof, or iii) a combination thereof. For example, the hard mask layer 113 contains TiN.

[0128] A first photoresist 115 is placed on the hard mask layer 113 in Figure 4A.

[0129] Next, the first photoresist 115 is patterned to form a pattern of the first photoresist 115 having a first opening with a width t as shown in Figure 4B. Then, the hard mask layer 113 is etched by the pattern of the first photoresist 115 to open a portion of the buffer layer 111 as shown in Figure 4C. After that, for example, using ashing, the pattern of the first photoresist 115 is removed as shown in Figure 4D to form a pattern of the exposed hard mask layer 113.

[0130] Next, as shown in Figure 4E, a filler layer 117 is formed to cover the pattern of the hard mask layer 113, filling the openings in the pattern of the hard mask layer 113. The filler layer 117 includes, for example, hydrogen silsesquioxane (HSQ) or methylsilsesquioxane (MSQ).

[0131] Next, as shown in Figure 4F, a second photoresist 119 is formed on top of the filler layer 117, and then the second photoresist 119 is patterned to form a pattern of the second photoresist 119 having a second opening with width v, as shown in Figure 4G. Then, for example, using RIE (Reactive Ion Etching), the filler layer 117, a portion of the pattern of the hard mask layer 113, a portion of the buffer layer 111, and a portion of the second dielectric layer 109 located below the pattern of the second photoresist 119 are etched to partially form via holes, as shown in Figure 4H, and then the pattern of the second photoresist 119 and the filler layer 117 are removed.

[0132] Next, as shown in Figure 4I, the buffer layer 111, the second dielectric layer 109, and the second diffusion barrier layer 107 are etched using, for example, a dry etching process, according to the pattern of the hard mask layer 113, until the via holes reach the metal layer 101, thereby forming trenches and via hole patterns. The etching gas used in the dry etching process is, for example, carbon fluoride gas (e.g., CHF3, C2F6, CF4, C4F8, C2HF5, etc.).

[0133] As a result of the dry etching described above, as shown in Figure 4I, a large amount of residue R may be present on the inner walls of the trench and via hole patterns. The residue R includes etching gas residue, polymer residue, metal-containing residue, or any combination thereof. The etching gas residue includes the reaction product with the etching gas itself and / or any substance that came into contact with the etching gas during the etching process using the etching gas (e.g., substances contained in the buffer layer 111, the second dielectric layer 109, etc.). The polymer residue is a polymer derived from various organic substances contained in the second photoresist 119, the second dielectric layer 109, the buffer layer 111, the second diffusion barrier layer 107, etc. For example, the polymer residue is a polymer containing carbon, silicon, fluorine, or any combination thereof. The metal-containing residue is, for example, a residue containing metal contained in the pattern of the hard mask layer 113.

[0134] The residue R in Figure 4I must be removed because it increases the electrical resistance of the semiconductor device or causes an electrical short circuit in the bit line electrodes that are formed later. On the other hand, for the sake of process simplification, the residue R and the pattern of the hard mask layer 113 must be removed simultaneously. Furthermore, the metal layer 101 must not be substantially damaged when removing the residue R and the pattern of the hard mask layer 113.

[0135] To this end, by bringing a composition containing the aforementioned oxidizing agent, ammonium-based buffer, and etching modifier into contact with the substrate of Figure 4I, which includes a hard mask layer 113 pattern and a metal-containing film including the metal layer 101, the substrate of Figure 4J can be fabricated in which i) residue R generated on the inner walls of the trench and via hole patterns is removed, ii) the pattern of the hard mask layer 113 is removed, and iii) the metal layer 101 is not substantially damaged. Although not limited by any particular theory, for example, the pattern of the hard mask layer 113 is removed by the oxidizing agent and ammonium-based buffer, and the residue R is removed by the etching modifier, while at the same time, the metal layer 101 is not substantially etched. Then, by filling the trench and via hole patterns of Figure 4J with a metallic substance, bit line electrodes and the like can be formed.

[0136] Examples 1 and 2, Comparative Examples 1 to 4 and 6 The substances listed in Table 1 were weighed according to Table 1 and mixed to produce the compositions of Examples 1 and 2, and Comparative Examples 1 to 4 and 6, as oxidizing agents, buffering agents, and etching modifiers. The remainder of each composition is water (deionized water).

[0137] Comparative Example 5 The substances listed in Table 1 were weighed according to Table 1 as oxidizing agents and buffers, and then mixed to produce the composition of Comparative Example 5. The remainder of each composition is water (deionized water).

[0138] Evaluation Example 1 The composition of Example 1 was placed in three separate beakers and heated to 50°C. The plasma-etched copper film, cobalt film, and titanium nitride film were then immersed in the respective beakers for 10 minutes, 5 minutes, and 0.5 minutes, respectively. The thicknesses of the copper and cobalt films were measured using XRF (X-Ray Fluorescence Spectrometry) (S8 Tiger, BRUKER), and the thickness of the titanium nitride film was measured using an ellipsometer (M-2000, JAWoolam). The etching rates of the composition of Example 1 for the copper film (hereinafter referred to as "Cu film etching rate") (Å / min), the etching rate for the cobalt film (hereinafter referred to as "Co film etching rate") (Å / min), and the etching rate for the titanium nitride film (hereinafter referred to as "TiN film etching rate") (Å / min) were evaluated. Next, the etching rate of the TiN film was divided by the etching rate of the Cu film to evaluate R(TiN / Cu), and the etching rate of the TiN film was divided by the etching rate of the Co film to evaluate R(TiN / Co). The results were then summarized in Table 1.

[0139] The above tests were repeated using each of the compositions from Example 2 and Comparative Examples 1 to 6, and the results are summarized in Table 1.

[0140] Next, a substrate containing the composition of Example 1 (25°C) was immersed in a dip-type bath in which trenches and via hole patterns for forming bit line electrodes were formed, and which had residue present on the inner walls of the trenches and via hole patterns for 5 minutes. After rinsing and drying, the residue removal status was evaluated by AFM (Atomic Force Microscopy) topography analysis, and the results are summarized in Table 1. The substrate is a substrate in which trenches and via hole patterns as shown in Figure 4I were formed. Of the substrate, the metal layer 101 contains copper, the second dielectric layer 109 contains silicon oxide, the hard mask layer 113 contains titanium nitride, the buffer layer 111 contains carbon-doped silicon oxide, the second diffusion barrier layer 107 contains aluminum oxide, and the etching gas used in the dry etching process was CF4.

[0141] The above tests were repeated using each of the compositions from Example 2 and Comparative Examples 1 to 6, and the results are summarized in Table 1.

[0142] [Table 1] [ka]

[0143] Table 1 confirms that the compositions of Examples 1 and 2 exhibit higher etching selectivity between the titanium nitride film and the copper film, and between the titanium nitride film and the cobalt film, compared to the compositions of Comparative Examples 1 to 6. At the same time, it can be confirmed that they have excellent removal performance for residues generated during the metal-containing film deposition process and / or patterning process.

Claims

1. It comprises an oxidizing agent, an ammonium-based buffer, and an etching controller. The content of the oxidizing agent is 16 wt% to 50 wt% per 100 wt% of the composition. The etching modifier comprises a compound represented by chemical formula 1, and is a composition: 【Chemistry 1】 In the aforementioned chemical formula 1, R １ is C １２ -C ５０ Alkyl or C １２ -C ５０ It is an alkenyl group, R ２ is hydrogen, C １ -C ５０ -alkyl group, or C ２ -C ５０ -alkenyl group, and L １ is C １ -C ２０ It is an alkylene group, T １ is a linking group represented by one of the chemical formulas 2(1) to 2(3), 【Chemistry 2】 The aforementioned X is hydrogen, an alkali metal, or an ammonium group. The aforementioned R １ and R ２ At least one of the methylene groups contained therein is optionally substituted with O or S. The aforementioned R １ , R ２ and L １ At least one of the hydrogen atoms contained in is selectively a halogen atom, C １ -C ３０ Alkoxy group, or C １ -C ３０ Substituted with alkylthio groups, In the above chemical formulas 2(1) to 2(3), * represents L １ It is a junction site with, and *' is O － This is a linked site.

2. The composition according to claim 1, wherein the oxidizing agent comprises hydrogen peroxide.

3. The composition according to claim 1, wherein the content of the oxidizing agent is 20 wt% to 30 wt% per 100 wt% of the composition.

4. The ammonium buffer is N(A) １１ ) (A １２ ) (A １３ ) (A １４ It includes a group represented by ), A １１ ~A １４ These are, independently of each other, hydrogen and C １ -C ３０ Alkyl alkyl group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Carbon ring group, or C １ -C ３０ The composition according to claim 1, wherein the group is a heterocyclic group.

5. The composition according to claim 1, wherein the ammonium buffer does not contain fluorine (F).

6. The composition according to claim 1, wherein the ammonium buffer comprises a hydroxide, acetate, bicarbonate, benzoate, carbonate, formate, nitrate, hydrogensulfate, carbamate, sulfamate, citrate, phosphate, sulfite, sulfobenzoate, oxalate, lactate, tartrate, dihydrogencitrate, glutamate, salicylate, bioxalate, octanoate, propionate, glycolate, or gluconate.

7. The composition according to claim 1, wherein the ammonium buffer comprises at least one of the compounds represented by chemical formula 11-1, chemical formula 11-2, chemical formula 11-3, and chemical formula 11-4: [Chemical formula 11-1] [N(A １１ )(A １２ )(A １３ )(A １４ )] ３ PO ４ [Chemical formula 11-2] [N(A １１ )(A １２ )(A １３ )(A １４ )] ２ @OO ４ [Chemical formula 11-3] [N(A １１ )(A １２ )(A １３ )(A １４ )]H ２ PO ４ [Chemical formula 11-4] [N(A １１ )(A １２ )(A １３ )(A １４ )]OH In the above chemical formulas 11-1 to 11-4, A １１ ~A １４ These are, independently of each other, hydrogen and C １ -C ３０ Alkyl alkyl group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Carbon ring group, or C １ -C ３０ It is a heterocyclic group.

8. The composition according to claim 1, wherein the content of the ammonium buffer is 0.01 wt% to 10 wt% per 100 wt% of the composition.

9. The composition according to claim 1, wherein the content of the ammonium buffer is 0.01 wt% to 4 wt% per 100 wt% of the composition.

10. In the above chemical formula 1, R １ is C １３ -C ２０ Alkyl or C １３ -C ２０ The composition according to claim 1, wherein the group is an alkenyl group.

11. In the above chemical formula 1, L １ is C １ -C ４ The composition according to claim 1, wherein the group is alkylene.

12. The composition according to claim 1, wherein the content of the etching modifier is 0.001 wt% to 10 wt% per 100 wt% of the composition.

13. The steps include preparing a substrate to which a metal-containing film is provided, A method for treating a metal-containing film, comprising the step of bringing the metal-containing film into contact with the composition described in any one of claims 1 to 12.

14. The method for treating a metal-containing film according to claim 13, wherein the metal contained in the metal-containing film includes titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

15. The metal-containing film comprises a metal, a metal nitride, a metal oxide, a metal oxynitride, or any combination thereof. A method for treating a metal-containing film according to claim 13, wherein each of the metal, the metal nitride, the metal oxide, and the metal oxynitride includes titanium (Ti), indium (In), aluminum (Al), cobalt (Co), lanthanum (La), scandium (Sc), gallium (Ga), tungsten (W), molybdenum (Mo), ruthenium (Ru), zinc (Zn), hafnium (Hf), copper (Cu), or any combination thereof.

16. The method for treating a metal-containing film according to claim 13, wherein a portion or more of the metal-containing film is etched or cleaned during the contact step between the metal-containing film and the composition.

17. The metal-containing film comprises a first region and a second region. The method for treating a metal-containing film according to claim 13, wherein the second etching rate at which the composition etches the second region is greater than the first etching rate at which the composition etches the first region.

18. The method for treating a metal-containing film according to claim 17, wherein the first region contains at least one of cobalt and copper, and the second region contains titanium nitride.

19. During the contact step between the metal-containing film and the composition, residues on the surface of the metal-containing film are removed, thereby cleaning a portion or more of the metal-containing film. The method for treating a metal-containing film according to claim 13, wherein the residue includes etching gas residue, polymer residue, metal-containing residue, or any combination thereof.

20. The steps include preparing a substrate to which a metal-containing film is provided, A step of bringing the metal-containing film into contact with the composition according to any one of claims 1 to 12, A method for manufacturing a semiconductor device, comprising the step of carrying out subsequent manufacturing processes to produce a semiconductor device.

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