Polishing slurry and method of manufacturing semiconductor device

Abstract

Disclosed are a polishing slurry and a method of manufacturing a semiconductor device using the same, the polishing slurry including a first histidine derivative including an abrasive, an oxidizing agent, and a substituted or unsubstituted cyclic imide group.

Description

[0001] Cross-reference to related applications

[0002] This application is based on and claims priority to Korean Patent Application Nos. 10-2024-0167456 and 10-2025-0168734, filed with the Korean Intellectual Property Office on November 21, 2024 and November 10, 2025, respectively, the contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to polishing slurries and methods for manufacturing semiconductor devices. Background Technology

[0004] Recently, due to the miniaturization of electronic devices and subsequently integrated circuits, various methods for forming microstructures such as metal lines with widths of a few nanometers, contact holes, or shallow trench isolation have been studied.

[0005] In forming such microstructures, polishing processes can be performed to make the surface of the microstructures flat and smooth, and chemical mechanical polishing (CMP) is one such polishing process. Chemical mechanical polishing is a process in which a polishing slurry comprising an abrasive is provided between a semiconductor substrate, which includes the object to be polished, and a polishing pad to planarize the surface of the semiconductor substrate. Summary of the Invention

[0006] To improve the performance of chemical mechanical polishing, it may be necessary to increase the polishing rate of the object to be polished, such as metal, while reducing or preventing losses or defects in the object to be polished, such as dishing, which may be caused by corrosion or over-etching.

[0007] One embodiment provides a polishing slurry that can remove the object to be polished at a high polishing rate and reduce or prevent loss or defects in the object to be polished due to excessive corrosion or etching.

[0008] Another embodiment provides a method for manufacturing semiconductor devices using the polishing slurry.

[0009] According to one embodiment, the polishing slurry includes an abrasive, an oxidizing agent, and a first histidine derivative containing substituted or unsubstituted cyclic imide groups.

[0010] The first histidine derivative can be represented by chemical formula 1-1.

[0011]

[0012] In chemical formula 1-1,

[0013] X 1It can be a substituted or unsubstituted cyclic imide group.

[0014] R 1 R 2a R 2b R 3a and R 3b Each of these groups can independently be hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano, and

[0015] R 1 R 2a R 2b R 3a and R 3b They can exist independently or two adjacent ones can combine (bond) to form a ring.

[0016] X 1 It can be represented by any one of the chemical formulas A to C.

[0017]

[0018] In chemical formulas A to C,

[0019] R 4 To R 9 Each of these can be independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano.

[0020] R 4 To R 9 They can exist independently, or two adjacent ones can combine to form a ring.

[0021] n can be an integer from 1 to 5, and

[0022] *This can be a connection point with chemical formula 1-1.

[0023] X 1 It can be represented by any one of the chemical formulas B-1 to B-5.

[0024]

[0025] In chemical formulas B-1 to B-5,

[0026] R 4a R 5 R6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b Each of these can be independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano.

[0027] R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b They can exist independently, or two adjacent ones can combine to form a ring.

[0028] m can be an integer from 0 to 5, and

[0029] *This can be a connection point with chemical formula 1-1.

[0030] The polishing slurry may further include a second histidine derivative comprising substituted or unsubstituted ammonium acid groups.

[0031] The second histidine derivative can be represented by chemical formula 1-2.

[0032]

[0033] In chemical formulas 1-2,

[0034] X 2It can be a substituted or unsubstituted amyl acid group.

[0035] R 1 R 2a R 2b R 3a and R 3b Each of these groups can independently be hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano, and

[0036] R 1 R 2a R 2b R 3a and R 3b They can exist independently, or two adjacent ones can combine to form a ring. X 2 It can be represented by any of the chemical formulas D to F.

[0037]

[0038] In chemical formulas D to F,

[0039] R 4 To R 9 Each of these can be independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano.

[0040] R 4 To R 9 They can exist independently, or two adjacent ones can combine to form a ring.

[0041] n can be an integer from 1 to 5, and

[0042] *This can be a connection point with chemical formulas 1-2.

[0043] X 2 It can be represented by any one of the chemical formulas E-1 to E-5.

[0044]

[0045] In chemical formulas E-1 to E-5

[0046] R 4a R 5 R 6 R 7 R 7aR 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b Each of these can be independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano.

[0047] R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b They can exist independently, or two adjacent ones can combine to form a ring.

[0048] m can be an integer from 0 to 5, and

[0049] *This can be a connection point with chemical formulas 1-2.

[0050] The first histidine derivative may be represented by chemical formula 1-1, and the polishing slurry may further include a second histidine derivative represented by chemical formula 1-2.

[0051] Abrasives may include oxide abrasives, nitride abrasives, carbon abrasives, or combinations thereof.

[0052] Abrasives may include silicon dioxide, cerium dioxide, aluminum oxide, zirconium oxide, titanium dioxide, or combinations thereof.

[0053] The polishing slurry may further include a dispersion medium, and based on the polishing slurry, may include an abrasive in an amount from about 0.001% by weight to about 20% by weight.

[0054] Oxidizing agents may include hydrogen peroxide, peracetic acid, percarbonate, urea peroxide, perchloric acid, persulfate, or combinations thereof.

[0055] The oxidant and the first histidine derivative may be included in the polishing slurry in a molar ratio of about 0.01:10 to about 10:0.01.

[0056] The polishing slurry may further include a dispersion medium, and based on the polishing slurry, may each include an oxidant and a first histidine derivative in amounts of about 0.001% to about 5% by weight.

[0057] The pH of the polishing slurry can be from about 1.0 to about 10.0.

[0058] Polishing slurry may further include chelating agents, surfactants, dispersants, pH adjusters, dispersion media, or combinations thereof.

[0059] According to another embodiment, a method of manufacturing a semiconductor device includes forming a conductive layer on an insulating layer having openings, supplying a polishing slurry on the conductive layer, and chemically and mechanically polishing the conductive layer to form embedded conductive patterns in the openings of the insulating layer, wherein the polishing slurry includes an abrasive, an oxidant, and a first histidine derivative comprising substituted or unsubstituted cyclic imide groups.

[0060] The first histidine derivative can be represented by chemical formula 1-1.

[0061] In chemical formula 1-1, X 1 It can be represented by any one of the chemical formulas A to C.

[0062] In chemical formula 1-1, X 1 It can be represented by any one of the chemical formulas B-1 to B-5.

[0063] The polishing slurry may further include a second histidine derivative comprising substituted or unsubstituted ammonium acid groups.

[0064] The second histidine derivative can be represented by chemical formula 1-2.

[0065] In chemical formula 1-2, X 2 It can be represented by any of the chemical formulas D to F.

[0066] In chemical formula 1-2, X 2 It can be represented by any one of the chemical formulas E-1 to E-5.

[0067] The conductive layer may include a molybdenum-containing layer.

[0068] The removal rate of the molybdenum-containing layer can be greater than or equal to about 110 Å / min, and the static etching rate of the molybdenum-containing layer can be less than about 80 Å / min.

[0069] The ratio of the removal rate of the molybdenum-containing layer to the static etching rate can be greater than or equal to about 3.

[0070] According to another embodiment, a compound represented by chemical formula 1-1 is provided.

[0071] According to another embodiment, a compound represented by chemical formulas 1-2 is provided.

[0072] It can remove the object to be polished at a high polishing rate, while effectively reducing or preventing loss or defects in the object to be polished caused by excessive corrosion or etching. Attached Figure Description

[0073] Figures 1 to 4 This is a cross-sectional view illustrating an example of a method for manufacturing a semiconductor device according to an embodiment.

[0074] Figure 5 This is a schematic diagram illustrating a chemical mechanical polishing apparatus according to an example.

[0075] Figure 6 This is a graph showing the polishing rate and etching rate of the molybdenum layer using polishing slurries according to the preparation examples and comparative examples.

[0076] Figure 7 This is a graph showing the ratio of polishing rate to etching rate of the molybdenum layer using polishing slurries according to the preparation examples and comparative examples. Detailed Implementation

[0077] Example implementations will be described in detail below and can be readily performed by those skilled in the art. However, this disclosure may be embodied in many different forms and is not to be construed as limited to the exemplary implementations set forth herein.

[0078] In the accompanying drawings, the thickness of layers, films, panels, regions, etc., is exaggerated for clarity. Throughout the specification, the same reference numerals denote the same elements. It will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it may be directly on said other element, or there may be intermediate elements present. Conversely, when an element is referred to as being "directly on" another element, there are no intermediate elements present.

[0079] As used herein, unless otherwise defined, 'substituted' means that the hydrogen atom of a compound or group is replaced by a substituent selected from the following: halogen atom, hydroxyl, nitro, cyano, amino, azide, amido, hydrazine, hydrazone, carbonyl, carbamoyl, thiol, ester, carboxyl or a salt thereof, sulfonic acid or a salt thereof, phosphate or a salt thereof, silyl, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C7 to C30 arylalkyl, C1 to C30 alkoxy, C1 to C20 heteroalkyl, C3 to C20 heteroaryl, C3 to C20 heteroarylalkyl, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C3 to C30 heterocycloalkyl, and combinations thereof.

[0080] As used herein, unless otherwise defined, 'heterogeneous' means 1 to 4 heteroatoms selected from N, O, S, Se, Te, Si, and P.

[0081] In the following text, the term 'combination' includes mixtures and stacked structures of two or more types.

[0082] It will be further understood that, when used in this specification, the terms "comprising" or "including" specify the presence of the stated features, regions, integrals, steps, operations, elements, and / or components (assemblies), but do not exclude the presence or addition of one or more other features, regions, integrals, steps, operations, elements, components (assemblies), and / or collections thereof. All scopes listed herein include endpoints.

[0083] The polishing slurry according to the embodiments is described below.

[0084] In the manufacturing process of semiconductor devices, polishing slurries can be used to planarize solid surfaces, such as the surface of semiconductor substrates (including thin films or layers such as insulating or metal layers), or to remove steps on solid surfaces.

[0085] The polishing slurry according to the embodiments includes abrasives, oxidants, and additives.

[0086] The abrasive can be abrasive particles capable of removing the object to be polished, and can be applied to a solid surface covering the object to be polished to chemically and / or physically remove the object.

[0087] The abrasive may have a predetermined hardness that enables it to remove the object to be polished, and may have a hardness, for example, higher than the hardness of the object to be polished (e.g., a metal or a semi-metal) or its oxide (e.g., a metal oxide or a semi-metal oxide).

[0088] The abrasive may be, for example, spherical, plate-like, linear, and / or irregularly shaped particles, and the particle size (average particle size, major axis, or length) of the abrasive may be, for example, in the range of about 1 nm to about 150 nm. The abrasive may include fine abrasives, for example, greater than or equal to about 1 nm and less than about 50 nm.

[0089] The abrasive may include, for example, oxide abrasives, nitride abrasives, carbon abrasives or combinations thereof, and may be silicon dioxide, cerium dioxide, aluminum oxide, zirconium oxide, titanium dioxide, silicon nitride, SiC, diamond, fullerene, derivatives thereof or combinations thereof, but is not limited thereto.

[0090] The abrasive may be included in amounts of less than or equal to about 20% by weight based on the polishing slurry, for example, about 0.001% by weight to about 20% by weight, about 0.001% by weight to about 15% by weight, about 0.001% by weight to about 10% by weight, about 0.001% by weight to about 8% by weight, about 0.001% by weight to about 5% by weight, about 0.001% by weight to about 3% by weight, about 0.01% by weight to about 2% by weight, about 0.1% by weight to about 1.5% by weight, about 0.2% by weight to about 1% by weight, or about 0.3% by weight to about 0.7% by weight.

[0091] Oxidizing agents can oxidize the object to be polished, and, for example, when a polishing slurry is applied to an object comprising a metal or half-metal, the surface of the object to be polished can be oxidized to form a metal oxide or half-metal oxide. The object to be polished oxidized by the oxidizing agent (e.g., a metal oxide or half-metal oxide) may have a relatively lower hardness than the metal or half-metal and / or may be more brittle than the metal or half-metal, and can be effectively removed by the abrasive due to the difference in mechanical strength between the object to be polished and the oxidized object.

[0092] There are no restrictions on the oxidizing agent, as long as it can oxidize the object to be polished, and it may include, for example, hydrogen peroxide, peracetic acid, percarbonate, urea peroxide, perchloric acid, persulfate, or combinations thereof.

[0093] The oxidant may be included in the following amounts: less than or equal to about 5% by weight based on the total weight of the polishing slurry, and within the above range, about 0.001% by weight to about 5% by weight, about 0.001% by weight to about 4% by weight, about 0.001% by weight to about 3% by weight, about 0.001% by weight to about 2% by weight, about 0.001% by weight to about 1% by weight, about 0.001% by weight to about 0.5% by weight, about 0.01% by weight to about 0.3% by weight, about 0.02% by weight to about 0.1% by weight, or about 0.03% by weight to about 0.05% by weight.

[0094] Additives may include one or more types of histidine derivatives. Histidine derivatives can act as corrosion inhibitors and can effectively prevent or reduce corrosion and / or over-etching of the object to be polished or its oxides (i.e., oxidized objects to be polished) during or after the polishing process.

[0095] Histidine derivatives may include histidine derivatives in which a substituted or unsubstituted cyclic imide group replaces an amino group in substituted or unsubstituted histidine (hereinafter referred to as "first histidine derivatives"). The cyclic imide group may have a ring structure comprising two carbonyl groups bonded to nitrogen.

[0096] The first histidine derivative can be represented by chemical formula 1-1.

[0097]

[0098] In chemical formula 1-1,

[0099] X 1 It can be a substituted or unsubstituted cyclic imide group.

[0100] R 1 R 2a R 2b R 3a and R 3b Each of these groups can independently be hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano, and

[0101] R 1 R 2a R 2b R 3a and R 3b They can exist independently or two adjacent ones can be combined to form a ring.

[0102] The first histidine derivative represented by formula 1-1 can be obtained by reacting a histidine comprising a substituted or unsubstituted imidazole group and an amino group with a cyclic anhydride, and the substituted or unsubstituted cyclic imide group (X) of formula 1-1. 1 The specific type of histidine derivative can be determined depending on the type of cyclic anhydride. However, it is not limited to this, and the first histidine derivative can be obtained by various methods.

[0103] For example, in chemical formula 1-1, R 1 R 2a R 2b R 3a and R 3bEach of these can be hydrogen, deuterium, C1 to C20 alkyl, halogen-substituted C1 to C20 alkyl, C2 to C20 alkenyl, halogen-substituted C2 to C20 alkenyl, C2 to C20 alkynyl, halogen-substituted C2 to C20 alkynyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, carboxyl, hydroxyl, cyano, halogen (F, Cl, Br or I) or a combination thereof.

[0104] For example, in chemical formula 1-1, R 1 R 2a R 2b R 3a and R 3b Each of these can be independently hydrogen, deuterium, methyl, ethyl, propyl, butyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, halogen-substituted methyl, halogen-substituted ethyl, halogen-substituted propyl, halogen-substituted butyl, halogen-substituted vinyl, halogen-substituted propenyl, halogen-substituted butenyl, halogen-substituted ethynyl, halogen-substituted propynyl, halogen-substituted butynyl, phenyl, biphenyl, naphthyl, halogen-substituted phenyl, halogen-substituted biphenyl, halogen-substituted naphthyl, carboxyl, halogen (F, Cl, Br or I) or combinations thereof.

[0105] For example, in chemical formula 1-1, R 1 R 2a R 2b R 3a and R 3b Each can be hydrogen independently.

[0106] For example, in chemical formula 1-1, X 1 It can be represented by any one of the chemical formulas A to C.

[0107]

[0108] In chemical formulas A to C,

[0109] R 4 To R 9 Each of these can be independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano.

[0110] R 4 To R 9 They can exist independently, or two adjacent ones can combine to form a ring.

[0111] n can be an integer from 1 to 5, and

[0112] *This can be a connection point with chemical formula 1-1.

[0113] For example, in chemical formulas A through C, R 4 To R 9 Each of these can be hydrogen, deuterium, C1 to C20 alkyl, halogen-substituted C1 to C20 alkyl, C2 to C20 alkenyl, halogen-substituted C2 to C20 alkenyl, C2 to C20 alkynyl, halogen-substituted C2 to C20 alkynyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, carboxyl, hydroxyl, cyano, halogen (F, Cl, Br or I) or a combination thereof.

[0114] For example, in chemical formulas A through C, R 4 To R 9 Each of these can be independently hydrogen, deuterium, methyl, ethyl, propyl, butyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, halogen-substituted methyl, halogen-substituted ethyl, halogen-substituted propyl, halogen-substituted butyl, halogen-substituted vinyl, halogen-substituted propenyl, halogen-substituted butenyl, halogen-substituted ethynyl, halogen-substituted propynyl, halogen-substituted butynyl, phenyl, biphenyl, naphthyl, halogen-substituted phenyl, halogen-substituted biphenyl, halogen-substituted naphthyl, carboxyl, halogen (F, Cl, Br or I) or combinations thereof.

[0115] For example, in chemical formula A, R 4 and R 5 Each can be hydrogen.

[0116] For example, in chemical formula A, R 4 and R 5 One of them can be hydrogen and R 4 and R 5 Another may be a C1 to C20 alkyl, a halogen-substituted C1 to C20 alkyl, a C2 to C20 alkenyl, a halogen-substituted C2 to C20 alkenyl, a C2 to C20 alkynyl, a halogen-substituted C2 to C20 alkynyl, a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted naphthyl, a carboxyl, a hydroxyl, a cyano, a halogen (F, Cl, Br or I), or a combination thereof.

[0117] For example, in chemical formula A, R 4 and R 5 They can combine to form rings. In this document, rings may include substituted or unsubstituted C3 to C20 aliphatic rings, substituted or unsubstituted C6 to C20 aromatic rings, or combinations thereof.

[0118] For example, in chemical formula B, R 4 To R 7 Each can be hydrogen.

[0119] For example, in chemical formula B, R 4 To R 6 Each can be hydrogen and R 7 It may be a C1 to C20 alkyl, a halogen-substituted C1 to C20 alkyl, a C2 to C20 alkenyl, a halogen-substituted C2 to C20 alkenyl, a C2 to C20 alkynyl, a halogen-substituted C2 to C20 alkynyl, a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted naphthyl, a carboxyl, a hydroxyl, a cyano, a halogen (F, Cl, Br or I) or a combination thereof.

[0120] For example, in chemical formula B, R 4 To R 7 Two can combine to form a ring. In this document, the ring may include substituted or unsubstituted C3 to C20 aliphatic rings, substituted or unsubstituted C6 to C20 aromatic rings, or combinations thereof.

[0121] For example, in chemical formula B, n can be 1, 2, or 3.

[0122] For example, in the chemical formula C, R 4 R 6 R 8 and R 9 Each can be hydrogen.

[0123] For example, in the chemical formula C, R 4 R 6 R 8 and R 9 Two can combine to form a ring. In this document, the ring may include substituted or unsubstituted C3 to C20 aliphatic rings, substituted or unsubstituted C6 to C20 aromatic rings, or combinations thereof.

[0124] For example, in the chemical formula C, n can be 1, 2, or 3.

[0125] For example, in chemical formula 1-1, X 1 It can be represented by any one of the chemical formulas B-1 to B-5.

[0126]

[0127] In chemical formulas B-1 to B-5,

[0128] R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b Each of these can be independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano.

[0129] R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b They can exist independently, or two adjacent ones can combine to form a ring.

[0130] m can be an integer from 0 to 5, and

[0131] *This can be a connection point with chemical formula 1-1.

[0132] For example, in chemical formulas B-1 to B-5, R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13bEach of these can be hydrogen, deuterium, C1 to C20 alkyl, halogen-substituted C1 to C20 alkyl, C2 to C20 alkenyl, halogen-substituted C2 to C20 alkenyl, C2 to C20 alkynyl, halogen-substituted C2 to C20 alkynyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, carboxyl, hydroxyl, cyano, halogen (F, Cl, Br or I) or a combination thereof.

[0133] For example, in chemical formulas B-1 to B-5, R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b Each of these can be independently hydrogen, deuterium, methyl, ethyl, propyl, butyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, halogen-substituted methyl, halogen-substituted ethyl, halogen-substituted propyl, halogen-substituted butyl, halogen-substituted vinyl, halogen-substituted propenyl, halogen-substituted butenyl, halogen-substituted ethynyl, halogen-substituted propynyl, halogen-substituted butynyl, phenyl, biphenyl, naphthyl, halogen-substituted phenyl, halogen-substituted biphenyl, halogen-substituted naphthyl, carboxyl, halogen (F, Cl, Br or I) or combinations thereof.

[0134] For example, in chemical formulas B-1 to B-5, m can be 0, 1, 2, or 3.

[0135] For example, in chemical formulas B-1 to B-5, R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13R 13a and R 13b Each can be hydrogen independently.

[0136] For example, in chemical formulas B-1 to B-3, R 10a With R 13a They can combine to form rings. In this document, rings may include substituted or unsubstituted C3 to C20 aliphatic rings, substituted or unsubstituted C6 to C20 aromatic rings, or combinations thereof.

[0137] For example, in chemical formulas B-1 to B-3, R 11a and R 13a They can combine to form rings. In this document, rings may include substituted or unsubstituted C3 to C20 aliphatic rings, substituted or unsubstituted C6 to C20 aromatic rings, or combinations thereof.

[0138] For example, in chemical formula B-4, R 10 To R 13 Any two of them can be combined to form a ring. In this document, the ring may include substituted or unsubstituted C3 to C20 aliphatic rings, substituted or unsubstituted C6 to C20 aromatic rings, or combinations thereof.

[0139] For example, in chemical formula B-4, R 10 To R 13 Any one of them can be a carboxyl group.

[0140] Histidine derivatives may further include histidine derivatives in which a substituted or unsubstituted ammonium acid group replaces the amino group in substituted or unsubstituted histidine (hereinafter referred to as "second histidine derivatives"). The ammonium acid group may have an acyclic structure comprising one or more amide groups and one or more carboxylic acid groups.

[0141] The second histidine derivative can be represented by chemical formula 1-2.

[0142]

[0143] In chemical formulas 1-2,

[0144] X 2 It can be a substituted or unsubstituted amyl acid group.

[0145] R 1 R 2a R 2b R 3a and R 3bEach of these groups can independently be hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano, and

[0146] R 1 R 2a R 2b R 3a and R 3b They can exist independently or two adjacent ones can be combined to form a ring.

[0147] The second histidine derivative represented by formula 1-2 can be obtained, for example, by a ring-opening reaction when a histidine containing a substituted or unsubstituted imidazole group and an amino group reacts with a cyclic anhydride, and the substituted or unsubstituted amic acid group (X) of formula 1-2. 2 The determination can depend on the type of cyclic anhydride. However, it is not limited to this, and the second histidine derivative can be obtained by various methods.

[0148] For example, in chemical formula 1-2, R 1 R 2a R 2b R 3a and R 3b Each of these can be hydrogen, deuterium, C1 to C20 alkyl, halogen-substituted C1 to C20 alkyl, C2 to C20 alkenyl, halogen-substituted C2 to C20 alkenyl, C2 to C20 alkynyl, halogen-substituted C2 to C20 alkynyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, carboxyl, hydroxyl, cyano, halogen (F, Cl, Br or I) or a combination thereof.

[0149] For example, in chemical formula 1-2, R 1 R 2a R 2b R 3a and R 3b Each of these can be independently hydrogen, deuterium, methyl, ethyl, propyl, butyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, halogen-substituted methyl, halogen-substituted ethyl, halogen-substituted propyl, halogen-substituted butyl, halogen-substituted vinyl, halogen-substituted propenyl, halogen-substituted butenyl, halogen-substituted ethynyl, halogen-substituted propynyl, halogen-substituted butynyl, phenyl, biphenyl, naphthyl, halogen-substituted phenyl, halogen-substituted biphenyl, halogen-substituted naphthyl, carboxyl, halogen (F, Cl, Br or I) or combinations thereof.

[0150] For example, in chemical formula 1-2, R 1 R2a R 2b R 3a and R 3b Each can be hydrogen independently.

[0151] For example, in chemical formula 1-2, X 1 It can be represented by any of the chemical formulas D to F.

[0152]

[0153] In chemical formulas D to F,

[0154] R 4 To R 9 Each of these can be independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano.

[0155] R 4 To R 9 They can exist independently, or two adjacent ones can combine to form a ring.

[0156] n can be an integer from 1 to 5, and

[0157] *This can be a connection point with chemical formulas 1-2.

[0158] For example, in chemical formulas D to F, R 4 To R 9 Each of these can be hydrogen, deuterium, C1 to C20 alkyl, halogen-substituted C1 to C20 alkyl, C2 to C20 alkenyl, halogen-substituted C2 to C20 alkenyl, C2 to C20 alkynyl, halogen-substituted C2 to C20 alkynyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, carboxyl, hydroxyl, cyano, halogen (F, Cl, Br or I) or a combination thereof.

[0159] For example, in chemical formulas D to F, R 4 To R 9 Each of these can be independently hydrogen, deuterium, methyl, ethyl, propyl, butyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, halogen-substituted methyl, halogen-substituted ethyl, halogen-substituted propyl, halogen-substituted butyl, halogen-substituted vinyl, halogen-substituted propenyl, halogen-substituted butenyl, halogen-substituted ethynyl, halogen-substituted propynyl, halogen-substituted butynyl, phenyl, biphenyl, naphthyl, halogen-substituted phenyl, halogen-substituted biphenyl, halogen-substituted naphthyl, carboxyl, halogen (F, Cl, Br or I) or combinations thereof.

[0160] For example, in chemical formula D, R 4 and R 5 Each can be hydrogen.

[0161] For example, in chemical formula D, R 4 and R 5 One of them can be hydrogen and R 4 and R 5 Another may be a C1 to C20 alkyl, a halogen-substituted C1 to C20 alkyl, a C2 to C20 alkenyl, a halogen-substituted C2 to C20 alkenyl, a C2 to C20 alkynyl, a halogen-substituted C2 to C20 alkynyl, a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted naphthyl, a carboxyl, a hydroxyl, a cyano, a halogen (F, Cl, Br or I), or a combination thereof.

[0162] For example, in chemical formula D, R 4 and R 5 They can combine to form rings. In this document, rings may include substituted or unsubstituted C3 to C20 aliphatic rings, substituted or unsubstituted C6 to C20 aromatic rings, or combinations thereof.

[0163] For example, in chemical formula E, R 4 To R 7 Each can be hydrogen.

[0164] For example, in chemical formula E, R 4 To R 6 Each can be hydrogen and R 7 It may be a C1 to C20 alkyl, a halogen-substituted C1 to C20 alkyl, a C2 to C20 alkenyl, a halogen-substituted C2 to C20 alkenyl, a C2 to C20 alkynyl, a halogen-substituted C2 to C20 alkynyl, a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted naphthyl, a carboxyl, a hydroxyl, a cyano, a halogen (F, Cl, Br or I) or a combination thereof.

[0165] For example, in chemical formula E, R 4 To R 7 Two can combine to form a ring. In this document, the ring may include substituted or unsubstituted C3 to C20 aliphatic rings, substituted or unsubstituted C6 to C20 aromatic rings, or combinations thereof.

[0166] For example, in the chemical formula E, n can be 1, 2, or 3.

[0167] For example, in the chemical formula F, R 4 R 6 R 8 and R 9 Each can be hydrogen.

[0168] For example, in the chemical formula F, R4 R 6 R 8 and R 9 Two can combine to form a ring. In this document, the ring may include substituted or unsubstituted C3 to C20 aliphatic rings, substituted or unsubstituted C6 to C20 aromatic rings, or combinations thereof.

[0169] For example, in the chemical formula F, n can be 1, 2, or 3.

[0170] For example, in chemical formula 1-2, X 2 It can be represented by any one of the chemical formulas E-1 to E-5.

[0171]

[0172] In chemical formulas E-1 to E-5

[0173] R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b Each of these can be independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano.

[0174] R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13R 13a and R 13b They can exist independently, or two adjacent ones can combine to form a ring.

[0175] m can be an integer from 0 to 5, and

[0176] *This can be a connection point with chemical formulas 1-2.

[0177] For example, in chemical formulas E-1 to E-5, R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b Each of these can be hydrogen, deuterium, C1 to C20 alkyl, halogen-substituted C1 to C20 alkyl, C2 to C20 alkenyl, halogen-substituted C2 to C20 alkenyl, C2 to C20 alkynyl, halogen-substituted C2 to C20 alkynyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, carboxyl, hydroxyl, cyano, halogen (F, Cl, Br or I) or a combination thereof.

[0178] For example, in chemical formulas E-1 to E-5, R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13bEach of these can be independently hydrogen, deuterium, methyl, ethyl, propyl, butyl, vinyl, propenyl, butenyl, ethynyl, propynyl, butynyl, halogen-substituted methyl, halogen-substituted ethyl, halogen-substituted propyl, halogen-substituted butyl, halogen-substituted vinyl, halogen-substituted propenyl, halogen-substituted butenyl, halogen-substituted ethynyl, halogen-substituted propynyl, halogen-substituted butynyl, phenyl, biphenyl, naphthyl, halogen-substituted phenyl, halogen-substituted biphenyl, halogen-substituted naphthyl, carboxyl, halogen (F, Cl, Br or I) or combinations thereof.

[0179] For example, in chemical formulas E-1 to E-5, m can be 0, 1, 2, or 3.

[0180] For example, in chemical formulas E-1 to E-5, R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b Each can be hydrogen independently.

[0181] For example, in chemical formulas E-1 to E-3, R 10a With R 13a They can combine to form rings. In this document, rings may include substituted or unsubstituted C3 to C20 aliphatic rings, substituted or unsubstituted C6 to C20 aromatic rings, or combinations thereof.

[0182] For example, in chemical formulas E-1 to E-3, R 11a and R 13a They can combine to form rings. In this document, rings may include substituted or unsubstituted C3 to C20 aliphatic rings, substituted or unsubstituted C6 to C20 aromatic rings, or combinations thereof.

[0183] For example, in chemical formula E-4, R 10 To R 13 Any two of them can be combined to form a ring. In this document, the ring may include substituted or unsubstituted C3 to C20 aliphatic rings, substituted or unsubstituted C6 to C20 aromatic rings, or combinations thereof.

[0184] For example, in chemical formula E-4, R10 To R 13 Any one of them can be a carboxyl group.

[0185] Histidine derivatives may include a first histidine derivative, a second histidine derivative, or a combination thereof. For example, a histidine derivative may include a first histidine derivative and optionally a second histidine derivative.

[0186] Histidine derivatives (e.g., a first histidine derivative, or a first histidine derivative and a second histidine derivative) may be included in an amount of less than or equal to about 5% by weight of the polishing slurry, and within the above range, may be included in an amount of about 0.001% to about 5% by weight, about 0.001% to about 4% by weight, about 0.001% to about 3% by weight, about 0.001% to about 2% by weight, about 0.001% to about 1% by weight, about 0.001% to about 0.5% by weight, about 0.01% to about 0.3% by weight, about 0.01% to about 0.1% by weight, or about 0.02% to about 0.04% by weight of the polishing slurry.

[0187] Histidine derivatives (e.g., first histidine derivative, second histidine derivative) may be included based on a concentration of less than or equal to about 0.1 mol / L of the polishing slurry, and within the above range, may be included based on a concentration of about 0.001 to about 0.1 mol / L, about 0.001 to about 0.08 mol / L, about 0.001 to about 0.06 mol / L, about 0.001 to about 0.05 mol / L, about 0.005 to about 0.03 mol / L, about 0.007 to about 0.02 mol / L, or about 0.008 to about 0.015 mol / L of the polishing slurry.

[0188] The oxidant and histidine derivative may be included in an appropriate molar ratio to improve the polishing rate and reduce corrosion or over-etching, for example, in a molar ratio of about 0.01:10 to about 10:0.01. Within the above range, the oxidant and histidine derivative may be included in a molar ratio of about 0.1:10 to about 10:0.1, about 1:10 to about 10:1, about 2:8 to about 8:2, about 3:7 to about 7:3, about 4:6 to about 6:4 or about 5:5.

[0189] Additives may further include chelating agents, surfactants, dispersants, pH adjusters, reaction catalysts, or combinations thereof.

[0190] The chelating agent may be phosphoric acid, nitric acid, citric acid, malonic acid, their salts or combinations thereof, but is not limited thereto.

[0191] The surfactant may be an ionic or nonionic surfactant, and may be, for example, a copolymer of ethylene oxide, a copolymer of propylene oxide, an amine compound, or a combination thereof, but is not limited thereto.

[0192] Dispersants can promote the dispersion of abrasives and may include, for example, water-soluble monomers, water-soluble oligomers, water-soluble polymers, metal salts, or combinations thereof. The weight-average molecular weight of the water-soluble polymer may be, for example, less than or equal to about 10,000 g / mol, for example, less than or equal to about 5,000 g / mol, for example, less than or equal to about 3,000 g / mol. Metal salts may be, for example, copper salts, nickel salts, cobalt salts, manganese salts, tantalum salts, ruthenium salts, or combinations thereof. Dispersants may be poly(meth)acrylic acid, poly(meth)acrylic acid-co-maleic acid, polyacrylonitrile-co-butadiene-acrylic acid, carboxylic acids, sulfonates, sulfonic acids, phosphate esters, cellulose, glycols, their salts, or combinations thereof, but are not limited thereto.

[0193] pH adjusters can adjust the pH of polishing slurries and can be, for example, inorganic acids, organic acids, inorganic bases, organic bases, their salts, or combinations thereof. Inorganic acids may include nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, hydrobromic acid, or iodic acid; inorganic bases may include potassium hydroxide, sodium hydroxide, or their salts; and organic acids may include, but are not limited to, formic acid, malonic acid, maleic acid, oxalic acid, adipic acid, citric acid, acetic acid, propionic acid, fumaric acid, lactic acid, salicylic acid, benzoic acid, succinic acid, phthalic acid, butyric acid, glutamic acid, glycolic acid, lactic acid, aspartic acid, or tartaric acid, but are not limited thereto.

[0194] The reaction catalyst can promote the oxidation reaction of the object to be polished by catalyzing the decomposition of the oxidant. The reaction catalyst can be, for example, a metal ionic compound that can effectively generate free radicals, and can be a catalyst used, for example, in a Fenton reaction or a Fenton-like reaction. The reaction catalyst may include, for example, cations and anions. Cations include iron (Fe) ions, chromium (Cr) ions, manganese (Mn) ions, cobalt (Co) ions, cerium (Ce) ions, potassium (K) ions, silver (Ag) ions, copper (Cu) ions, molybdenum (Mo) ions, niobium (Nb) ions, nickel (Ni) ions, osmium (Os) ions, lead (Pb) ions, tin (Sn) ions, titanium (Ti) ions, vanadium (V) ions, or combinations thereof. Anions include, but are not limited to, nitrate, sulfate, fluoride, chloride, bromide, iodide, fluorate, chlorate, bromate, iodate, perchlorate, perbromate, periodate, cyanide, oxalate, citrate, acetate, acetylacetonate, gluconate, or combinations thereof. For example, the reaction catalyst may be an iron ion catalyst, such as ferric nitrate (II), ferric nitrate (III), ferric sulfate (II), ferric sulfate (III), ferric oxalate (II), ferric oxalate (III), or combinations thereof, but is not limited thereto.

[0195] Each component of the additive may be included independently in trace amounts, for example, from about 1 ppm to about 100,000 ppm, but is not limited thereto.

[0196] The polishing slurry may further include a dispersion medium or solvent (hereinafter referred to as 'dispersion medium') capable of dispersing and / or dissolving the above-mentioned components, and the dispersion medium may be, for example, water. The water may be, for example, distilled water and / or deionized water.

[0197] The dispersion medium may be included as a balance excluding solids such as abrasives, oxidants, and additives.

[0198] The pH of the polishing slurry can be from about 1.0 to about 10.0, and within the above range it can be from about 1.0 to about 7.0 or from about 1.0 to about 5.0.

[0199] Polishing slurries can be used in the formation of various structures. For example, they can be used in the polishing processes of conductive materials such as metal layers, or insulating materials such as shallow trench isolation (STI) or insulating layers. For instance, polishing slurries can be used to polish conductive materials such as metal lines, vias, and / or electrodes in semiconductor substrates, and can be used to polish conductive materials such as tungsten, molybdenum, aluminum, copper, nickel, or alloys thereof, and can be used to polish molybdenum-containing (Mo) layers or molybdenum alloys.

[0200] The following describes examples of methods for manufacturing semiconductor devices using polishing slurry according to embodiments.

[0201] A method for manufacturing a semiconductor device according to an embodiment includes performing chemical mechanical polishing (CMP) on all or part of the surface of an object to be polished. The object to be polished can be of various structures, such as a semiconductor substrate like a silicon wafer (including thin films or layers such as insulating or metal layers), and the polished surface can include metals such as molybdenum, aluminum, copper, or nickel, alloys thereof, or metal oxides or half-metal oxides produced during the chemical mechanical polishing process; oxides such as silicon oxide or molybdenum oxide; nitrides such as silicon nitride, aluminum nitride, titanium nitride, or gallium nitride; carbides such as silicon carbide; semiconductors such as silicon or germanium; compound semiconductors such as InP, GaAs; organic or inorganic compounds such as tetraethyl orthosilicate (TEOS); or combinations thereof.

[0202] For example, polishing slurry can be used to polish conductive materials such as metal layers in semiconductor substrates, and can be used to form metal lines, vias and / or electrodes from conductive layers including, for example, molybdenum (Mo) or Mo alloys.

[0203] The following describes examples of methods for manufacturing semiconductor devices using the aforementioned polishing slurry.

[0204] Figures 1 to 4 This is a cross-sectional view illustrating an example of a method for manufacturing a semiconductor device according to an embodiment.

[0205] refer to Figure 1 An insulating layer 20 is formed on the semiconductor substrate 10. The insulating layer 20 may include oxides, nitrides, and / or oxynitrides. The insulating layer 20 may be a dielectric layer. Next, the insulating layer 20 is etched to form an opening 20a. The opening 20a may include trenches, vias, and / or contact holes. For example, the opening 20a may have a width of less than about 10 nm, for example, from 0.1 nm to 10 nm, but is not limited thereto. Next, a barrier layer 30 is formed on the inner wall of the opening 20a. The barrier layer 30 may include, for example, Ta and / or TaN, but is not limited thereto.

[0206] refer to Figure 2 The interior and top of the opening 20a are filled or coated with metal to form a conductive layer 40. The conductive layer 40 may include, for example, metals such as tungsten, molybdenum, aluminum, copper, or nickel, alloys thereof, or combinations thereof, and may include, for example, molybdenum (Mo) or Mo alloys. For example, when the barrier layer 30 is a Ta layer and the conductive layer 40 is a Mo-containing layer, a higher Ta-to-Mo polishing selectivity in the polishing slurry is desirable, and for example, a higher than about 50:1 is desirable.

[0207] refer to Figure 3 The surface of the conductive layer 40 can be planarized to substantially match the surface of the insulating layer 20 to form an embedded conductive pattern 40a. Planarization can be performed by chemical mechanical polishing (CMP) using a CMP apparatus, and the polishing slurry described above can be used. This will be described later.

[0208] Reference Figure 4 A capping layer 50 is formed on the embedded conductive pattern 40a and the insulating layer 20. The capping layer 50 may include, but is not limited to, SiN and / or SiC.

[0209] The planarization used to form the embedded conductive pattern 40a is described below. As mentioned above, planarization can be performed using a CMP device.

[0210] Figure 5 This is a schematic diagram illustrating a CMP device based on an example.

[0211] refer to Figure 5 According to the example, the CMP apparatus 100 may include, for example, a lower base (not shown); a platen 120 rotatably provided on the upper surface of the lower base; a polishing head 130; a polishing pad 150 on the platen 120; a pad adjuster 160; and at least one polishing slurry supply device 140 disposed adjacent to the polishing pad 150 to supply polishing slurry to the polishing pad 150.

[0212] The platform 120 may be rotatable on the surface of the lower base. For example, the platform 120 may receive rotational power from a motor (not shown) disposed in the lower base, and thus may be rotated in a certain direction, such as clockwise or counterclockwise, by means of a rotation shaft 120S perpendicular to the surface of the platform 120.

[0213] The polishing head 130 can be disposed on the stage 120 and can hold the subject to be polished. The subject to be polished can be a semiconductor substrate 10, such as a wafer. The polishing head 130 may include a rotation axis 130S for rotating the subject to be polished. During polishing, the rotation direction of the polishing head 130 may be opposite to the rotation direction of the stage 120.

[0214] A polishing pad 150 may be disposed on a stage 120 and supported by the stage 120. The polishing pad 150 may rotate together with the stage 120. The polishing pad 150 may have a roughened polishing surface 150S. The polishing surface 150S can mechanically polish the surface of the semiconductor substrate 10 by directly contacting it. The polishing pad 150 may be made of a porous material having multiple microspaces, and the multiple microspaces may contain polishing slurry. The polishing surface 150S of the polishing pad 150 may include a surface that directly contacts the body to be polished and a predetermined depth therefrom, and the predetermined depth may be about 10% to about 100%, about 20% to about 100%, about 30% to about 100%, about 40% to about 100%, or about 50% to about 100% of the thickness of the polishing pad 150. The polishing surface 150S of the polishing pad 150 may, for example, be flat. The polishing surface 150S of the polishing pad 150 may have, for example, protrusions or grooves.

[0215] The pad adjuster 160 can be adjacent to the polishing pad 150 and can maintain the state of the polishing surface, so that the surface of the semiconductor substrate 10 can be effectively polished while the polishing process is being performed.

[0216] A polishing slurry supply device 140 may be adjacent to a polishing pad 150 and may supply polishing slurry from a polishing slurry tank 145 to the polishing pad 150. The polishing slurry supply device 140 may include nozzles capable of supplying polishing slurry onto the polishing pad 150 during the polishing process. The polishing slurry supply device 140 may supply polishing slurry.

[0217] CMP can be performed, for example, by setting the semiconductor substrate 10 and the polishing pad 150 to face each other, supplying polishing slurry from the polishing slurry supply device 140 between the semiconductor substrate 10 and the polishing pad 150, and polishing by bringing the polishing pad 150 into contact with the surface of the semiconductor substrate 10.

[0218] For example, the polishing slurry can be supplied at a rate of approximately 10 ml / min to approximately 300 ml / min.

[0219] Polishing can be performed by mechanical friction through contacting the polishing pad 150 with the surface of the semiconductor substrate 10 and rotating it. For example, a pressure of about 1 psi to about 5 psi can be applied during polishing.

[0220] For example, the oxidizing agent in the polishing slurry can oxidize the surface of the object to be polished (e.g., a metal such as molybdenum) to form a metal oxide (e.g., molybdenum oxide) of a predetermined thickness within the object. During polishing, the abrasive can physically and / or chemically remove the metal oxide on the polishing surface. Histidine derivatives in the polishing slurry can act as corrosion inhibitors to effectively prevent or reduce defects caused by excessive corrosion or over-etching of the surface of the object to be polished (e.g., a metal such as molybdenum) during polishing. The prevention of oxidation and corrosion or over-etching of the polished surface can occur simultaneously or sequentially.

[0221] In this way, polishing slurries, by including abrasives, oxidants, and histidine derivatives, can increase the polishing rate of the object to be polished, while effectively reducing or preventing losses or defects caused by excessive corrosion or etching.

[0222] For example, the conductive layer 40 may include a Mo-containing layer, and the removal rate (RR) of the Mo-containing layer may be greater than or equal to about 110 Å / min, and within the aforementioned range, about 110 Å / min to about 1000 Å / min, about 120 Å / min to about 1000 Å / min, about 130 Å / min to about 1000 Å / min, about 130 Å / min to about 500 Å / min, about 135 Å / min to about 300 Å / min, about 140 Å / min to about 200 Å / min, or about 140 Å / min. The etch rate of the Mo-containing layer can be from about Å / min to about 150 Å / min, and the etch rate (static etch rate, SER) of the Mo-containing layer can be less than about 80 Å / min, and within the above range, greater than or equal to about 1 Å / min and less than about 80 Å / min, about 3 Å / min to about 70 Å / min, about 5 Å / min to about 60 Å / min, about 5 Å / min to about 40 Å / min, about 6 Å / min to about 20 Å / min, about 7 Å / min to about 15 Å / min, or about 7.5 Å / min to about 12 Å / min. For example, the ratio of the polishing rate of the Mo-containing layer to the static etch rate can be greater than or equal to about 3, and within the above range, about 3 to about 80, about 5 to about 80, about 7 to about 80, about 9 to about 80, about 10 to about 80, about 12 to about 80, about 12 to about 50, about 12 to about 40, or about 12 to about 20.

[0223] Although the above describes a method for manufacturing semiconductor devices based on examples, it is not limited to this and can be applied to semiconductor devices with various structures.

[0224] In the following description, implementation methods are illustrated in more detail with reference to embodiments. However, these embodiments are exemplary, and the scope of the claims is not limited thereto.

[0225] Synthesis Examples

[0226] Synthesis Example 1

[0227] To prepare an itaconic anhydride solution, 3 g of itaconic anhydride was dissolved in 20 mL of acetic acid in a 250 mL round-bottom flask. In another flask, 4.0 g of L-histidine was dissolved in 30 mL of acetic acid and added dropwise to the itaconic anhydride solution. The reaction was carried out overnight at room temperature. The resulting product was then precipitated in acetone, and the acetone was decanted to obtain the precipitate. Subsequently, the precipitate was dissolved in water, precipitated twice more in acetone, and lyophilized to give 5.97 g of histidine derivatives (compounds 1-1a and 1-2a) as crystalline powder. The yield was 93%.

[0228]

[0229] 1 H NMR (D2O), δ (ppm): 3.02 (1H, dd), 3.1-3.3 (1H, dd, 2H, s), 4.46(1H, t), 5.67 (1H, s), 6.17 (1H, s), 7.14 (1H, s), 8.48 (1H, s).

[0230] Synthesis Example 2

[0231] 2.557 g of maleic anhydride was dissolved in 40 mL of acetic acid in a 250 mL round-bottom flask to prepare a maleic anhydride solution. In another flask, 4.0 g of L-histidine was dissolved in 40 mL of acetic acid and added dropwise to the maleic anhydride solution. The reaction was carried out overnight at room temperature. The product obtained was then precipitated in a large amount of acetone, and the acetone was decanted to obtain the precipitate. Subsequently, the precipitate was dissolved in water, precipitated twice more in acetone, and lyophilized to give 5.29 g of histidine derivatives (compounds 1-1b and 1-2b) as crystalline powder. The yield was 81%.

[0232]

[0233] 1 H NMR (D2O), δ (ppm): 3.11 (1H, dd), 3.21 (1H, dd), 4.56 (1H, t), 6.28 (2H, s), 7.18 (1H, s), 8.49 (1H, s).

[0234] Preparation Examples

[0235] Preparation Example 1

[0236] A polishing slurry with pH 2.0 was prepared by mixing 0.5 wt% colloidal silica (average particle diameter: 30 nm), 0.034 wt% (0.01 mol / L) hydrogen peroxide, 0.0249 wt% (0.01 mol / L) histidine derivative obtained in Synthesis Example 1, a small amount of nitric acid and the balance of deionized water.

[0237] Preparation Example 2

[0238] The polishing slurry was prepared in the same manner as in Preparation Example 1, except that 0.235% by weight (0.01 mol / L) of the histidine derivative obtained in Synthesis Example 2 was used instead of the histidine derivative obtained in Synthesis Example 1.

[0239] Preparation of Comparative Example 1

[0240] The polishing slurry was prepared in the same manner as in Preparation Example 1, except that the histidine derivative obtained in Synthesis Example 1 was not included.

[0241] Preparation of Comparative Example 2

[0242] The polishing slurry was prepared in the same manner as in Preparation Example 1, except that L-histidine (0.01 mol / L) represented by chemical formula A was used instead of the histidine derivative obtained in Synthesis Example 1.

[0243]

[0244] Evaluation I

[0245] The polishing rate (removal rate, RR) of each Mo layer was evaluated based on the polishing slurries prepared according to Examples 1 and 2 and Comparative Examples 1 and 2.

[0246] CMP is performed under the following conditions.

[0247] (1) CMP equipment: GNP POLI-400L (G&P Technology, Inc.)

[0248] (2) The substrate to be polished: a 40mm × 40mm silicon wafer sample with a 5000Å thick Mo layer formed by PVD.

[0249] (3) Polishing head rotation speed: 87 rpm

[0250] (4) Polishing table rotation speed: 93 rpm

[0251] (5) Applied pressure: 3 psi

[0252] (6) Initial temperature: 24℃

[0253] (7) Polishing slurry: Polishing slurries (45°C) were prepared according to Preparation Examples 1 and 2 and Comparative Examples 1 and 2.

[0254] (8) Polishing slurry supply flow rate: 130ml / minute.

[0255] (9) Polishing time: 1 minute

[0256] The chemical mechanical polishing rate (removal rate, RR) was calculated according to Equation 1. In Equation 1, the thickness of the Mo layer was calculated according to Equation 2 by measuring the thin-film resistance and volume resistivity using a ohmmeter (model "RS-100", KLA Tencor) with the DC 4 probe method.

[0257] [Calculate Equation 1]

[0258] Removal rate (RR, Å / min) = (Thickness of Mo layer before polishing (Å) - Thickness of Mo layer after polishing (Å)) / Polishing time (min)

[0259] [Calculate Equation 2]

[0260] Mo layer thickness (Å) = [volume resistivity (Ω·m) ÷ thin layer resistance (Ω)] x 10 10

[0261] Evaluation II

[0262] The etching rate (static etching rate, SER) of each Mo layer was evaluated based on the polishing slurries prepared according to Examples 1 and 2 and Comparative Examples 1 and 2.

[0263] A 40 mm × 40 mm silicon wafer covered with a 5000 Å thick Mo layer formed by PVD was immersed in polishing slurries prepared according to Preparation Examples 1 and 2 and Comparative Examples 1 and 2 for 30 minutes each. The silicon wafer was then removed and washed with deionized water. The thickness of the obtained Mo layer before and after immersion was then measured using the same method as described above, and this thickness was used to calculate the static etching rate (SER, Å / min) according to Equation 3 below.

[0264] [Calculate Equation 3]

[0265] Static etching rate (SER, Å / min) = (Mo layer thickness before immersion (Å) - Mo layer thickness after immersion (Å)) / Immersion time (min)

[0266] The results are shown in Table 1 and... Figure 6 and 7 middle.

[0267] Figure 6 This is a graph showing the polishing rate and etching rate of the polishing slurry for the Mo layer according to the preparation examples and comparative examples, and Figure 7 This is a graph showing the ratio of polishing rate to etching rate of the polishing slurry for the Mo layer according to the preparation examples and comparative examples.

[0268] Table 1

[0269]

[0270] *RR: Removal rate

[0271] *SER: Static Etching Rate

[0272] Refer to Table 1 and Figure 6 and 7 The polishing slurries prepared according to Examples 1 and 2 exhibited significantly lower static etching rates than the polishing slurry prepared according to Comparative Example 1. Therefore, it can be confirmed that the histidine derivative (corrosion inhibitor) obtained in the synthesis examples can effectively reduce corrosion or over-etching of the Mo layer.

[0273] Furthermore, compared to the polishing slurry prepared according to Comparative Example 2, the polishing slurries prepared according to Examples 1 and 2 can increase the polishing rate (removal rate) while reducing the static etching rate. Therefore, it can be confirmed that, compared to histidine, the histidine derivative obtained in the synthesis examples can effectively increase the polishing rate (removal rate) while reducing corrosion or over-etching.

[0274] Therefore, it can be confirmed that, compared with the polishing slurries prepared according to Comparative Examples 1 and 2, the polishing slurries prepared according to Examples 1 and 2 can increase the ratio of the polishing rate (removal rate) of the Mo layer to the static etching rate by more than 5 times.

[0275] While this disclosure has been described in conjunction with exemplary embodiments now considered practical, it will be understood that the invention is not limited to the disclosed embodiments. Rather, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. Polishing slurry, including: Abrasive, Oxidizing agents, and A first histidine derivative containing a substituted or unsubstituted cyclic imide group.

2. The polishing slurry according to claim 1, wherein the first histidine derivative is represented by chemical formula 1-1: in, In chemical formula 1-1, X 1 For substituted or unsubstituted cyclic imide groups, R 1 R 2a R 2b R 3a and R 3b Each of the following groups is independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano. R 1 R 2a R 2b R 3a and R 3b They exist independently or their adjacent pairs combine to form a ring.

3. The polishing slurry according to claim 2, wherein X 1 Any one of the chemical formulas A through C: in, In chemical formulas A to C, R 4 To R 9 Each of the following groups is independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkoxy, substituted or unsubstituted C1 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano. R 4 To R 9 They exist independently or their adjacent pairs combine to form a ring. n is an integer from 1 to 5, and * indicates the connection point with chemical formula 1-1.

4. The polishing slurry according to claim 3, wherein X 1 Any one of the chemical formulas B-1 to B-5: in, In chemical formulas B-1 to B-5, R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b Each of the following groups is independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkoxy, substituted or unsubstituted C1 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano. R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b They exist independently or their adjacent pairs combine to form a ring. m is an integer from 0 to 5, and * indicates the connection point with chemical formula 1-1.

5. The polishing slurry according to claim 1 or 2, further comprising a second histidine derivative containing a substituted or unsubstituted ammonium acid group.

6. The polishing slurry according to claim 5, wherein the second histidine derivative is represented by chemical formulas 1-2: in, In chemical formulas 1-2, X 2 It is a substituted or unsubstituted amyl acid group. R 1 R 2a R 2b R 3a and R 3b Each of the following groups is independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano. R 1 R 2a R 2b R 3a and R 3b They exist independently or their adjacent pairs combine to form a ring.

7. The polishing slurry according to claim 6, wherein X 2 Any representation from chemical formula D to F: in, In chemical formulas D to F, R 4 To R 9 Each of the following groups is independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkoxy, substituted or unsubstituted C1 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano. R 4 To R 9 They exist independently or their adjacent pairs combine to form a ring. n is an integer from 1 to 5, and * indicates the connection point with chemical formulas 1-2.

8. The polishing slurry according to claim 6, wherein X 2 Any one of the chemical formulas E-1 to E-5: in, In chemical formulas E-1 to E-5 R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b Each of the following groups is independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkoxy, substituted or unsubstituted C1 to C20 aryl, carboxyl, hydroxyl, halogen, or cyano. R 4a R 5 R 6 R 7 R 7a R 8 R 9 R 10 R 10a R 10b R 11 R 11a R 11b R 12 R 12a R 12b R 13 R 13a and R 13b They exist independently or their adjacent pairs combine to form a ring. m is an integer from 0 to 5, and * indicates the connection point with chemical formulas 1-2.

9. The polishing slurry according to claim 1, wherein the oxidant and the first histidine derivative are included in the polishing slurry in a molar ratio of 0.01:10 to 10:0.

01.

10. The polishing slurry according to claim 1, further comprising a dispersion medium. The oxidant and the first histidine derivative are each included in an amount of 0.001% to 5% by weight based on the polishing slurry.

11. A method for manufacturing a semiconductor device, the method comprising: A conductive layer is formed on an insulating layer with openings. The polishing slurry according to any one of claims 1 to 10 is supplied on the conductive layer, and The conductive layer is chemically and mechanically polished to form embedded conductive patterns in the openings of the insulating layer.

12. The method of claim 11, wherein the conductive layer comprises a molybdenum-containing layer.

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