Polishing slurry and method for manufacturing semiconductor devices

Abstract

The present invention provides a polishing slurry containing an abrasive, an oxidizing agent, and a histidine derivative having a substituted or unsubstituted ring imide group, and a method for manufacturing a semiconductor device using the same. [Solution] The method involves forming an insulating layer 20 on a semiconductor substrate 10. The insulating layer 20 comprises an oxide, nitride and / or oxynitride, and may be, for example, a dielectric layer. Next, the insulating layer 20 is etched to form an opening, a barrier layer 30 is formed on the wall surface of the opening, the inside and top of the opening is filled with a metal such as molybdenum (Mo) or a molybdenum alloy to form a conductive layer, the surface of the conductive layer is planarized to substantially coincide with the surface of the insulating layer 20 to form a filled conductive pattern 40a, and a capping layer 50 is formed on the filled conductive pattern 40a and the insulating layer 20.

Description

[Technical Field]

[0001] This invention relates to a polishing slurry and a method for manufacturing semiconductor devices. [Background technology]

[0002] With the miniaturization of electronic devices and the resulting miniaturization of integrated circuits, various methods are being studied for forming microstructures such as metal wiring, contact holes, or shallow trench isolation with a width of several nanometers.

[0003] In the process of forming such microstructures, a polishing process can be performed to create a flat surface for the microstructure, and one such polishing process is chemical mechanical polishing (CMP). Chemical mechanical polishing is a process in which a polishing slurry containing an abrasive is placed between the semiconductor substrate containing the object to be polished and the polishing pad, and the object to be polished is polished to flatten the surface of the semiconductor substrate. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] To improve the performance of chemical mechanical polishing, it is necessary to increase the polishing speed of the object being polished, such as a metal layer, while simultaneously reducing the loss or defects of the object being polished, such as dishing, which can occur due to corrosion or over-etching. [Means for solving the problem]

[0005] One embodiment provides a polishing slurry that can remove the workpiece at a high polishing speed and can reduce or prevent loss or defects of the workpiece due to excessive corrosion or over-etching.

[0006] Other embodiments provide a method for manufacturing a semiconductor device using the polishing slurry.

[0007] According to one embodiment, a polishing slurry is provided that includes an abrasive, an oxidizing agent, and a first histidine derivative having a substituted or unsubstituted cyclic imide group.

[0008] The first histidine derivative can be represented by Chemical Formula 1-1 below.

[0009]

Chem.

[0010] In Chemical Formula 1-1, X 1 can be a substituted or unsubstituted cyclic imide group, R 1 、R 2a 、R 2b 、R 3a 、and R 3b can each independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxy group, a halogen, or a cyano group, R 1 、R 2a 、R 2b 、R 3a 、and R 3b can each independently exist or two of these can combine to form a ring.

[0011] X in Chemical Formula 1-1 1 can be represented by any one of Chemical Formulas A to C below.

[0012]

Chem.

[0013] In the aforementioned chemical formulas A to C, R 4 From R 9 Each of these can independently be hydrogen, deuterium, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R 4 From R 9 These can exist independently, or two of them can combine to form a ring. n can be an integer from 1 to 5. * may be a linking point with the aforementioned chemical formula 1-1.

[0014] X of the above chemical formula 1-1 1 It can be represented by one of the following chemical formulas B-1 to B-5.

[0015] [ka]

[0016] [ka]

[0017] [ka]

[0018] In the above 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 , R11a , R 11b , R 12 , R 12a , R 12b , R 13 , R 13a , and R 13b Each of these can independently be hydrogen, deuterium, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. 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 These can exist independently, or two adjacent elements can join together to form a ring. m can be an integer from 0 to 5. * may be a linking point with the aforementioned chemical formula 1-1.

[0019] The polishing slurry may further contain a secondary histidine derivative having a substituted or unsubstituted amic acid group.

[0020] The second histidine derivative can be represented by the following chemical formulas 1-2.

[0021] [ka]

[0022] In the above chemical formula 1-2, X 2 This can be a substituted or unsubstituted amic acid group. R 1 , R 2a , R 2b , R 3a , and R 3b Each of these can independently be hydrogen, deuterium, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R 1 , R 2a , R 2b , R 3a , and R 3b These elements can exist independently, or two of them can combine to form a ring.

[0023] X of the above chemical formula 1-2 2 It can be represented by one of the following chemical formulas D through F.

[0024] [ka]

[0025] In the aforementioned chemical formulas D to F, R 4 From R 9 Each of these can independently be hydrogen, deuterium, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R 4 From R 9 These can exist independently, or two of them can combine to form a ring. n can be an integer from 1 to 5. * may be a connection point with the chemical formula 1-2.

[0026] X of the chemical formula 1-2 2 can be represented by any one of the following chemical formulas E-1 to E-5.

[0027] [Chemical formula]

[0028] [Chemical formula]

[0029] [Chemical formula]

[0030] In the 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 can each independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxy group, a halogen or a cyano group, R 4a 、R 5 、R 6 、R 7 、R7a , 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 may each independently exist or two adjacent ones of these may combine to form a ring. m can be an integer from 0 to 5. * can be the connection point with the chemical formula 1-2.

[0031] The first histidine derivative can be represented by the chemical formula 1-1, and the polishing slurry can further contain a second histidine derivative having a substituted or unsubstituted amic acid group represented by the chemical formula 1-2.

[0032] The abrasive can include an oxide abrasive, a nitride abrasive, a carbonaceous abrasive, or a combination thereof.

[0033] The abrasive can include silica, ceria, alumina, zirconia, titania, or a combination thereof.

[0034] The polishing slurry can further contain a dispersion medium, and the abrasive may be contained in the polishing slurry at about 0.001 wt% to 20 wt%.

[0035] The oxidizing agent can include hydrogen peroxide, peracetic acid, percarbonate, urea peroxide, perchloric acid, persulfate, or a combination thereof.

[0036] The oxidizing agent and the first histidine derivative may be contained in the polishing slurry at a molar ratio of about 0.01:10 to 10:0.01.

[0037] The polishing slurry may further contain a dispersion medium, and the oxidizing agent and the first histidine derivative may each be present in an amount of about 0.001% to 5% by weight relative to the polishing slurry.

[0038] The pH of the polishing slurry may range from 1.0 to 10.0.

[0039] The polishing slurry may further contain a chelating agent, a surfactant, a dispersant, a pH adjuster, a dispersion medium, or a combination thereof.

[0040] Another embodiment provides a method for manufacturing a semiconductor device, comprising the steps of forming a conductive layer on an insulating layer having an opening, supplying a polishing slurry onto the conductive layer, and performing chemical mechanical polishing on the conductive layer to form a conductive pattern filled in the opening, wherein the polishing slurry comprises an abrasive, an oxidizing agent, and a first histidine derivative having a substituted or unsubstituted ring imide group.

[0041] The first histidine derivative can be represented by the chemical formula 1-1.

[0042] X of the above chemical formula 1-1 1 This can be represented by any one of the chemical formulas A through C mentioned above.

[0043] X of the above chemical formula 1-1 1 This can be represented by any one of the above chemical formulas B-1 to B-5.

[0044] The polishing slurry may further contain a secondary histidine derivative having a substituted or unsubstituted amic acid group.

[0045] The second histidine derivative can be represented by the chemical formulas 1-2.

[0046] X of the above chemical formula 1-2 2 This can be represented by any one of the chemical formulas D through F mentioned above.

[0047] X of the above chemical formula 1-2 2 This can be represented by any one of the above chemical formulas E-1 to E-5.

[0048] The conductive layer may include a molybdenum-containing layer.

[0049] The polishing rate of the molybdenum-containing layer may be approximately 110 Å / min or more, and the etching rate of the molybdenum-containing layer may be less than approximately 80 Å / min.

[0050] The ratio of the polishing rate to the etching rate of the molybdenum-containing layer may be approximately 3 or more.

[0051] Furthermore, other embodiments provide the compound shown in chemical formula 1-1.

[0052] Furthermore, other embodiments provide compounds represented by the chemical formulas 1-2.

[0053] This method allows for the removal of the workpiece at a high polishing speed while effectively reducing the loss and defects of the workpiece due to excessive corrosion or over-etching. [Brief explanation of the drawing]

[0054] [Figure 1] This is a cross-sectional view showing an example of a method for manufacturing a semiconductor device according to one embodiment. [Figure 2] This is a cross-sectional view showing an example of a method for manufacturing a semiconductor device according to one embodiment. [Figure 3] This is a cross-sectional view showing an example of a method for manufacturing a semiconductor device according to one embodiment. [Figure 4] This is a cross-sectional view showing an example of a method for manufacturing a semiconductor device according to one embodiment. [Figure 5] This is a schematic diagram showing an example of chemical mechanical polishing equipment. [Figure 6] This graph shows the polishing rate and etching rate of the molybdenum layer of polishing slurry in a manufacturing example and a comparative manufacturing example. [Figure 7] This graph shows the ratio of polishing rate to etching rate relative to the molybdenum layer of polishing slurry, based on a manufacturing example and a comparative manufacturing example. [Modes for carrying out the invention]

[0055] The following examples will be described in detail so that they can be easily implemented by a person with ordinary skill in the art. However, the structures that are actually applied can be implemented in a variety of different forms and are not limited to the examples described herein.

[0056] In the drawings, thicknesses are shown enlarged to clearly represent various layers and regions. Similar parts are denoted by the same drawing reference numerals throughout the specification. When a layer, film, region, plate, or other part is described as being "on top of" another part, this includes not only when it is "directly on top" of the other part, but also when there is another part in between. Conversely, when one part is described as being "directly on top of" another part, it means that there is no other part in between.

[0057] Hereinafter, unless otherwise defined, "substituted" means that the hydrogen atoms in a compound are substituted with a substituent selected from halogen atoms, hydroxyl groups, alkoxy groups, nitro groups, cyano groups, amino groups, azide groups, amidino groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamyl groups, thiol groups, ester groups, carboxyl groups and their salts, sulfonic acid groups and their salts, phosphoric acid and its salts, silyl groups, C1-C20 alkyl groups, C2-C20 alkenyl groups, C2-C20 alkynyl groups, C6-C30 aryl groups, C7-C30 arylalkyl groups, C1-C30 alkoxy groups, C1-C20 heteroalkyl groups, C3-C20 heteroaryl groups, C3-C20 heteroarylalkyl groups, C3-C30 cycloalkyl groups, C3-C15 cycloalkenyl groups, C6-C15 cycloalkynyl groups, C3-C30 heterocycloalkyl groups, and combinations thereof.

[0058] Unless otherwise defined, "hetero" means containing one to four heteroatoms selected from N, O, S, Se, Te, Si, and P.

[0059] Hereinafter, "combination" includes mixed and layered structures of two or more components.

[0060] The following describes a polishing slurry according to one embodiment.

[0061] Polishing slurry can be used in the manufacturing process of semiconductor devices to flatten solid surfaces, such as the surface of a semiconductor substrate (including thin films such as insulating or metal layers), or to remove steps or unevenness on solid surfaces.

[0062] The polishing slurry according to one embodiment contains an abrasive, an oxidizing agent, and an additive.

[0063] Abrasives can be abrasive particles capable of removing an object to be abraded, and can be applied to a solid surface covering the object to be abraded to remove the object chemically and / or physically. Abrasives can have a certain hardness capable of removing the object to be abraded, and can, for example, have a higher hardness than the object to be abraded (e.g., a metal or semimetal) or its oxide (e.g., a metal oxide or semimetal oxide).

[0064] The abrasive can be, for example, spherical, plate-shaped, linear, and / or amorphous particles, and the particle size (average particle size, major axis, or length) of the abrasive can be, for example, between about 1 nm and 150 nm. The abrasive can also include, for example, fine abrasives between about 1 nm and less than about 50 nm.

[0065] The abrasives may include, for example, oxide abrasives, nitride abrasives, carbon abrasives, or combinations thereof, and may be, but are not limited to, silica, ceria, alumina, zirconia, titania, silicon nitride, SiC, diamond, fullerene, derivatives thereof, or combinations thereof.

[0066] The abrasive may be present in an amount of approximately 20% by weight or less relative to the polishing slurry, for example, from approximately 0.001% to 20% by weight, from approximately 0.001% to 15% by weight, from approximately 0.001% to 10% by weight, from approximately 0.001% to 8% by weight, from approximately 0.001% to 5% by weight, from approximately 0.001% to 3% by weight, from approximately 0.01% to 2% by weight, from approximately 0.1% to 1.5% by weight, from approximately 0.2% to 1% by weight, or from approximately 0.3% to 0.7% by weight.

[0067] Oxidizing agents can oxidize the material to be polished. For example, when applying a polishing slurry to a material containing a metal or semimetal, the surface of the material can be oxidized to form a metal oxide or semimetal oxide. The material oxidized by the oxidizing agent (e.g., a metal oxide or semimetal oxide) may have a relatively lower hardness than the metal or semimetal and may be easily brittle. Due to the difference in mechanical strength between the material to be polished and the oxidized material, it can be effectively removed by the aforementioned abrasive.

[0068] The oxidizing agent is not limited as long as it can oxidize the object to be polished, and may include, for example, hydrogen peroxide, peracetic acid, percarbonates, urea peroxide, perchloride acid, persulfates, or combinations thereof.

[0069] The oxidizing agent may be present in an amount of about 5% by weight or less relative to the polishing slurry, and within the above range, it may be present in amounts of about 0.001% to 5% by weight, 0.001% to 4% by weight, 0.001% to 3% by weight, 0.001% to 2% by weight, 0.001% to 1% by weight, 0.001% to 0.5% by weight, about 0.01% to 0.3% by weight, about 0.2% to 0.1% by weight, or about 0.03% to 0.05% by weight.

[0070] The additive may contain one or more histidine derivatives. Histidine derivatives can act as corrosion inhibitors and can effectively prevent or reduce corrosion and / or over-etching of the workpiece or its oxide (oxidized by the oxidizing agent) during or after the polishing process.

[0071] Histidine derivatives may include primary histidine derivatives having a substituted or unsubstituted cyclic imide group instead of the amino group of substituted or unsubstituted histidine. The cyclic imide group may have a ring structure containing two carbonyl groups bonded to nitrogen.

[0072] As an example, the first histidine derivative can be represented by the following chemical formula 1-1.

[0073] [ka]

[0074] In the above chemical formula 1-1, X 1 This can be a substituted or unsubstituted ring imide group, R 1 , R 2a , R 2b , R 3a , and R 3b Each of these can independently be hydrogen, deuterium, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R 1 , R 2a , R 2b , R 3a , and R 3b These elements can exist independently, or two adjacent elements can join together to form a ring.

[0075] The first histidine derivative shown in chemical formula 1-1 can be obtained by reacting a histidine having a substituted or unsubstituted imidazole group and an amino group with a cyclic acid anhydride, and the substituted or unsubstituted ring imide group (X) of chemical formula 1-1 1 The first histidine derivative can be determined by the type of cyclic acid anhydride. However, it is not limited to this, and the first histidine derivative can be obtained by various methods.

[0076] As an example, R in chemical formula 1-1 1 , R 2a , R 2b , R 3a , and R 3b Each of these can independently be hydrogen, deuterium, a C1-C20 alkyl group, a halogen-substituted C1-C20 alkyl group, a C2-C20 alkenyl group, a halogen-substituted C2-C20 alkenyl group, a C2-C20 alkynyl group, a halogen-substituted C2-C20 alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a carboxyl group, a hydroxyl group, a cyano group, a halogen (F, Cl, Br, or I), or a combination thereof.

[0077] As an example, R in chemical formula 1-1 1 , R 2a , R 2b , R 3a , and R 3bEach of these can independently be hydrogen, deuterium, methyl group, ethyl group, propyl group, butyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, halogen-substituted methyl group, halogen-substituted ethyl group, halogen-substituted propyl group, halogen-substituted butyl group, halogen-substituted ethenyl group, halogen-substituted propenyl group, halogen-substituted butenyl group, halogen-substituted ethynyl group, halogen-substituted propynyl group, halogen-substituted butynyl group, phenyl group, biphenyl group, naphthyl group, halogen-substituted phenyl group, halogen-substituted biphenyl group, halogen-substituted naphthyl group, carboxyl group, halogen (F, Cl, Br or I), or a combination thereof.

[0078] As an example, R in chemical formula 1-1 1 , R 2a , R 2b , R 3a , and R 3b Each of these can independently be hydrogen.

[0079] As an example, X in chemical formula 1-1 1 It can be represented by any one of the following chemical formulas A through C.

[0080] [ka]

[0081] In chemical formulas A through C, R 4 From R 9 Each of these can independently be hydrogen, deuterium, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R 4 From R 9 These can exist independently, or two adjacent elements can join together to form a ring. n can be an integer from 1 to 5. * may be a linking point with the aforementioned chemical formula 1-1.

[0082] For example, R in chemical formulas A through C 4 From R 9 Each of these can independently be hydrogen, deuterium, a C1-C20 alkyl group, a halogen-substituted C1-C20 alkyl group, a C2-C20 alkenyl group, a halogen-substituted C2-C20 alkenyl group, a C2-C20 alkynyl group, a halogen-substituted C2-C20 alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a carboxyl group, a hydroxyl group, a cyano group, a halogen (F, Cl, Br, or I), or a combination thereof.

[0083] For example, R in chemical formulas A through C 4 From R 9 Each of these can independently be hydrogen, deuterium, methyl group, ethyl group, propyl group, butyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, halogen-substituted methyl group, halogen-substituted ethyl group, halogen-substituted propyl group, halogen-substituted butyl group, halogen-substituted ethenyl group, halogen-substituted propenyl group, halogen-substituted butenyl group, halogen-substituted ethynyl group, halogen-substituted propynyl group, halogen-substituted butynyl group, phenyl group, biphenyl group, naphthyl group, halogen-substituted phenyl group, halogen-substituted biphenyl group, halogen-substituted naphthyl group, carboxyl group, halogen (F, Cl, Br or I), or a combination thereof.

[0084] For example, R in chemical formula A 4 and R 5 These can each be hydrogen.

[0085] For example, R in chemical formula A 4 and R 5 One of them can be hydrogen, R 4 and R 5The other of these may be a C1-C20 alkyl group, a halogen-substituted C1-C20 alkyl group, a C2-C20 alkenyl group, a halogen-substituted C2-C20 alkenyl group, a C2-C20 alkynyl group, a halogen-substituted C2-C20 alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a carboxyl group, a hydroxyl group, a cyano group, a halogen (F, Cl, Br or I), or a combination thereof.

[0086] For example, R in chemical formula A 4 and R 5 These can combine to form a ring, where the ring may include a substituted or unsubstituted C3-C20 aliphatic ring, a substituted or unsubstituted C6-C20 aromatic ring, or a combination thereof.

[0087] For example, R in chemical formula B 4 From R 7 These can each be hydrogen.

[0088] For example, R in chemical formula B 4 From R 6 Each of these can be hydrogen, and R 7 This can be a C1-C20 alkyl group, a halogen-substituted C1-C20 alkyl group, a C2-C20 alkenyl group, a halogen-substituted C2-C20 alkenyl group, a C2-C20 alkynyl group, a halogen-substituted C2-C20 alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a carboxyl group, a hydroxyl group, a cyano group, a halogen (F, Cl, Br or I), or a combination thereof.

[0089] For example, R in chemical formula B 4 From R 7 Two of these can combine to form a ring, which may include substituted or unsubstituted C3-C20 aliphatic rings, substituted or unsubstituted C6-C20 aromatic rings, or a combination thereof.

[0090] For example, n in chemical formula B can be 1, 2, or 3.

[0091] For example, the R of the chemical formula C 4 , R 6 , R 8 , and R 9 These can each be hydrogen.

[0092] For example, the R of the chemical formula C 4 , R 6 , R 8 , and R 9 Two of these can combine to form a ring, which may include substituted or unsubstituted C3-C20 aliphatic rings, substituted or unsubstituted C6-C20 aromatic rings, or a combination thereof.

[0093] For example, n in the chemical formula C can be 1, 2, or 3.

[0094] As an example, X in chemical formula 1-1 1 It can be represented by one of the following chemical formulas B-1 to B-5.

[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098] 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 , R10b , R 11 , R 11a , R 11b , R 12 , R 12a , R 12b , R 13 , R 13a , and R 13b Each of these can independently be hydrogen, deuterium, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. 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 These can exist independently, or two adjacent elements can join together to form a ring. m can be an integer from 0 to 5. * may be a linking point with the aforementioned chemical formula 1-1.

[0099] For example, R in chemical formulas B-1 to B-5 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 independently be hydrogen, deuterium, a C1-C20 alkyl group, a halogen-substituted C1-C20 alkyl group, a C2-C20 alkenyl group, a halogen-substituted C2-C20 alkenyl group, a C2-C20 alkynyl group, a halogen-substituted C2-C20 alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a carboxyl group, a hydroxyl group, a cyano group, a halogen (F, Cl, Br, or I), or a combination thereof.

[0100] For example, R in chemical formulas B-1 to B-5 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 independently be hydrogen, deuterium, methyl group, ethyl group, propyl group, butyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, halogen-substituted methyl group, halogen-substituted ethyl group, halogen-substituted propyl group, halogen-substituted butyl group, halogen-substituted ethenyl group, halogen-substituted propenyl group, halogen-substituted butenyl group, halogen-substituted ethynyl group, halogen-substituted propynyl group, halogen-substituted butynyl group, phenyl group, biphenyl group, naphthyl group, halogen-substituted phenyl group, halogen-substituted biphenyl group, halogen-substituted naphthyl group, carboxyl group, halogen (F, Cl, Br or I), or a combination thereof.

[0101] For example, the value of m in chemical formulas B-1 to B-5 can be 0, 1, 2, or 3.

[0102] For example, R in chemical formulas B-1 to B-5 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 independently be hydrogen.

[0103] For example, R in chemical formulas B-1 to B-3 10a and R 13a These can bond to form a ring, where the ring may include substituted or unsubstituted C3-C20 aliphatic rings, substituted or unsubstituted C6-C20 aromatic rings, or combinations thereof.

[0104] For example, R in chemical formulas B-1 to B-3 11a and R 13a These can bond to form a ring, where the ring may include substituted or unsubstituted C3-C20 aliphatic rings, substituted or unsubstituted C6-C20 aromatic rings, or combinations thereof.

[0105] For example, R in chemical formula B-4 10 From R 13 Any two of these can combine to form a ring, where the ring may include substituted or unsubstituted C3-C20 aliphatic rings, substituted or unsubstituted C6-C20 aromatic rings, or a combination thereof.

[0106] As an example, R in chemical formula B-4 10 From R 13Any one of them may be a carboxyl group.

[0107] The histidine derivative can include a second histidine derivative having a substituted or unsubstituted amic acid group in place of the amino group of substituted or unsubstituted histidine. The amic acid group can have an acyclic structure containing one or more amide groups and one or more carboxylic acids or carboxylates.

[0108] As an example, the second histidine derivative can be represented by Chemical Formula 1-2 below.

[0109]

Chemical Formula

[0110] In Chemical Formula 1-2, X 2 can be a substituted or unsubstituted amic acid group, R 1 、R 2a 、R 2b 、R 3a 、and R 3b can each independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxy group, a halogen or a cyano group, R 1 、R 2a 、R 2b 、R 3a 、and R 3b can each independently exist or two adjacent ones of these can combine to form a ring.

[0111] The second histidine derivative shown in Chemical Formula 1-2 can be obtained, for example, by a ring-opening reaction or the like when reacting histidine having a substituted or unsubstituted imidazole group and an amino group with a cyclic anhydride. The substituted or unsubstituted amic acid (X 2 ) of Chemical Formula 1-2 can be determined by the type of cyclic anhydride. However, it is not limited thereto, and the second histidine derivative can be obtained by various methods.

[0112] For example, R 1 , R 2a , R 2b , R 3a , and R 3b of Chemical Formula 1-2 can each independently be hydrogen, deuterium, a C1 to C20 alkyl group, a halogen-substituted C1 to C20 alkyl group, a C2 to C20 alkenyl group, a halogen-substituted C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a halogen-substituted C2 to C20 alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a carboxyl group, a hydroxy group, a cyano group, a halogen (F, Cl, Br or I), or a combination thereof.

[0113] For example, R 1 , R 2a , R 2b , R 3a , and R 3b of Chemical Formula 1-2 can each independently be hydrogen, deuterium, a methyl group, an ethyl group, a propyl group, a butyl group, an ethenyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, a butynyl group, a halogen-substituted methyl group, a halogen-substituted ethyl group, a halogen-substituted propyl group, a halogen-substituted butyl group, a halogen-substituted ethenyl group, a halogen-substituted propenyl group, a halogen-substituted butenyl group, a halogen-substituted ethynyl group, a halogen-substituted propynyl group, a halogen-substituted butynyl group, a phenyl group, a biphenyl group, a naphthyl group, a halogen-substituted phenyl group, a halogen-substituted biphenyl group, a halogen-substituted naphthyl group, a carboxyl group, a halogen (F, Cl, Br or I), or a combination thereof.

[0114] For example, R in chemical formula 1-2 1 , R 2a , R 2b , R 3a , and R 3b Each of these can independently be hydrogen.

[0115] As an example, X in chemical formula 1-2 2 It can be represented by one of the following chemical formulas D through F.

[0116] [ka]

[0117] In chemical formulas D through F, R 4 From R 9 Each of these can independently be hydrogen, deuterium, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R 4 From R 9 These can exist independently, or two of them can combine to form a ring. n can be an integer from 1 to 5. * may be a linking point with chemical formula 1-2.

[0118] For example, R in chemical formulas D through F 4 From R 9Each of these can independently be hydrogen, deuterium, a C1-C20 alkyl group, a halogen-substituted C1-C20 alkyl group, a C2-C20 alkenyl group, a halogen-substituted C2-C20 alkenyl group, a C2-C20 alkynyl group, a halogen-substituted C2-C20 alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a carboxyl group, a hydroxyl group, a cyano group, a halogen (F, Cl, Br, or I), or a combination thereof.

[0119] For example, R in chemical formulas D through F 4 From R 9 Each of these can independently be hydrogen, deuterium, methyl group, ethyl group, propyl group, butyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, halogen-substituted methyl group, halogen-substituted ethyl group, halogen-substituted propyl group, halogen-substituted butyl group, halogen-substituted ethenyl group, halogen-substituted propenyl group, halogen-substituted butenyl group, halogen-substituted ethynyl group, halogen-substituted propynyl group, halogen-substituted butynyl group, phenyl group, biphenyl group, naphthyl group, halogen-substituted phenyl group, halogen-substituted biphenyl group, halogen-substituted naphthyl group, carboxyl group, halogen (F, Cl, Br or I), or a combination thereof.

[0120] For example, R in chemical formula D 4 and R 5 These can each be hydrogen.

[0121] For example, R in chemical formula D 4 and R 5 One of them can be hydrogen, R 4 and R 5The other of these may be a C1-C20 alkyl group, a halogen-substituted C1-C20 alkyl group, a C2-C20 alkenyl group, a halogen-substituted C2-C20 alkenyl group, a C2-C20 alkynyl group, a halogen-substituted C2-C20 alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a carboxyl group, a hydroxyl group, a cyano group, a halogen (F, Cl, Br or I), or a combination thereof.

[0122] For example, R in chemical formula D 4 and R 5 These can combine to form a ring, where the ring may include a substituted or unsubstituted C3-C20 aliphatic ring, a substituted or unsubstituted C6-C20 aromatic ring, or a combination thereof.

[0123] For example, the R of chemical formula E 4 From R 7 These can each be hydrogen.

[0124] For example, the R of chemical formula E 4 From R 6 Each of them can be hydrogen, and R 7 This can be a C1-C20 alkyl group, a halogen-substituted C1-C20 alkyl group, a C2-C20 alkenyl group, a halogen-substituted C2-C20 alkenyl group, a C2-C20 alkynyl group, a halogen-substituted C2-C20 alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a carboxyl group, a hydroxyl group, a cyano group, a halogen (F, Cl, Br or I), or a combination thereof.

[0125] For example, the R of chemical formula E 4 From R 7 Two of these can combine to form a ring, which may include substituted or unsubstituted C3-C20 aliphatic rings, substituted or unsubstituted C6-C20 aromatic rings, or a combination thereof.

[0126] For example, n in Chemical Formula E can be 1, 2, or 3.

[0127] For example, R in Chemical Formula F 4 , R 6 , R 8 , and R 9 can each be hydrogen.

[0128] For example, two of R 4 , R 6 , R 8 , and R 9 in Chemical Formula F can combine to form a ring. Here, the ring can include a substituted or unsubstituted C3 to C20 aliphatic ring, a substituted or unsubstituted C6 to C20 aromatic ring, or a combination of these.

[0129] For example, n in Chemical Formula F can be 1, 2, or 3.

[0130] As an example, X in Chemical Formula 1-2 2 can be represented by any one of the following Chemical Formulas E-1 to E-5.

[0131]

Chemical Formula

[0132]

Chemical Formula

[0133]

Chemical Formula

[0134] In Chemical Formulas E-1 to E-5, R 4a , R 5 , R 6 , R 7 , R 7a , R 8 , R 9 , R <000​​​10b , R 11 , R 11a , R 11b , R 12 , R 12a , R 12b , R 13 , R 13a , and R 13b Each of these can independently be hydrogen, deuterium, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. 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 These can exist independently, or two adjacent elements can join together to form a ring. m can be an integer from 0 to 5. * may be a linking point with chemical formula 1-2.

[0135] For example, R in chemical formulas E-1 to E-5 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 independently be hydrogen, deuterium, a C1-C20 alkyl group, a halogen-substituted C1-C20 alkyl group, a C2-C20 alkenyl group, a halogen-substituted C2-C20 alkenyl group, a C2-C20 alkynyl group, a halogen-substituted C2-C20 alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a carboxyl group, a hydroxyl group, a cyano group, a halogen (F, Cl, Br, or I), or a combination thereof.

[0136] For example, R in chemical formulas E-1 to E-5 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 independently be hydrogen, deuterium, methyl group, ethyl group, propyl group, butyl group, ethenyl group, propenyl group, butenyl group, ethynyl group, propynyl group, butynyl group, halogen-substituted methyl group, halogen-substituted ethyl group, halogen-substituted propyl group, halogen-substituted butyl group, halogen-substituted ethenyl group, halogen-substituted propenyl group, halogen-substituted butenyl group, halogen-substituted ethynyl group, halogen-substituted propynyl group, halogen-substituted butynyl group, phenyl group, biphenyl group, naphthyl group, halogen-substituted phenyl group, halogen-substituted biphenyl group, halogen-substituted naphthyl group, carboxyl group, halogen (F, Cl, Br or I), or a combination thereof.

[0137] For example, the value of m in chemical formulas E-1 to E-5 can be 0, 1, 2, or 3.

[0138] For example, R in chemical formulas E-1 to E-5 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 independently be hydrogen.

[0139] For example, R in chemical formulas E-1 to E-3 10a and R 13a These can bond to form a ring, where the ring may include substituted or unsubstituted C3-C20 aliphatic rings, substituted or unsubstituted C6-C20 aromatic rings, or combinations thereof.

[0140] For example, R in chemical formulas E-1 to E-3 11a and R 13a These can bond to form a ring, where the ring may include substituted or unsubstituted C3-C20 aliphatic rings, substituted or unsubstituted C6-C20 aromatic rings, or combinations thereof.

[0141] For example, R in chemical formula E-4 10 From R 13 Any two of these can combine to form a ring, where the ring may include substituted or unsubstituted C3-C20 aliphatic rings, substituted or unsubstituted C6-C20 aromatic rings, or a combination thereof.

[0142] For example, R in chemical formula E-4 10 From R 13One of these may be a carboxyl group.

[0143] The histidine derivative may include the first histidine derivative described above, the second histidine derivative described above, or a combination thereof.

[0144] The aforementioned histidine derivative (first histidine derivative) may be present in an amount of about 5% by weight or less relative to the polishing slurry, and within the above range, it may be present in amounts of about 0.001% to 5% by weight, 0.001% to 4% by weight, 0.001% to 3% by weight, 0.001% to 2% by weight, 0.001% to 1% by weight, 0.001% to 0.5% by weight, about 0.01% to 0.3% by weight, about 0.01% to 0.1% by weight, or about 0.02% to 0.04% by weight.

[0145] The aforementioned histidine derivative (first histidine derivative) may be included in the polishing slurry at a concentration of about 0.1 mol / L or less, and within the above range, it may be included at concentrations of about 0.001 to 0.1 mol / L, about 0.001 to 0.08 mol / L, about 0.001 to 0.06 mol / L, about 0.001 to 0.05 mol / L, about 0.005 to 0.3 mol / L, about 0.007 to 0.02 mol / L, or about 0.008 to 0.015 mol / L.

[0146] The oxidizing agent and histidine derivative (first histidine derivative) may be included in appropriate proportions to increase 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 oxidizing agent and histidine derivative may be included in molar ratios of about 0.1:10 to 10:0.1, about 1:10 to 10:1, about 2:8 to 8:2, about 3:7 to 7:3, about 4:6 to 6:4, or about 5:5.

[0147] The additives may further include chelating agents, surfactants, dispersants, pH adjusters, reaction catalysts, or combinations thereof.

[0148] The chelating agent may be, but is not limited to, phosphoric acid, nitric acid, citrate, malonic acid, salts thereof, or combinations thereof.

[0149] The surfactant may be an ionic or nonionic surfactant, and may be, but not limited to, an ethylene oxide copolymer, a propylene oxide copolymer, an amine compound, or a combination thereof.

[0150] 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 water-soluble polymers may be, for example, about 10,000 or less, for example, about 5,000 or less, for example, about 3,000 or less. Metal salts may be, for example, copper salts, nickel salts, cobalt salts, manganese salts, tantalum salts, ruthenium salts, or combinations thereof. Dispersants may be selected from, but are not limited to, poly(meth)acrylic acid, poly(meth)acrylonitrile-co-butadiene-acrylic acid, carboxylic acids, sulfonic acid esters, sulfonic acids, phosphate esters, cellulose, diols, salts thereof, or combinations thereof.

[0151] pH adjusters can adjust the pH of the polishing slurry and may be, for example, inorganic acids, organic acids, salts thereof, or combinations thereof. Inorganic acids may include, for example, nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, bromate, iodic acid, potassium hydroxide, sodium hydroxide, or salts thereof, 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, glutaric acid, glutamic acid, glycolic acid, lactic acid, aspartic acid, tartaric acid, or salts thereof.

[0152] A reaction catalyst can accelerate the oxidation reaction of the material to be polished by decomposing the oxidizing agent. The reaction catalyst may be, for example, a metal ion compound capable of effectively generating radicals, and may be a catalyst used in the Fenton reaction or a Fenton-like reaction. The reaction catalyst may include cations such as 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, along with nitrates, sulfates, fluorides, chlorides, bromides, iodides, fluorates, chlorates, bromates, and iodates. The reaction catalyst may include, but is not limited to, anions comprising (iodate), perchlorate, perbromate, periodate, cyanide salt, oxalate, citrate, acetate, acetyl acetonate, gluconate, or combinations thereof. For example, the reaction catalyst may be an iron ion catalyst, which may include, but is not limited to, iron(II) nitrate, iron(III) nitrate, iron(II) sulfate, iron(III) sulfate, iron(II) oxalate, iron(III) oxalate, or combinations thereof.

[0153] Each component of the additive may, but is not limited to, be present in trace amounts ranging from approximately 1 ppm to 100,000 ppm, independently of the others.

[0154] The polishing slurry may further contain a dispersion medium or solvent (hereinafter referred to as "dispersion medium") capable of dissolving and / or dispersing the aforementioned components, the dispersion medium being, for example, water. The water may be, for example, distilled water and / or deionized water. The dispersion medium may be contained in the remainder after removing solids such as abrasives, oxidizing agents, and additives.

[0155] The pH of the polishing slurry may be between 1.0 and 10.0, and within that range, it may be between 1.0 and 7.0 or between 1.0 and 5.0.

[0156] The aforementioned polishing slurry can be applied to the formation of various structures, for example, in the polishing process of conductive materials such as metal layers or in the polishing process of insulators such as shallow trench isolation (STI) or insulating films. As an example, the polishing slurry can be used to polish conductive layers for forming conductive patterns such as metal wires, vias, or electrodes in semiconductor substrates, for example, in polishing tungsten, molybdenum, aluminum, copper, nickel, or alloys thereof, for example, in polishing molybdenum-containing layers such as molybdenum (Mo) or molybdenum alloys.

[0157] The following describes an example of a semiconductor device manufacturing method using the polishing slurry mentioned above.

[0158] A method for manufacturing a semiconductor device according to one embodiment includes the step of performing chemical mechanical polishing (CMP) on the surface of an object to be polished. The object to be polished can be a variety of structures, for example, a semiconductor substrate such as a silicon wafer (including thin films such as dielectric layers or metal layers), and the polished surface can include metals such as molybdenum, aluminum, copper or nickel, alloys thereof or metal oxides or quasimetallic 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 and GaAs; inorganic compounds such as tetraethyl orthosilicate (TEOS); or combinations thereof.

[0159] For example, polishing slurry can be used to polish conductive layers, such as metal layers within semiconductor substrates, and can be used to form metal wiring, vias, or electrodes from metal layers containing molybdenum (Mo) or its alloys.

[0160] The following describes an example of a semiconductor device manufacturing method using the polishing slurry mentioned above.

[0161] Figures 1 to 4 are cross-sectional views showing an example of a semiconductor device manufacturing method according to one embodiment.

[0162] Referring to Figure 1, an insulating layer 20 is formed on the semiconductor substrate 10. The insulating layer 20 may contain oxides, nitrides and / or oxynitrides, and may, for example, be a dielectric layer. Next, the insulating layer 20 is etched to form an opening 20a. The opening 20a may include trenches, via holes and / or contact holes. The opening 20a may have a width of less than about 10 nm. Next, a barrier layer 30 is formed on the wall surface of the opening 20a. The barrier layer 30 may, but is not limited to, Ta and / or TaN.

[0163] Referring to Figure 2, the inside and top of the opening 20a are filled with a metal such as molybdenum (Mo) or a molybdenum alloy to form a conductive layer 40. The conductive layer 40 can 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 a molybdenum alloy.

[0164] Referring to Figure 3, the surface of the conductive layer 40 is planarized to substantially coincide with the surface of the insulating layer 20 to form a filled conductive pattern 40a. Planarization can be performed by chemical mechanical polishing using chemical mechanical polishing (CMP) equipment, and the aforementioned polishing slurry can be used. This will be described later. As an example, if the barrier layer 30 is a Ta layer and the conductive layer 40 is a molybdenum (Mo)-containing layer, then a higher polishing selectivity of Ta to Mo in the polishing slurry is better, for example, a value higher than approximately 50:1 is better.

[0165] Referring to Figure 4, a capping layer 50 is formed on the embedded conductive pattern 40a and the insulating layer 20. The capping layer 50 may, but is not limited to, SiN and / or SiC.

[0166] The following describes the planarization step for forming the embedded conductive pattern 40a. The planarization step can be performed by chemical mechanical polishing using chemical mechanical polishing (CMP) equipment, as described above.

[0167] Figure 5 is a schematic diagram showing an example of chemical mechanical polishing equipment.

[0168] Referring to Figure 5, an example of a chemical mechanical polishing setup 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 positioned on the platen 120; a pad conditioner 160; and at least one polishing slurry supply device 140 positioned adjacent to the polishing pad 150 for supplying polishing slurry to the polishing pad 150.

[0169] The platen 120 can be provided rotatably on the surface of the lower base. For example, the platen 120 may be powered by rotational energy transmitted from a motor (not shown) located within the lower base, thereby allowing it to rotate in a constant direction, such as clockwise or counterclockwise, on a rotation axis 120S perpendicular to the surface of the platen 120.

[0170] The polishing head 130 can be positioned on top of the platen 120 and can hold the object to be polished. The object to be polished may be, for example, a semiconductor substrate 10 such as a wafer. The polishing head 130 may include a rotating shaft 130S for rotating the object to be polished. When polishing is performed, the rotation direction of the polishing head 130 may be opposite to the rotation direction of the platen 120.

[0171] The polishing pad 150 can be positioned on top of the platen 120 so as to be supported by the platen 120. The polishing pad 150 can rotate together with the platen 120. The polishing pad 150 can have a roughly formed polishing surface 150S. Such a polishing surface 150S can mechanically polish the surface of the semiconductor substrate 10 in direct contact with it. The polishing pad 150 can be made of a porous material having a plurality of microspaces, the plurality of microspaces can contain a polishing slurry. The polishing surface 150S of the polishing pad 150 can include a surface that is in direct contact with the object to be polished and a predetermined depth therefrom, the predetermined depth can be about 10% to 100%, about 20% to 100%, about 30% to 100%, about 40% to 100%, or about 50% to 100% of the thickness of the polishing pad 150. The polishing surface 150S of the polishing pad 150 can be, for example, flat. The polishing surface 150S of the polishing pad 150 may have, for example, protrusions or grooves.

[0172] The pad conditioner 160 can be positioned adjacent to the polishing pad 150 and can maintain the condition of the polishing surface so that the surface of the semiconductor substrate 10 is effectively polished during the polishing process.

[0173] The polishing slurry supply device 140 can be positioned adjacent to the polishing pad 150 and can supply polishing slurry to the polishing pad 150 from the polishing slurry tank 145. The polishing slurry supply device 140 may include a nozzle that can supply polishing slurry onto the polishing pad 150 during the polishing process. The polishing slurry supply device 140 can supply the aforementioned polishing slurry.

[0174] Chemical mechanical polishing can be performed, for example, by the steps of: positioning the semiconductor substrate 10 and the polishing pad 150 facing each other; supplying the aforementioned polishing slurry from the polishing slurry supply device 140 between the semiconductor substrate 10 and the polishing pad 150; and bringing the surface of the semiconductor substrate 10 and the polishing pad 150 into contact to perform polishing.

[0175] For example, the polishing slurry can be supplied at a rate of, for instance, approximately 10 ml / min to 300 ml / min.

[0176] The polishing stage can be performed by bringing the polishing pad 150 into contact with the surface of the semiconductor substrate 10 and rotating it, thereby generating mechanical friction. For example, a pressure of approximately 1 psi to 5 psi can be applied during the polishing stage.

[0177] For example, the oxidizing agent in the aforementioned polishing slurry can oxidize the polishing surface (e.g., a metal such as molybdenum) to form a metal oxide (e.g., molybdenum oxide) to a predetermined thickness on the polishing surface, and the polishing agent in the polishing stage can physically and / or chemically remove the metal oxide from the polishing surface to perform polishing. The histidine derivative in the aforementioned polishing slurry can effectively prevent defects caused by excessive corrosion or over-etching of the polishing surface (e.g., a metal such as molybdenum) during the polishing stage as a corrosion inhibitor. Such oxidation of the polishing surface and prevention of corrosion or over-etching can be performed simultaneously or sequentially.

[0178] In this way, the polishing slurry, by containing an abrasive, an oxidizing agent, and the aforementioned histidine derivative, can increase the polishing speed of the workpiece while effectively reducing or preventing losses and defects due to excessive corrosion or over-etching.

[0179] For example, the conductive layer 40 may include a molybdenum-containing layer, and the removal rate (RR) of the molybdenum-containing layer may be about 110 Å / min or more, and within the range of about 110 Å / min to 1000 Å / min, about 120 Å / min to 1000 Å / min, about 130 Å / min to 1000 Å / min, about 130 Å / min to 500 Å / min, about 135 Å / min to 300 Å / min, about 140 Å / min to 200 Å / min, or about 140 Å / min to 150 Å / min, and the etching rate (static etching) of the molybdenum-containing layer The polishing rate (SER) may be less than approximately 80 Å / min, and within the range it may be approximately 1 Å / min or more but less than 80 Å / min, approximately 3 Å / min to 70 Å / min, approximately 5 Å / min to 60 Å / min, approximately 5 Å / min to 40 Å / min, approximately 6 Å / min to 20 Å / min, approximately 7 Å / min to 15 Å / min, or approximately 7.5 Å / min to 12 Å / min. For example, the ratio of the polishing rate to the etching rate of the molybdenum-containing layer may be approximately 3 or more, and within the range it may be approximately 3 to 80, approximately 5 to 80, approximately 7 to 80, approximately 9 to 80, approximately 10 to 80, approximately 12 to 80, approximately 12 to 50, approximately 12 to 40, or approximately 12 to 20.

[0180] The above describes one example of a semiconductor device manufacturing method, but it is not limited to this and can be applied to semiconductor devices of various structures.

[0181] The above-mentioned embodiments will be described in more detail below through the examples provided. However, the following embodiments are for illustrative purposes only and do not limit the scope of rights.

[0182] Example of synthesis Synthesis Example 1 Prepare an itaconic anhydride solution by dissolving 3 g of itaconic anhydride in 20 mL of acetic acid in a 250 mL round-bottom flask. In another flask, dissolve 4.0 g of L-histidine in 30 mL of acetic acid, and add it dropwise to the itaconic anhydride solution. The reaction is carried out overnight at room temperature. Precipitate the resulting reaction product in acetone, and drain the acetone to obtain the precipitate. Next, dissolve the precipitate in water, reprecipitate twice in acetone, and freeze-dry to obtain 5.97 g of histidine derivatives of compounds 1-1a and 1-2a in crystalline powder form. The yield is 93%.

[0183] [ka] 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).

[0184] Synthesis Example 2 Prepare a maleic anhydride solution by dissolving 2.557 g of maleic anhydride in 40 mL of acetic acid in a 250 mL round-bottom flask. In another flask, dissolve 4.0 g of L-histidine in 40 mL of acetic acid, and add it dropwise to the maleic anhydride solution. The reaction is carried out overnight at room temperature. Precipitate the resulting reaction product in acetone, and drain the acetone to obtain the precipitate. Next, dissolve the precipitate in water, reprecipitate twice in acetone, and freeze-dry to obtain 5.29 g of histidine derivatives of compounds 1-1b and 1-2b in crystalline powder form. The yield is 81%.

[0185] [ka] 1H 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).

[0186] Manufacturing example Manufacturing Example 1 A pH 2.0 polishing slurry is prepared by mixing 0.5 wt% colloidal silica (average particle size 30 nm), 0.034 wt% (0.01 mol / L) hydrogen peroxide, 0.0249 wt% (0.01 mol / L) histidine derivative obtained from Synthesis Example 1, a small amount of nitric acid, and the remaining amount of deionized water.

[0187] Manufacturing Example 2 A polishing slurry is prepared in the same manner as in Preparation Example 1, except that it contains 0.235% by weight (0.01 mol / L) of the histidine derivative obtained from Synthesis Example 2 instead of compound 1-1 obtained from Synthesis Example 1.

[0188] Comparative Manufacturing Example 1 A polishing slurry is prepared in the same manner as in Production Example 1, except that it does not contain the histidine derivative obtained from Synthesis Example 1.

[0189] Comparative Manufacturing Example 2 A polishing slurry is prepared in the same manner as in Production Example 1, except that it contains L-histidine (Sigma-Aldrich) shown in the following chemical formula A instead of the histidine derivative obtained from Synthesis Example 1.

[0190] [ka]

[0191] Rating I The removal rate (RR) of the molybdenum layer of the polishing slurry produced by manufacturing examples 1 and 2 will be evaluated.

[0192] Chemical mechanical polishing (CMP) will be performed under the following conditions.

[0193] (1) CMP equipment: GNP POLI-400L (G&P Technology, Inc.) (2) Object to be polished: 40mm x 40mm silicon wafer coupon with a 5000Å thick molybdenum layer formed by PVD (3) Polishing head rotation speed: 87 rpm (4) Polishing platen rotation speed: 93 rpm (5) Applied pressure: 3 psi (6)Initial temperature: 24℃ (7) Polishing slurry: Polishing slurry according to production examples 1 and 2 (45°C) (8) Polishing slurry supply flow rate: 130 ml / min (9) Polishing time: 1 minute The chemical mechanical polishing rate (RR) is calculated using the following formula 1.

[0194] The thickness of the molybdenum layer in calculation formula 1 is measured using a resistance meter (KLA Tencor, model "RS-100") with the DC4-probe method, and calculated from the sheet resistance and volume resistivity of the molybdenum layer using calculation formula 2 below.

[0195] [Formula 1] Polishing speed (RR, Å / min) = (Thickness of molybdenum layer before polishing (Å) - Thickness of molybdenum layer after polishing (Å)) / Polishing time (min) [Formula 2] Molybdenum layer thickness (Å) = [Volume resistivity (Ω·m) ÷ Sheet resistance (Ω)] x 10 10 Evaluation II The etching rate (static etching rate, SER) of the molybdenum layer of the polishing slurry produced by Manufacturing Examples 1 and 2 will be evaluated.

[0196] A 40mm x 40mm silicon wafer, on which a 5000 Å thick molybdenum layer has been formed by PVD, is immersed for 30 minutes in the polishing slurry according to Manufacturing Examples 1 and 2 and Comparative Manufacturing Examples 1 and 2. The silicon wafer is then removed and washed with deionized water. The thickness of the molybdenum layer before and after immersion is measured using the same method as described above, and the etching rate (SER, Å / min) is calculated using the following formula 3.

[0197] [Formula 3] Etching rate (SER, Å / min) = (Thickness of molybdenum layer before immersion (Å) - Thickness of molybdenum layer after immersion (Å)) / Immersion time (min) The results are shown in Table 1 and Figures 6 and 7.

[0198] Figure 6 is a graph showing the polishing rate and etching rate of the molybdenum layer of the polishing slurry for the manufacturing example and the comparative manufacturing example, and Figure 7 is a graph showing the ratio of the polishing rate and etching rate of the molybdenum layer of the polishing slurry for the manufacturing example and the comparative manufacturing example.

[0199] [Table 1]

[0200] Referring to Table 1 and Figures 6 and 7, it can be confirmed that the polishing slurries produced in Production Examples 1 and 2 can significantly reduce the etching rate compared to the polishing slurry produced in Comparative Production Example 1. From this, it can be confirmed that the histidine derivative (corrosion inhibitor) obtained from the synthesis examples can effectively reduce corrosion or over-etching of the molybdenum layer.

[0201] Furthermore, it was confirmed that the polishing slurries produced in Production Examples 1 and 2 could increase the polishing speed and decrease the etching speed compared to the polishing slurry produced in Comparative Production Example 2. From this, it was confirmed that the histidine derivative obtained from the synthesis examples could increase the polishing speed and effectively reduce corrosion or over-etching compared to histidine. From this, it was confirmed that the polishing slurries produced in Production Examples 1 and 2 had a polishing speed ratio to the etching speed of the molybdenum layer that was more than five times higher compared to the polishing slurries produced in Comparative Production Examples 1 and 2.

[0202] Although preferred embodiments have been described in detail above, the scope of the rights is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concepts defined in the following claims also fall within the scope of the rights. [Explanation of symbols]

[0203] 10: Semiconductor substrates 20: Insulating layer 20a: Opening 30: Barrier layer 40: Conductive layer 40a: Embedded conductive pattern 50: Capping layer 100:Chemical mechanical polishing equipment 120: Platen 130: Polishing head 140: Polishing slurry supply unit 150: Polishing pad 150S: Polishing surface of polishing pad 160: Pad Conditioner

Claims

1. Abrasives, Oxidizing agents, and, Primary histidine derivatives having substituted or unsubstituted ring imide groups A polishing slurry containing [amount].

2. The first histidine derivative is the polishing slurry according to claim 1, represented by the following chemical formula 1-1: 【Chemistry 1】 In the above chemical formula 1-1, X １ These are substituted or unsubstituted ring imide groups, R １ , R ２ａ , R ２ｂ , R ３ａ , and R ３ｂ Each of these is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R １ 、R ２ａ 、R ２ｂ 、R ３ａ 、and R ３ｂ exist independently or two of these combine to form a ring.

3. X of the above chemical formula 1-1 １ The polishing slurry according to claim 2, which is represented by any one of the following chemical formulas A to C: 【Chemistry 2】 In the aforementioned chemical formulas A to C, R ４ From R ９ Each of these is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R ４ From R ９ These can exist independently, or two of them can combine to form a ring. n is an integer from 1 to 5. * indicates the connection point with the aforementioned chemical formula 1-1.

4. X of the above chemical formula 1-1 １ The polishing slurry according to claim 2, represented by any one of the following chemical formulas B-1 to B-5: 【Transformation 3】 In the aforementioned 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 is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. 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 These can exist independently, or two adjacent elements can join together to form a ring. m is an integer from 0 to 5. * indicates the connection point with the aforementioned chemical formula 1-1.

5. The polishing slurry according to claim 1, further comprising a secondary histidine derivative having a substituted or unsubstituted amic acid group.

6. The second histidine derivative is the polishing slurry according to claim 5, represented by the following chemical formulas 1-2: 【Chemistry 4】 In the aforementioned chemical formula 1-2, X ２ These are substituted or unsubstituted amic acid groups, R １ , R ２ａ , R ２ｂ , R ３ａ , and R ３ｂ Each of these is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R １ , R ２ａ , R ２ｂ , R ３ａ , and R ３ｂ These elements can exist independently, or two of them can combine to form a ring.

7. X of the above chemical formula 1-2 ２ The polishing slurry according to claim 6, represented by any one of the following chemical formulas D to F: 【Transformation 5】 In the aforementioned chemical formulas D to F, R ４ From R ９ Each of these is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R ４ From R ９ These can exist independently, or two of them can combine to form a ring. n is an integer from 1 to 5. * indicates the connection point with chemical formula 1-2.

8. X of the above chemical formula 1-2 ２ The polishing slurry according to claim 6, represented by any one of the following chemical formulas E-1 to E-5: 【Transformation 6】 In the aforementioned 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 are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a carboxyl group, a hydroxy group, a halogen or a cyano group, 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 exist independently of each other, or two adjacent ones of these combine to form a ring, m is an integer from 0 to 5. * indicates the connection point with chemical formula 1-2.

9. The first histidine derivative is shown in the following chemical formula 1-1, The polishing slurry according to claim 1, further comprising a secondary histidine derivative having a substituted or unsubstituted amic acid group as shown in the following chemical formulas 1-2. 【Transformation 7】 In the aforementioned chemical formula 1-1 or 1-2, X １ These are substituted or unsubstituted ring imide groups, X ２ These are substituted or unsubstituted amic acid groups, R １ , R ２ａ , R ２ｂ , R ３ａ , and R ３ｂ Each of these is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R １ , R ２ａ , R ２ｂ , R ３ａ , and R ３ｂ These elements can exist independently, or two of them can combine to form a ring.

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

01.

11. Further containing a dispersion medium, The polishing slurry according to claim 1, wherein the oxidizing agent and the first histidine derivative are each contained in an amount of 0.001% to 5% by weight relative to the polishing slurry.

12. A step of forming a conductive layer on an insulating layer having an opening, The steps include supplying polishing slurry onto the conductive layer, and The step of performing chemical and mechanical polishing on the conductive layer to form a conductive pattern filled in the opening, Includes, The aforementioned polishing slurry is Abrasives, Oxidizing agents, and, A primary histidine derivative having a substituted or unsubstituted ring imide group, A method for manufacturing semiconductor devices, including

13. The first histidine derivative is represented by the following chemical formula 1-1, and is used in the method for manufacturing the semiconductor device according to claim 12: 【Transformation 8】 In the above chemical formula 1-1, X １ These are substituted or unsubstituted ring imide groups, R １ , R ２ａ , R ２ｂ , R ３ａ , and R ３ｂ Each of these is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R １ , R ２ａ , R ２ｂ , R ３ａ , and R ３ｂ These elements can exist independently, or two of them can combine to form a ring.

14. X of the above chemical formula 1-1 １ The method for manufacturing a semiconductor device according to claim 13, which is represented by any one of the following chemical formulas A to C: 【Chemistry 9】 In the aforementioned chemical formulas A to C, R ４ From R ９ Each of these is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R ４ From R ９ These can exist independently, or two of them can combine to form a ring. n is an integer from 1 to 5. * indicates the connection point with the aforementioned chemical formula 1-1.

15. X of the above chemical formula 1-1 １ The method for manufacturing a semiconductor device according to claim 13, represented by any one of the following chemical formulas B-1 to B-5: 【Chemistry 10】 In the aforementioned 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 is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. 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 These can exist independently, or two adjacent elements can join together to form a ring. m is an integer from 0 to 5. * indicates the connection point with the aforementioned chemical formula 1-1.

16. The method for manufacturing a semiconductor device according to claim 12, wherein the polishing slurry further comprises a secondary histidine derivative having a substituted or unsubstituted amic acid group.

17. The second histidine derivative is represented by the following chemical formula 1-2, and is used in the method for manufacturing the semiconductor device according to claim 16: 【Chemistry 11】 In the aforementioned chemical formula 1-2, X ２ These are substituted or unsubstituted amic acid groups, R １ , R ２ａ , R ２ｂ , R ３ａ , and R ３ｂ Each of these is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R １ , R ２ａ , R ２ｂ , R ３ａ , and R ３ｂ These elements can exist independently, or two of them can combine to form a ring.

18. X of the above chemical formula 1-2 ２ The method for manufacturing a semiconductor device according to claim 17, represented by any one of the following chemical formulas D to F: 【Chemistry 12】 In the aforementioned chemical formulas D to F, R ４ From R ９ Each of these is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. R ４ From R ９ These can exist independently, or two of them can combine to form a ring. n is an integer from 1 to 5. * indicates the connection point with chemical formula 1-2.

19. X of the above chemical formula 1-2 ２ The method for manufacturing a semiconductor device according to claim 17, represented by any one of the following chemical formulas E-1 to E-5: 【Chemistry 13】 In the aforementioned 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 is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a carboxyl group, a hydroxyl group, a halogen, or a cyano group. 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 These can exist independently, or two adjacent elements can join together to form a ring. m is an integer from 0 to 5. * indicates the connection point with chemical formula 1-2.

20. The method for manufacturing a semiconductor device according to claim 12, wherein the conductive layer includes a molybdenum-containing layer.

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