METHOD FOR FORMING METAL OXIDE PATTERN AND METHOD FOR MANUFACTURING SEMICONDUCTOR DEVICE

Abstract

The present invention provides a method for forming a pattern of a metal oxide, the method being capable of selectively etching an etching object that contains a metal oxide over a non-etching object, while being capable of forming a metal oxide pattern having the shape of the pattern of the non-etching object that serves as a template for the pattern formation of the metal oxide. According to the present invention, a pattern of a metal oxide is formed by etching a metal oxide, which contains an oxide of at least one of tin and indium, with use of an etching gas. According to the present invention, a predetermined pattern of a template layer (21) is transferred to a metal oxide layer (22) by bringing an etching gas that contains a halon into contact with a member to be etched in the presence of a plasma so as to etch the member to be etched, while applying a bias power to a lower electrode (2) that supports the member to be etched, thereby selectively etching the metal oxide layer (22) over a silicon substrate (24), the template layer (21) and a base layer (23).

Description

[Technical Field]

[0001] The present invention relates to a method for forming a metal oxide pattern and a method for manufacturing a semiconductor device. [Background technology]

[0002] Metal oxides such as tin oxide and indium oxide are used as spacers for forming fin patterns in fin field-effect transistors (FinFETs) and as hard masks for extreme ultraviolet (EUV) lithography. Indium tin oxide (ITO), a mixture of tin oxide and indium oxide, is used to manufacture transparent electrodes. In the semiconductor manufacturing process described above, when microfabricating a metal oxide into a desired shape, there is a step of etching the metal oxide by plasma etching using an etching gas. In this semiconductor manufacturing process, it is important that the etching target (metal oxide) can be selectively etched by the etching gas compared to non-etching targets such as masks that are not etched by the etching gas (i.e., etching selectivity). Hydrogen halides have been proposed as etching gases for etching metal oxides. For example, Patent Documents 1 and 2 disclose techniques for etching tin oxide by plasma etching using etching gases containing hydrogen bromide or hydrogen chloride. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-510994 [Patent Document 2] Japanese Patent Publication No. 6742, 2018 Summary of the Invention [Problem to be solved by the invention]

[0004] However, in the techniques disclosed in Patent Documents 1 and 2, there is a risk that the plasma of the etching gas may etch or embrittle carbon-containing materials such as photoresist and amorphous carbon. Therefore, when the non-etching target of the etched member is formed of a carbon-containing material, the pattern shape of the non-etching target, which serves as a template for forming a metal oxide pattern, may be distorted, and it may be impossible to form a metal oxide pattern in the desired shape.

[0005] An object of the present invention is to provide a method for forming a metal oxide pattern, which can selectively etch an etching target containing a metal oxide compared to a non-etching target, and can form a metal oxide pattern having a shape that follows the pattern shape of the non-etching target, which serves as a template for forming the metal oxide pattern, and a method for manufacturing a semiconductor device. [Means for solving the problem]

[0006] In order to solve the above problems, one aspect of the present invention is as follows [1] to

[14] . [1] A method for forming a pattern of a metal oxide containing at least one of tin and indium oxide by using an etching gas, comprising: a preparation step of preparing an etched member having a substrate, a metal oxide layer containing the metal oxide and laminated on the substrate directly or via an underlayer, and a template layer containing a carbon-containing material and laminated on the metal oxide layer, wherein the metal oxide layer is an etching target that is to be etched with the etching gas, and the substrate, the underlayer, and the template layer are non-etching targets that are not to be etched with the etching gas; a template fabrication step of forming a predetermined pattern on the template layer of the member to be etched; an etching step of using, as the etching gas, a gas containing halon, which has a fluorine atom, a bromine atom, and a carbon atom in its molecule and the number of carbon atoms is 1 to 3, bringing the etching gas into contact with the member to be etched, the template layer of which has been formed with the predetermined pattern in the template preparation step, in the presence of plasma, and performing etching while applying bias power to a lower electrode supporting the member to be etched, thereby selectively etching the metal oxide layer compared to the base material, the template layer, and the underlayer, thereby transferring the predetermined pattern of the template layer to the metal oxide layer; A method for forming a metal oxide pattern comprising:

[0007] [2] The method for forming a metal oxide pattern according to [1], wherein the etching gas is a mixed gas containing the halon and an inert gas. [3] The method for forming a metal oxide pattern according to [1], wherein the etching gas is a mixed gas containing the halon, an inert gas, and a fluorine-containing compound other than the halon. [4] The method for forming a metal oxide pattern according to [2] or [3], wherein the concentration of the halon in the mixed gas is 1% by volume or more and 50% by volume or less.

[0008] [5] The method for forming a metal oxide pattern according to any one of [1] to [4], wherein the carbon-containing material is at least one of a photoresist and amorphous carbon. [6] The method for forming a metal oxide pattern according to any one of [1] to [5], wherein the metal oxide layer is laminated on the substrate via the underlayer containing a silicon-containing material. [7] The method for forming a metal oxide pattern according to [6], wherein the silicon-containing material is at least one of polysilicon, silicon oxide, and silicon nitride.

[0009] [8] The method for forming a metal oxide pattern according to any one of [1] to [7], wherein the halon is at least one of bromofluoromethane, bromofluoroethylene, and bromofluoropropene. [9] The method for forming a metal oxide pattern according to [8], wherein the bromofluoromethane is dibromodifluoromethane.

[0010]

[10] The method for forming a metal oxide pattern according to [8], wherein the bromofluoroethylene is at least one of bromotrifluoroethylene, 1-bromo-2,2-difluoroethylene, (E)-1-bromo-1,2-difluoroethylene, (Z)-1-bromo-1,2-difluoroethylene, 1-bromo-1-fluoroethylene, (E)-1-bromo-2-fluoroethylene, (Z)-1-bromo-2-fluoroethylene, 1,1-dibromo-2-fluoroethylene, (E)-1,2-dibromo-2-fluoroethylene, (Z)-1,2-dibromo-2-fluoroethylene, and tribromofluoroethylene.

[0011]

[11] The method for forming a metal oxide pattern according to [8], wherein the bromofluoropropene is at least one of (E)-1-bromo-3,3,3-trifluoromethylpropene, (Z)-1-bromo-3,3,3-trifluoromethylpropene, and 2-bromo-3,3,3-trifluoromethylpropene.

[0012]

[12] The method for forming a metal oxide pattern according to any one of [1] to

[11] , wherein etching is carried out under a process pressure of 1 Pa or more and 10 Pa or less.

[13] The method for forming a metal oxide pattern according to any one of [1] to

[12] , wherein the etching is carried out while applying a bias power of 10 W or more and 1200 W or less to a lower electrode supporting the member to be etched.

[0013]

[14] A method for manufacturing a semiconductor element by using the method for forming a metal oxide pattern according to any one of [1] to

[13] , the member to be etched is a semiconductor substrate having the etching object and the non-etching object, A method for manufacturing a semiconductor device, comprising a processing step of removing at least a part of the etching object from the semiconductor substrate by etching. [Effects of the Invention]

[0014] According to the present invention, an etching object containing a metal oxide can be selectively etched compared to a non-etching object, and a metal oxide pattern can be formed in a shape that follows the pattern shape of the non-etching object, which serves as a template for forming a metal oxide pattern. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a schematic diagram of an example of a plasma etching apparatus for explaining an embodiment of a metal oxide pattern formation method according to the present invention. [Figure 2] 1A and 1B are cross-sectional views illustrating an example of a member to be etched before etching and an example of a member to be etched after etching. [Figure 3] FIG. 10 is a cross-sectional view of an etched member illustrating the results of Comparative Example 7. DETAILED DESCRIPTION OF THE INVENTION

[0016] An embodiment of the present invention will be described below. Note that this embodiment is merely an example of the present invention, and the present invention is not limited to this embodiment. Furthermore, various modifications and improvements can be made to this embodiment, and such modifications and improvements can also be included in the present invention.

[0017] The metal oxide pattern forming method according to this embodiment is a method for forming a metal oxide pattern by etching a metal oxide containing at least one of tin (Sn) and indium (In) oxide using an etching gas. This metal oxide pattern forming method includes a preparation step of preparing a member to be etched, a template preparation step of preparing a template in the member to be etched, and an etching step of etching the member to be etched.

[0018] The preparation step is a step of preparing an etched member having a substrate, a metal oxide layer containing the metal oxide and laminated on the substrate directly or via an underlayer, and a template layer containing a carbon-containing material and laminated on the metal oxide layer. The metal oxide layer is an etching target that is to be etched with an etching gas, and the substrate, underlayer, and template layer are non-etching targets that are not to be etched with the etching gas. From the viewpoint of adhesion to the substrate, it is preferable that the metal oxide layer is laminated on the substrate via an underlayer containing a silicon-containing material.

[0019] The template fabrication step is a step of forming a predetermined pattern on a template layer of a member to be etched to fabricate an etching template. The etching step is a step of etching the metal oxide layer using, as an etching gas, a gas containing halon, which has fluorine atoms, bromine atoms, and carbon atoms in its molecule and has 1 to 3 carbon atoms.

[0020] More specifically, this is a process in which an etching gas is brought into contact with an etched member, on which a predetermined pattern has been formed in a template layer in the template fabrication process, in the presence of plasma, and etching is carried out while applying bias power to a lower electrode supporting the etched member, thereby selectively etching the metal oxide layer compared to the substrate, template layer, and underlayer, and transferring the predetermined pattern of the template layer to the metal oxide layer.

[0021] When the etching gas is brought into contact with the member to be etched, the halon in the etching gas reacts with the oxide in the etching target, causing etching of the metal oxide layer, which is the etching target. In contrast, the substrate, template layer, and underlayer containing a silicon-containing material, which are the non-etching targets, hardly react with the halon, so etching of the non-etching targets hardly progresses. Therefore, according to the metal oxide pattern formation method of this embodiment, the etching target can be selectively etched compared to the non-etching target.

[0022] For example, etching can be performed so that the ratio of the etching rate of the object to be etched to the etching rate of the object not to be etched is 2 or more, and from the viewpoint of controlling etching more stably, etching can be performed so that the ratio of the etching rates is 4 or more.

[0023] Furthermore, according to the metal oxide pattern formation method of this embodiment, the template layer is not easily etched, and therefore the pattern shape formed on the template layer is not easily distorted. Therefore, according to the metal oxide pattern formation method of this embodiment, a metal oxide pattern can be formed in a shape that follows the pattern shape of the template layer that serves as a template for metal oxide pattern formation, and therefore, the metal oxide can be formed into a pattern of a desired shape.

[0024] The method for forming a metal oxide pattern according to this embodiment can be used in the manufacture of semiconductor devices. That is, the method for manufacturing a semiconductor device according to this embodiment is a method for manufacturing a semiconductor device using the method for forming a metal oxide pattern according to this embodiment, in which the member to be etched is a semiconductor substrate having an etching target and a non-etching target, and the method includes a process of removing at least a part of the etching target from the semiconductor substrate by etching.

[0025] Therefore, if the metal oxide pattern formation method according to this embodiment is applied to the manufacturing process of a semiconductor device, it becomes possible to, for example, transfer a pattern formed in a photoresist to a metal oxide layer, or to remove a metal oxide film or residue present on a film of an object not to be etched.

[0026] The metal oxide pattern forming method and semiconductor device manufacturing method according to this embodiment will be described in more detail below. The etching in the metal oxide pattern formation method according to this embodiment can be achieved by plasma etching. The type of plasma source used in plasma etching is not particularly limited, and commercially available devices may be used. Examples include high-frequency discharge plasmas such as inductively coupled plasma (ICP) and capacitively coupled plasma (CCP), and microwave discharge plasmas such as electron cyclotron resonance plasma (ECRP).

[0027] The plasma etching apparatus shown in FIG. 1, which will be described in detail later, uses an ICP as a plasma source. Furthermore, in the metal oxide pattern formation method according to this embodiment, the plasma generation chamber may be separated from the chamber in which the member to be etched is placed, and plasma may be generated in the plasma generation chamber (i.e., remote plasma may be used).

[0028] [Etching gas] The etching gas used in the metal oxide pattern formation method according to this embodiment is a gas containing halon, which has fluorine atoms, bromine atoms, and carbon atoms in its molecule and has a carbon atom count of 1 to 3. Halon in the present invention refers to halogenated hydrocarbons in which some or all of the hydrogen atoms in hydrocarbons have been substituted with halogen atoms, and which contain fluorine atoms and bromine atoms.

[0029] The type of halon is not particularly limited as long as it has a fluorine atom, a bromine atom, and a carbon atom in the molecule and the number of carbon atoms is from 1 to 3, but at least one of bromofluoromethane, bromofluoroethylene, and bromofluoropropene, which are easily available and easy to handle, is preferred. Bromofluoromethane refers to a compound of the above halons that has one carbon atom, bromofluoroethylene refers to an unsaturated compound of the above halons that has two carbon atoms, and bromofluoropropene refers to an unsaturated compound of the above halons that has three carbon atoms. In any of bromofluoromethane, bromofluoroethylene, and bromofluoropropene, the numbers of fluorine atoms and bromine atoms are not particularly limited.

[0030] Specific examples of bromofluoromethane include bromotrifluoromethane (CBrF), dibromodifluoromethane (CBrF), tribromofluoromethane (CBrF), bromodifluoromethane (CHBrF), and monobromomonofluoromethane (CHBrF). Dibromodifluoromethane is particularly preferred because it can be easily vaporized at room temperature and pressure and has a relatively small environmental impact.

[0031] Specific examples of bromofluoroethylene include bromotrifluoroethylene, 1-bromo-2,2-difluoroethylene, (E)-1-bromo-1,2-difluoroethylene, (Z)-1-bromo-1,2-difluoroethylene, 1-bromo-1-fluoroethylene, (E)-1-bromo-2-fluoroethylene, (Z)-1-bromo-2-fluoroethylene, 1,1-dibromo-2-fluoroethylene, (E)-1,2-dibromo-2-fluoroethylene, (Z)-1,2-dibromo-2-fluoroethylene, and tribromofluoroethylene.

[0032] Among these, bromofluoroethylene having one bromine atom is more preferred from the viewpoint of easy vaporization at room temperature and normal pressure. Examples of bromofluoroethylene having one bromine atom include bromotrifluoroethylene, 1-bromo-2,2-difluoroethylene, (E)-1-bromo-1,2-difluoroethylene, (Z)-1-bromo-1,2-difluoroethylene, 1-bromo-1-fluoroethylene, (E)-1-bromo-2-fluoroethylene, and (Z)-1-bromo-2-fluoroethylene.

[0033] As a specific example of the bromofluoropropene, a bromofluoropropene having one bromine atom is preferred from the viewpoint of being easily vaporized at room temperature and normal pressure. Examples of the bromofluoropropene having one bromine atom include CH x BrF 5-x An example is halon, which is represented by the rational formula: (x is an integer between 0 and 4).

[0034] Specifically, (E)-1-bromopentafluoropropene, (Z)-1-bromopentafluoropropene, 2-bromopentafluoropropene, 3-bromopentafluoropropene, 2-bromo-3,3,3-trifluoropropene, (E)-1-bromo-1,3,3,3-tetrafluoropropene, (Z)-1-bromo-1,3,3,3-tetrafluoropropene, (E)-2-bromo-1,3,3,3-tetrafluoropropene, (Z)-2-bromo-1,3,3,3-tetrafluoropropene, bromopropene, (E)-1-bromo-2,3,3,3-tetrafluoropropene, (Z)-2-bromo-1,3,3,3-tetrafluoropropene, (Z)-1-bromo-3,3,3-trifluoropropene, (E)-1-bromo-3,3,3-trifluoropropene, 3-bromo-2,3,3-trifluoropropene, (E)-1-bromo-1,2-difluoropropene, (Z)-1-bromo-1,2-difluoropropene, (E)-1-bromo-1,3-difluoropropene, (Z )-1-bromo-1,3-difluoropropene, (E)-1-bromo-2,3-difluoropropene, (Z)-1-bromo-2,3-difluoropropene, (E)-1-bromo-1,3-difluoropropene, (Z)-1-bromo-1,3-difluoropropene, (E)-1-bromo-1-fluoropropene, (Z)-1-bromo-1-fluoropropene, (E)-1-bromo-2-fluoropropene, (Z)-1-bromo-2-fluoropropene, (E)-1-bromo-3-fluoro propene, (Z)-1-bromo-3-fluoropropene, (E)-2-bromo-1-fluoropropene, (Z)-2-bromo-1-fluoropropene, (E)-2-bromo-3-fluoropropene, (Z)-2-bromo-3-fluoropropene, (E)-3-bromo-1-fluoropropene, (Z)-3-bromo-1-fluoropropene, (E)-3-bromo-2-fluoropropene, (Z)-3-bromo-2-fluoropropene, 3-bromo-3-fluoropropene, and the like. The halons such as bromofluoromethane, bromofluoroethylene, and bromofluoropropene may be used alone or in combination of two or more.

[0035] The etching gas may be a gas formed only from halon, or may be a mixed gas containing halon and an inert gas, or may be a mixed gas containing halon, an inert gas, and a fluorine-containing compound other than halon. The type of inert gas is not particularly limited, but examples thereof include nitrogen gas (N), helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe). These inert gases may be used alone or in combination of two or more.

[0036] By adding a fluorine-containing compound or an oxidizing gas to the etching gas, the etching rate and etching selectivity of the material to be etched can be controlled in some cases. The fluorine-containing compound used in the mixed gas is a compound that has a fluorine atom in its molecule and is gaseous at room temperature and normal pressure, and is a compound other than the above-mentioned halons, such as fluorine gas (F), oxygen difluoride (F2O), chlorine trifluoride (ClF3), bromine pentafluoride (BrF5), iodine heptafluoride (IF7), nitrogen trifluoride (NF3), sulfur hexafluoride (SF6), and fluorocarbons. Examples of fluorocarbons include tetrafluoromethane (CF), trifluoromethane (CHF), difluoromethane (CHF), fluoromethane (CHF), hexafluoroethane (CF), octafluoropropane (CF), octafluorocyclobutane (CF), hexafluoro-1,3-butadiene (CF), and carbonyl fluoride (COF).

[0037] The oxidizing gas is not particularly limited as long as it has at least one of an oxygen atom, a chlorine atom, and a bromine atom in its molecule and is a compound other than the above-mentioned halons and fluorine-containing compounds. Examples of the oxidizing gas include oxygen gas (O), ozone (O), nitrous oxide (NO), nitric oxide (NO), nitrogen dioxide (NO), chlorine gas (Cl), hydrogen chloride (HCl), bromine (Br), hydrogen bromide (HBr), sulfur dioxide (SO), sulfur trioxide (SO), and silicon tetrachloride (SiCl).

[0038] The concentration of halon in the mixed gas is not particularly limited and can be more than 0% by volume and less than 100% by volume, but may be adjusted taking into consideration the ignitability of the plasma, etc. To ensure sufficient ignitability of the plasma, the concentration of halon in the mixed gas is preferably 1% by volume or more and 50% by volume or less, and more preferably 5% by volume or more and 30% by volume or less.

[0039] If the concentration of halon in the mixed gas is within the above numerical range, a high etching selectivity ratio is likely to be achieved, for example, an etching selectivity ratio of 3 or more. Here, the etching selectivity ratio is a value calculated by dividing the etching rate of an object to be etched by the etching rate of an object not to be etched.

[0040] The concentration of the fluorine-containing compound in the mixed gas is not particularly limited, and although it depends on the type of fluorine-containing compound, it can be 0.5% by volume or more and 80% by volume or less. However, in consideration of the ignition property of the plasma, it is preferably 1% by volume or more and 40% by volume or less, and more preferably 5% by volume or more and 20% by volume or less.

[0041] The amount of etching gas used in the metal oxide pattern formation method according to this embodiment, for example, the total flow rate of the etching gas into a chamber in which plasma etching is performed in a plasma etching apparatus, may be adjusted depending on the internal volume, exhaust capacity, process pressure, etc. of the chamber.

[0042] [Conditions for the etching process] The pressure conditions for the etching step in the metal oxide pattern formation method according to this embodiment are not particularly limited, but plasma etching is preferably carried out under a process pressure of 0.2 Pa to 30 Pa, more preferably 1 Pa to 15 Pa, even more preferably 1 Pa to 10 Pa, and particularly preferably 2 Pa to 8 Pa. Within the above pressure ranges, the plasma composition is stable, making it easy to improve the reproducibility of etching.

[0043] In a plasma etching apparatus, for example, high-frequency source power is applied to an RF (radio frequency) coil to form an electric field and a magnetic field, thereby converting an etching gas into plasma and generating plasma. The magnitude of the source power is not particularly limited, but is preferably greater than 0 W and less than 3000 W, more preferably greater than 100 W and less than 1500 W, and even more preferably greater than 200 W and less than 1000 W. If the magnitude of the source power is within the above numerical range, the etching rate of the object to be etched will be sufficiently high, and the etching selectivity will be sufficiently high.

[0044] The temperature conditions for the etching step in the metal oxide pattern formation method according to this embodiment are not particularly limited, but the temperature of the member to be etched (e.g., a semiconductor substrate) during plasma etching is preferably −20° C. or higher and 250° C. or lower, more preferably 0° C. or higher and 100° C. or lower, and even more preferably 20° C. or higher and 70° C. or lower. If the temperature of the member to be etched during plasma etching is within the above-mentioned range, for example, deformation due to alteration or sublimation of a resist film formed on a semiconductor substrate is suppressed, thereby enabling plasma etching to be performed with high patterning accuracy. Here, the temperature in the above-mentioned temperature conditions refers to the temperature of the member to be etched, but the temperature of a lower electrode supporting the member to be etched that is installed in the chamber of a plasma etching apparatus can also be used.

[0045] During plasma etching, it is necessary to apply a bias power exceeding 0 W to the lower electrode supporting the member to be etched. To sufficiently increase the etching selectivity of the material to be etched relative to the material not to be etched, the bias power applied to the lower electrode is preferably 10 W to 1200 W, more preferably 20 W to 800 W, and even more preferably 30 W to 300 W. The bias power is preferably 5% to 90% of the source power.

[0046] [Material to be etched] The member to be etched by the metal oxide pattern formation method according to this embodiment has an etching target and a non-etching target, but may be a member consisting of a portion formed of an etching target and a portion formed of a non-etching target, or may be a member having a portion formed of an etching target and a portion formed of a non-etching target, as well as something other than the etching target and the non-etching target. The shape of the member to be etched is not particularly limited, and may be, for example, a plate, foil, film, powder, or lump. An example of the member to be etched is the semiconductor substrate described above.

[0047] [Object to be etched] The etching target in the metal oxide pattern formation method according to this embodiment is a metal oxide layer containing at least one oxide of tin and indium, i.e., tin oxide, indium oxide, or indium tin oxide. Examples of tin oxide include SnO and SnO2, and examples of indium oxide include In2O3. The etching target, i.e., the metal oxide layer, may be formed solely from the oxide, or may have a portion formed solely from the oxide and a portion formed from another material, or may be formed from a mixture of the oxide and another material.

[0048] Furthermore, the etching target may not only be a material consisting essentially of an oxide of a specific metal (tin, indium) but also a material containing 10 mol % or more, more preferably 20 mol % or more, and even more preferably 30 mol % or more of an oxide of the specific metal. For example, the metal oxide pattern formation method according to this embodiment can be applied to materials containing impurities, or nitrides, oxynitrides, oxyfluorides, etc. of the specific metals.

[0049] The oxide here refers to a compound containing a metal and oxygen. y O z(wherein M is tin or indium, and y and z are any natural numbers), and is a compound containing at least 10 mol % or more of a metal, more preferably 15 mol % or more, and even more preferably 20 mol % or more. Specific examples include compounds represented by MO, MO, MO, MO, MO, MO, MO, and MO.

[0050] The nitrides referred to here refer to compounds containing metal and nitrogen. a N b (M is tin or indium, a and b are any natural numbers), and are compounds containing at least 10 mol % or more of metal, more preferably 15 mol % or more, and even more preferably 20 mol % or more. Specifically, M N, M N, M N 2, M N 4, M N, M 7 N 3, M 16 Examples include compounds represented by N2.

[0051] Furthermore, the term "oxynitride" as used herein refers to a compound containing metal, oxygen, and nitrogen. c N d O e (M is tin or indium, and c, d, and e are any natural numbers), and the compound contains at least 10 mol % or more of the metal, more preferably 15 mol % or more, and even more preferably 20 mol % or more.

[0052] Furthermore, the term "oxyfluoride" as used herein refers to a compound containing a metal, oxygen, and fluorine. f F g O h (M is tin or indium, and f, g, and h are any natural numbers), and is a compound containing at least 10 mol % or more of a metal, more preferably 15 mol % or more, and even more preferably 20 mol % or more. The shape of the material containing the specific metal is not particularly limited, and may be in the form of particles, lumps, film, foil, or powder.

[0053] [Objects not to be etched] The non-etching objects in the metal oxide pattern formation method according to this embodiment are a substrate, an optionally provided underlayer containing a silicon-containing material, and a template layer containing a carbon-containing material. The underlayer is a layer that serves as a base for the metal oxide layer and is preferably formed on the substrate. The template layer is a layer on which a pattern that serves as a template for a pattern to be formed in the metal oxide layer by etching is formed. The substrate is a part that forms the base of the pattern-formed body obtained by the metal oxide pattern formation method according to this embodiment, and is preferably a silicon substrate.

[0054] The silicon-containing material used in the underlayer refers to a compound having a silicon atom, and examples thereof include compounds having at least one of an oxygen atom and a nitrogen atom and a silicon atom, polysilicon, polysilicon carbon, amorphous silicon (Si), and silicon carbide. Examples of compounds having at least one of an oxygen atom and a nitrogen atom and a silicon atom include silicon oxide, silicon nitride, and silicon oxynitride.

[0055] Silicon oxide refers to a compound containing silicon and oxygen in any ratio, and an example thereof is silicon dioxide (SiO2). The purity of silicon oxide is not particularly limited, but is preferably 30% by mass or more, more preferably 60% by mass or more, and even more preferably 90% by mass or more.

[0056] Silicon nitride refers to a compound containing silicon and nitrogen in any ratio, and an example thereof is Si3N4. The purity of silicon nitride is not particularly limited, but is preferably 30% by mass or more, more preferably 60% by mass or more, and even more preferably 90% by mass or more. Silicon oxynitride refers to a compound having silicon, oxygen, and nitrogen in any ratio, and an example thereof is Si2N2O.

[0057] The carbon-containing material used in the template layer refers to a compound having carbon atoms, and examples thereof include amorphous carbon (C) and photoresist. Photoresists refer to photosensitive compositions whose physical properties, including solubility, change when exposed to light or electron beams. Examples include photoresists for g-line, h-line, i-line, KrF, ArF, F2, and EUV. The composition of the photoresist is not particularly limited as long as it is one commonly used in semiconductor manufacturing processes. Examples include compositions containing a polymer synthesized from at least one monomer selected from linear olefins, cyclic olefins, (meth)acryloyl group-containing compounds, epoxy group-containing compounds, siloxanes, and polyfunctional alcohols (e.g., glycols). In this specification, the term "(meth)acryloyl group" refers to at least one of an acryloyl group and a methacryloyl group.

[0058] Silicon-containing materials and carbon-containing materials react extremely slowly with the halon, so etching hardly progresses even when etching is performed by the metal oxide pattern formation method according to this embodiment. Furthermore, the vapor pressure of the reaction products of silicon-containing materials and carbon-containing materials with the halon is low, and the reaction products are deposited on the surface of the object not to be etched and function as a protective film, so etching hardly progresses even when etching is performed by the metal oxide pattern formation method according to this embodiment.

[0059] When an etching target member having an etching target and a non-etching target is etched using the method for forming a metal oxide pattern according to this embodiment, the etching target can be selectively etched while the non-etching target is hardly etched. Therefore, the pattern shape formed on the template layer, which is the non-etching target, is less likely to be distorted, and the pattern shape of the template layer can be accurately transferred to the metal oxide layer while suppressing damage to the base layer, which is the non-etching target.

[0060] For example, when a semiconductor substrate having a metal oxide layer formed of tin oxide, a template layer formed of at least one of photoresist and amorphous carbon, an underlayer formed of at least one of polysilicon, silicon oxide, and silicon nitride, and a plate-like base material such as a silicon substrate is etched using the metal oxide pattern formation method according to this embodiment, the tin oxide can be selectively etched, and the pattern formed on the template layer can be transferred to the metal oxide layer.

[0061] Below, we will explain an example of plasma etching of a tin oxide film, amorphous silicon film, silicon oxide film, silicon nitride film, and photoresist film formed on the surface of a semiconductor substrate (corresponding to a member to be etched) using the plasma etching apparatus shown in Figure 1. The plasma etching apparatus in Figure 1 is a plasma etching apparatus that uses an ICP as a plasma source. First, we will explain the plasma etching apparatus in Figure 1.

[0062] The plasma etching apparatus of FIG. 1 includes a chamber 1 in which plasma etching is performed, a lower electrode 2 that supports a member 20 to be etched inside the chamber 1, a bias power supply (not shown) that applies bias power to the lower electrode 2, an RF coil 15 that forms an electric field and a magnetic field inside the chamber 1 to convert the etching gas into plasma, a source power supply (not shown) that applies high-frequency source power to the RF coil 15, a vacuum pump 13 that reduces the pressure inside the chamber 1, a pressure gauge 14 that measures the pressure inside the chamber 1, a sensor 16 that captures plasma emission generated as plasma is generated, and a spectrometer 17 that disperses the plasma emission captured by the sensor 16 to monitor changes in the plasma emission over time.

[0063] 2, the member to be etched 20 includes a silicon substrate 24, an underlayer 23 formed on the surface of the silicon substrate 24, a metal oxide layer 22 laminated on the underlayer 23, and a template layer 21 laminated on the metal oxide layer 22. The template layer 21 is made of at least one of photoresist and amorphous carbon, and has a predetermined pattern to be transferred to the metal oxide layer 22.

[0064] The number of underlayers 23 may be one as shown in the figure, or two or more underlayers 23 may be provided between the metal oxide layer 22 and the silicon substrate 24. The underlayer 23 contains a silicon-containing material, and may also contain a metal material together with the silicon-containing material. Examples of metal materials include simple substances such as cobalt, nickel, copper, titanium, tantalum, ruthenium, germanium, aluminum, lanthanum, hafnium, and zirconium, as well as oxides, nitrides, oxynitrides, carbides, and metal silicides thereof.

[0065] For example, a CCD (Charge-Coupled Device) image sensor can be used as the sensor 16. However, instead of providing the sensor 16 and the spectroscope 17, a sight window may be provided in the chamber 1, and the interior of the chamber 1 may be visually observed through the sight window to confirm the change in plasma light emission over time.

[0066] The chamber 1 also includes an etching gas supply unit that supplies an etching gas to the interior of the chamber 1. The etching gas supply unit includes a halon gas supply unit 3 that supplies halon gas, an inert gas supply unit 4 that supplies an inert gas, an etching gas supply pipe 11 that connects the halon gas supply unit 3 to the chamber 1, and an inert gas supply pipe 12 that connects the inert gas supply unit 4 to an intermediate portion of the etching gas supply pipe 11.

[0067] When halon gas is supplied to the chamber 1 as an etching gas, the halon gas is sent from the halon gas supply unit 3 to the etching gas supply pipe 11, and the halon gas is supplied to the chamber 1 via the etching gas supply pipe 11.

[0068] The pressure in the chamber 1 before the etching gas is supplied is not particularly limited as long as it is equal to or lower than the supply pressure of the etching gas. For example, -5 The pressure is preferably 1 Pa or more but less than 100 kPa, and more preferably 1 Pa or more but less than 80 kPa.

[0069] Furthermore, when a mixed gas of halon gas and inert gas is supplied as the etching gas, halon gas is sent from the halon gas supply unit 3 to the etching gas supply pipe 11, and inert gas is sent from the inert gas supply unit 4 to the etching gas supply pipe 11 via the inert gas supply pipe 12. As a result, the halon gas and the inert gas are mixed in the middle of the etching gas supply pipe 11 to form a mixed gas, and this mixed gas is supplied to the chamber 1 via the etching gas supply pipe 11.

[0070] When a mixed gas of halon gas, inert gas, and fluorine-containing compound gas is supplied as the etching gas, the etching gas supply unit may be configured to have a fluorine-containing compound gas supply unit and a fluorine-containing compound gas supply pipe in addition to the halon gas supply unit 3, the inert gas supply unit 4, the etching gas supply pipe 11, and the inert gas supply pipe 12, and the same operation as in the case of supplying a mixed gas of halon gas and an inert gas as the etching gas may be performed.

[0071] When plasma etching is performed using such a plasma etching apparatus, a member to be etched 20 is placed on a lower electrode 2 disposed inside the chamber 1, and the pressure inside the chamber 1 is reduced using a vacuum pump 13 to, for example, between 1 Pa and 10 Pa. Then, an etching gas is supplied into the chamber 1 using an etching gas supply unit. When high-frequency (e.g., 13.56 MHz) source power is applied to the RF coil 15, an electric field and a magnetic field are formed inside the chamber 1, accelerating electrons. These accelerated electrons collide with halon molecules in the etching gas, generating new ions and electrons, resulting in a discharge and forming plasma. The generation of plasma can be confirmed using a sensor 16 and a spectrometer 17.

[0072] When plasma is generated, the metal oxide layer 22 formed on the surface of the member to be etched 20 is etched. Explaining this in detail with reference to FIG. 2, the region of the metal oxide layer 22 that is covered with the template layer 21 is not etched, and the exposed region that is not covered with the template layer 21 is etched. As a result, the pattern formed on the template layer 21 is transferred to the metal oxide layer 22, and a pattern having a shape that follows the shape of the pattern formed on the template layer 21 is formed on the metal oxide layer 22 (see the diagram drawn to the right of the arrow in FIG. 2).

[0073] Here, the polymer layer 50 shown in the diagram to the right of the arrow in FIG. 2 will be described. The polymer of this polymer layer 50 is derived from halon, an etching gas. For example, when the halon is 1-bromo-1-fluoroethylene, the 1-bromo-1-fluoroethylene is decomposed by plasma to generate CF2, which then generates polytetrafluoroethylene. The generated polytetrafluoroethylene is then deposited on the template layer 21, the metal oxide layer 22, and the underlayer 23 to form the polymer layer 50. Furthermore, the 1-bromo-1-fluoroethylene is decomposed by plasma to generate Br, which reacts with the template layer 21, the metal oxide layer 22, and the underlayer 23 to generate a substance with a low vapor pressure, and a film made of the substance with a low vapor pressure is formed on the surfaces of the template layer 21, the metal oxide layer 22, and the underlayer 23.

[0074] Etching of template layer 21 and underlayer 23 is suppressed by the deposition of polymers on the surfaces of template layer 21 and underlayer 23, or the formation of a film made of a substance with a low vapor pressure. This increases the etching selectivity described above. Furthermore, the pattern shape formed on template layer 21 is less likely to collapse, so the pattern shape of template layer 21 can be accurately transferred to metal oxide layer 22.

[0075] If the amount of polymer deposited is too small, the etching selectivity described above will decrease. On the other hand, if the amount of polymer deposited is too large, the pattern formed on the template layer 21 may be blocked by the polymer, preventing etching of the metal oxide layer 22 from proceeding. It is preferable that the polymer layer 50 be formed with a thin, uniform thickness on the top 30 and sidewalls 40 of the template layer 21. To achieve this, the polymer deposition rate is preferably 0.1 nm / min to 30 nm / min, and more preferably 1 nm / min to 20 nm / min.

[0076] The amount of etching gas supplied to the chamber 1 and the concentration of halon gas in the etching gas (mixed gas) can be adjusted by controlling the flow rates of the halon gas and the inert gas using mass flow controllers (not shown) installed in the etching gas supply pipe 11 and the inert gas supply pipe 12, respectively.

[0077] From the viewpoint of uniformly etching the surface of the member to be etched 20, the pressure of the etching gas supplied into the chamber 1 is preferably 0.01 Pa or more and 500 Pa or less, more preferably 0.1 Pa or more and 100 Pa or less, even more preferably 1 Pa or more and 30 Pa or less, and particularly preferably 2 Pa or more and 10 Pa or less. If the pressure of the etching gas in the chamber 1 is within the above range, the object to be etched is likely to be etched at a sufficient rate, and the ratio of the etching rate to the non-etched object, i.e., the etching selectivity, is likely to be high. [Example]

[0078] The present invention will be described in more detail below with reference to examples and comparative examples. Example 1 Plasma etching of the member to be etched was carried out using an ICP etching apparatus RIE-200iP manufactured by Samco Inc., which has a configuration substantially similar to that of the plasma etching apparatus shown in FIG. This member to be etched has the same configuration as the diagram drawn to the left of the arrow in Fig. 2. That is, a base layer 23 with a thickness of 100 nm is formed on a square silicon substrate 24 with sides of 2 inches, a metal oxide layer 22 with a thickness of 100 nm is formed on the base layer 23, and a template layer 21 with a thickness of 500 nm is formed on the metal oxide layer 22.

[0079] The underlayer 23 is made of polysilicon, the metal oxide layer 22 is made of tin oxide, and the template layer 21 is made of photoresist (TARF (registered trademark) manufactured by Tokyo Ohka Kogyo Co., Ltd.) or amorphous carbon. A line-and-space pattern with a width of 250 nm is formed on the template layer 21. When the template layer 21 is formed of photoresist, the photoresist is exposed to light through a photomask on which a predetermined pattern is drawn, and then the exposed portions are removed with a solvent, thereby performing patterning.

[0080] When the template layer 21 was made of amorphous carbon, it was patterned as follows. First, a silicon oxynitride film was formed on the amorphous carbon layer, and a patterned photoresist film was formed on top of it using the same method as described above. Then, the silicon oxynitride and amorphous carbon in areas where the photoresist was not formed were removed by plasma etching, and the pattern of the photoresist film was transferred to the silicon oxynitride film and amorphous carbon film. Finally, the silicon oxynitride film and photoresist film were removed to prepare an etched member having a patterned amorphous carbon layer.

[0081] The internal volume of the chamber is 46,000 cm 3 The etching gas was a mixed gas of 1-bromo-1-fluoroethylene gas and argon (Ar). The flow rate of 1-bromo-1-fluoroethylene gas was set to 10 sccm and the flow rate of argon to 90 sccm, so that the concentration of 1-bromo-1-fluoroethylene gas in the etching gas was adjusted to 10% by volume. Here, sccm is the volumetric flow rate (cm) per minute normalized under the conditions of 0°C and 1 atmosphere. 3 )

[0082] The process pressure inside the chamber was set to 3 Pa, the source power to 600 W, the bias power to 50 W, and the temperature of the material to be etched to 20°C. The flow rate of 1-bromo-1-fluoroethylene gas, the flow rate of argon, the process pressure, the source power, and the bias power were all constantly monitored, and plasma etching was performed for 5 minutes while confirming that there was no difference between the set value and the actual value.

[0083] After etching was completed, the etched member was removed from the chamber of the etching apparatus and analyzed using a scanning electron microscope (SEM). That is, the etched member was visually observed after etching was completed, and it was confirmed that the pattern shape of the template layer 21 had been transferred to the metal oxide layer 22. The etching rate of the metal oxide layer 22 was calculated by dividing the film thickness of the metal oxide layer 22 before etching by the etching time. The results are shown in Table 1.

[0084] Furthermore, since a polymer layer 50 consisting of a polymer derived from halon deposited on the surface of the etched member after etching was completed (see the diagram drawn to the left of the arrow in FIG. 2), the thickness of the polymer layer 50 formed on the top 30 and side wall 40 of the template layer 21 was measured. The deposition rate of the polymer on the top 30 and side wall 40 of the template layer 21 was calculated by dividing the thickness of the polymer layer 50 by the etching time. The results are shown in Table 1.

[0085] The SEM measurement conditions are as follows: Measuring equipment: JEOL Ltd. JSM-7900F Accelerating voltage: 5 kV Magnification: 10000x

[0086] [Table 1]

[0087] (Examples 2 to 18 and Comparative Examples 1 to 5) Plasma etching was performed in the same manner as in Example 1, except that the type of etching gas, the type of metal oxide forming metal oxide layer 22, the type of silicon-containing material forming underlayer 23, and various etching conditions were as shown in Table 1, and the etching rate of metal oxide layer 22 and the deposition rate of polymer on top portion 30 and sidewall portion 40 were calculated. The results are shown in Table 1. In the column for type of etching gas in Table 1, "HBr" stands for hydrogen bromide, "SF6" stands for sulfur hexafluoride, and "BCl3" stands for boron trichloride.

[0088] The results of Examples 1 to 3 reveal the following. Specifically, by using 1-bromo-1-fluoroethylene as the etching gas, the 100-nm-thick metal oxide layer was completely etched, revealing the underlayer, and etching of the template layer and underlayer barely progressed until polymer was deposited on the upper part of the underlayer and on the top and sidewalls of the template layer. This means that tin oxide, indium oxide, and indium tin oxide were selectively etched compared to the template layer and underlayer. As a result, the pattern of the template layer could be transferred to the metal oxide layer while suppressing etching of the template layer and underlayer.

[0089] The results of Examples 4 to 8 and 16 to 18 show that even when (E)-1-bromo-2-fluoroethylene, (Z)-1-bromo-2-fluoroethylene, dibromodifluoromethane, bromotrifluoroethylene, 1-bromo-2,2-difluoroethylene, (E)-1-bromo-3,3,3-trifluoromethylpropene, (Z)-1-bromo-3,3,3-trifluoromethylpropene, or 2-bromo-3,3,3-trifluoromethylpropene is used as the etching gas, the pattern of the template layer can be transferred to the metal oxide layer without any problems.

[0090] The results of Example 9 show that increasing the bias power improves the etching rate of the metal oxide layer (tin oxide) and suppresses the deposition of polymers. The results of Examples 10 and 11 show that the higher the temperature of the lower electrode, the more the etching rate of the metal oxide layer (tin oxide) improves and the more the deposition of polymer is suppressed. The results of Example 12 show that the pattern can be transferred to the metal oxide layer without any problems even if the pressure inside the chamber is increased.

[0091] The results of Example 13 show that even if the source power is increased, the pattern can be transferred to the metal oxide layer without any problems. The results of Examples 14 and 15 show that even when the silicon-containing material forming the underlayer is changed to silicon oxide or silicon nitride, the pattern of the template layer can be transferred to the metal oxide layer without etching the underlayer.

[0092] The results of Comparative Examples 1 to 4 show that when tetrafluoromethane, hydrogen bromide, sulfur hexafluoride, or boron trichloride is used as the etching gas, the etching rate of the template layer is higher than that of the metal oxide layer (tin oxide), and etching of the template layer, which is not the target of etching, proceeds preferentially over the metal oxide layer. Therefore, these gases are unsuitable for transferring a pattern to a metal oxide layer. The results of Comparative Example 5 show that the metal oxide layer is not etched when the bias power is 0 W. Therefore, setting the bias power to 0 W is not suitable for transferring a pattern to the metal oxide layer.

[0093] Example 19 Plasma etching was performed in the same manner as in Example 1, except that the thickness of metal oxide layer 22 was 20 nm, the thickness of template layer 21 was 200 nm, a line-and-space pattern with a width of 100 nm was formed on template layer 21, the pressure in the chamber was 1 Pa, the bias power was 100 W, and the etching time was 30 seconds, and the etching rate of metal oxide layer 22 and the deposition rate of polymer on top portion 30 and sidewall portion 40 were calculated. The results are shown in Table 2.

[0094] [Table 2]

[0095] (Examples 20 to 28 and Comparative Examples 6 to 8) Plasma etching was performed in the same manner as in Example 19, except that the type of etching gas and various etching conditions were as shown in Table 2, and the etching rate of the metal oxide layer 22 and the deposition rate of the polymer on the top portion 30 and the sidewall portion 40 were calculated. The results are shown in Table 2. Note that "CF4" listed in the column for type of etching gas in Table 2 stands for tetrafluoromethane, and "C4F8" stands for octafluorocyclobutane.

[0096] The results of Examples 19 to 21 show that plasma etching can be performed using a pattern with 100 nm line and space widths when 1-bromo-1-fluoroethylene is used as the etching gas. In particular, the thickness of the deposited polymer can be reduced by increasing the bias power or the temperature of the lower electrode.

[0097] Furthermore, the results of Examples 22 to 28 show that when bromotrifluoroethylene, 1-bromo-2,2-difluoroethylene, dibromodifluoromethane, (E)-1-bromo-2-fluoroethylene, or (Z)-1-bromo-2-fluoroethylene is used as the etching gas, the pattern formed on the template layer can be transferred to the metal oxide layer. Furthermore, by adding tetrafluoromethane or oxygen gas to the etching gas, the thickness of the polymer film deposited on the top and sidewalls can be reduced.

[0098] The results of Comparative Example 6 show that when tetrafluoromethane is used as the etching gas, the etching rate of the template layer is higher than that of the metal oxide layer (tin oxide), and etching of the template layer, which is not the target to be etched, proceeds preferentially over etching of the metal oxide layer. Therefore, tetrafluoromethane is unsuitable for transferring a pattern to a metal oxide layer.

[0099] The results of Comparative Example 7 show that when octafluorocyclobutane was used as the etching gas, a polymer layer 150 was deposited to cover the top of the template layer 121, as shown in FIG. 3, and the openings in the template layer 121 were blocked by the polymer layer 150, preventing etching of the metal oxide layer 122. Therefore, octafluorocyclobutane is unsuitable for transferring a pattern to a metal oxide layer. In FIG. 3, reference numeral 123 denotes an underlayer, and reference numeral 124 denotes a silicon substrate.

[0100] The results of Comparative Example 8 show that even if the etching conditions other than the bias power are the same as those of Example 21, the metal oxide layer is not etched when the bias power is 0 W. Therefore, setting the bias power to 0 W is not suitable for transferring a pattern to the metal oxide layer. [Explanation of symbols]

[0101] 1. Chamber 2. Bottom electrode 3. Halon Gas Supply Department 4. Inert gas supply section 11. Etching gas supply pipe 12 Inert gas supply piping 13. Vacuum pump 14. Pressure gauge 15. RF coil 16 Sensor 17...Spectrometer 20. Component to be etched 21. Template Layer 22 Metal oxide layer 23...base layer 24. Silicon substrate 30...Top 40 Side wall 50 polymer layers

Claims

1. A method for forming a pattern of a metal oxide containing at least one of tin and indium oxide by using an etching gas, the method comprising: a preparation step of preparing an etched member having a substrate, a metal oxide layer containing the metal oxide and laminated on the substrate directly or via an underlayer, and a template layer containing a carbon-containing material and laminated on the metal oxide layer, wherein the metal oxide layer is an etching target that is to be etched with the etching gas, and the substrate, the underlayer, and the template layer are non-etching targets that are not to be etched with the etching gas; a template fabrication step of forming a predetermined pattern on the template layer of the member to be etched; an etching step of using, as the etching gas, a gas containing halon, which has a fluorine atom, a bromine atom, and a carbon atom in its molecule and the number of carbon atoms is 1 to 3, bringing the etching gas into contact with the member to be etched, the template layer of which has been formed with the predetermined pattern in the template preparation step, in the presence of plasma, and performing etching while applying bias power to a lower electrode supporting the member to be etched, thereby selectively etching the metal oxide layer compared to the base material, the template layer, and the underlayer, thereby transferring the predetermined pattern of the template layer to the metal oxide layer; Equipped with The method for forming a metal oxide pattern is characterized in that the halon is at least one of bromotrifluoroethylene, 1-bromo-2,2-difluoroethylene, (E)-1-bromo-1,2-difluoroethylene, (Z)-1-bromo-1,2-difluoroethylene, 1-bromo-1-fluoroethylene, (E)-1-bromo-2-fluoroethylene, (Z)-1-bromo-2-fluoroethylene, 1,1-dibromo-2-fluoroethylene, (E)-1,2-dibromo-2-fluoroethylene, (Z)-1,2-dibromo-2-fluoroethylene, tribromofluoroethylene, (E)-1-bromo-3,3,3-trifluoromethylpropene, (Z)-1-bromo-3,3,3-trifluoromethylpropene, and 2-bromo-3,3,3-trifluoromethylpropene.

2. 2. The method for forming a metal oxide pattern according to claim 1, wherein the etching gas is a mixed gas containing the halon and an inert gas.

3. 2. The method for forming a metal oxide pattern according to claim 1, wherein the etching gas is a mixed gas containing the halon, an inert gas, and a fluorine-containing compound other than the halon.

4. 4. The method for forming a metal oxide pattern according to claim 2, wherein the concentration of said halon in said mixed gas is 1% by volume or more and 50% by volume or less.

5. 5. The method for forming a metal oxide pattern according to claim 1, wherein the carbon-containing material is at least one of a photoresist and amorphous carbon.

6. 6. The method for forming a metal oxide pattern according to claim 1, wherein the metal oxide layer is laminated on the substrate via the underlayer containing a silicon-containing material.

7. 7. The method for forming a metal oxide pattern according to claim 6, wherein the silicon-containing material is at least one of polysilicon, silicon oxide, and silicon nitride.

8. 8. The method for forming a metal oxide pattern according to claim 1, wherein etching is carried out under a process pressure of 1 Pa or more and 10 Pa or less.

9. 9. The method for forming a metal oxide pattern according to claim 1, wherein the etching is carried out while applying a bias power of 10 W or more and 1200 W or less to a lower electrode supporting the member to be etched.

10. A method for manufacturing a semiconductor element, comprising the steps of: manufacturing a semiconductor element using the method for forming a metal oxide pattern according to any one of claims 1 to 9; the member to be etched is a semiconductor substrate having the etching object and the non-etching object, A method for manufacturing a semiconductor device, comprising a processing step of removing at least a part of the etching object from the semiconductor substrate by etching.

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