Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/60—Wet etching
  • H10P50/64—Wet etching of semiconductor materials
  • H10P50/642—Chemical etching
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K13/00—Etching, surface-brightening or pickling compositions
  • C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
  • C30B29/02—Elements
  • C30B29/06—Silicon
• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
  • C30B33/08—Etching
• • C—CHEMISTRY; METALLURGY
  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
  • C30B33/08—Etching
  • C30B33/10—Etching in solutions or melts
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
  • H10D30/00—Field-effect transistors [FET]
  • H10D30/01—Manufacture or treatment
  • H10D30/019—Manufacture or treatment of FETs having stacked nanowire, nanosheet or nanoribbon channels
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
  • H10D30/00—Field-effect transistors [FET]
  • H10D30/01—Manufacture or treatment
  • H10D30/019—Manufacture or treatment of FETs having stacked nanowire, nanosheet or nanoribbon channels
  • H10D30/0191—Manufacture or treatment of FETs having stacked nanowire, nanosheet or nanoribbon channels forming stacked channels, e.g. changing their shapes or sizes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
  • H10D30/00—Field-effect transistors [FET]
  • H10D30/01—Manufacture or treatment
  • H10D30/021—Manufacture or treatment of FETs having insulated gates [IGFET]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
  • H10D30/00—Field-effect transistors [FET]
  • H10D30/60—Insulated-gate field-effect transistors [IGFET]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/69—Etching of wafers, substrates or parts of devices using masks for semiconductor materials
  • H10P50/691—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic

Definitions

• the present invention relates to an etching composition, an etching method, a method for manufacturing a semiconductor device, and a method for manufacturing a gate-all-around transistor.
• fins perpendicular to the silicon substrate by forming fins perpendicular to the silicon substrate to create a multi-gate element, not only can the number of transistors per unit area be increased, but off-state leakage current can also be suppressed. This improves the effect of the on-state current, achieving low power consumption and low heat generation. In addition, it exhibits excellent performance in ON/OFF control at low voltages.
• the nanosheet or nanowire that serves as the channel is covered with a gate electrode, increasing the contact area between the channel and gate electrode, thereby improving the transistor performance per unit area.
• an etching solution is required to selectively etch silicon or silicon germanium from a structure in which silicon and silicon germanium are alternately stacked.
• Patent Document 1 discloses an etching solution that contains an organic alkaline compound such as quaternary ammonium hydroxide and water, and has a dissolved oxygen concentration below a specified value.
• an etching solution that contains an organic alkaline compound but does not contain a thiol compound cannot suppress the dissolution of silicon germanium, and is inferior in the selective solubility of silicon relative to silicon germanium.
• Patent Document 1 does not have the performance required to etch narrow gaps.
• an etching composition containing an alkaline compound and a thiol compound suppresses the dissolution of silicon germanium, promotes the dissolution of silicon, and exhibits excellent selective solubility of silicon relative to silicon germanium.
• the gist of the present invention is as follows:
• An etching composition that dissolves silicon comprising an alkaline compound (A) and a thiol compound (B).
• thiol compound (B) includes at least one compound selected from the group consisting of thioglycerol, thioglycolic acid, ethanolamine thioglycolate, 8-mercaptooctanoic acid, 1-octanethiol, 1-undecanethiol, 1-dodecanethiol, 11-mercapto-1-undecanol, 11-mercaptoundecanoic acid, 16-mercaptohexadecanoic acid, 4,4'-dithiodibutyric acid, bis(2-hydroxyethyl)disulfide, and didodecanedisulfide.
• the thiol compound (B) includes at least one compound selected from the group consisting of thioglycerol, thioglycolic acid, ethanolamine thioglycolate, 8-mercaptooctanoic acid, 1-octanethiol, 1-undecanethiol,
• a method for manufacturing a semiconductor device comprising a step of etching silicon using an etching composition according to any one of [1] to [17].
• a method for manufacturing a gate-all-around transistor comprising a step of etching silicon using an etching composition according to any one of [1] to [17].
• the etching composition of the present invention inhibits the dissolution of silicon germanium, promotes the dissolution of silicon, and has excellent selective solubility of silicon relative to silicon germanium, and therefore can be suitably used as an etching solution that selectively dissolves silicon relative to silicon germanium.
• the etching method of the present invention, the manufacturing method of the semiconductor device of the present invention, and the manufacturing method of the gate-all-around transistor of the present invention which use such an etching composition of the present invention, suppress the dissolution of silicon germanium and promote the dissolution of silicon in the etching process, and due to the excellent selective solubility of silicon relative to silicon germanium, it is possible to perform high-precision etching and manufacture the desired product with a good yield.
• the etching composition of the present invention is an etching composition that dissolves silicon, which contains an alkali compound (A) (hereinafter may be referred to as “component (A)”) and a thiol compound (B) (hereinafter may be referred to as “component (B)").
• composition of the present invention contains an alkali compound (A) and a thiol compound (B), which inhibits the dissolution of silicon germanium and promotes the dissolution of silicon, and is excellent in the selective solubility of silicon in silicon germanium. In particular, it is excellent in the selective solubility of single crystal silicon in silicon germanium.
• the etching composition of the present invention preferably further contains water (hereinafter sometimes referred to as "component (C)").
• Component (A) is an alkaline compound.
• the etching composition of the present invention exhibits the effect of dissolving silicon or silicon germanium, or has excellent selective solubility of silicon relative to silicon germanium.
• the alkali compound of component (A) may be any compound that exhibits alkalinity, and examples thereof include primary to tertiary ammonium compounds, quaternary ammonium compounds (A1), alkoxides, metal amides, metal alkyls, pyridine compounds, heterocyclic amine compounds, primary to quaternary phosphonium compounds, and inorganic alkali compounds (A2). These alkaline compounds may be used alone or in combination of two or more.
• the quaternary ammonium compound (A1) (hereinafter sometimes referred to as “component (A1)”) is preferred because it has excellent stability in the atmosphere and excellent silicon solubility, and does not contain metals that can become impurities in semiconductor manufacturing, and the inorganic alkaline compound (A2) (hereinafter sometimes referred to as “component (A2)”) is preferred because it has excellent stability in the atmosphere and excellent silicon solubility.
• One or more of the quaternary ammonium compounds (A1) may be used in combination with one or more of the inorganic alkali compounds (A2).
• Component (A1) is a quaternary ammonium compound (A1).
• the etching composition of the present invention exhibits the effect of dissolving silicon or silicon germanium by containing the quaternary ammonium compound (A1).
• Component (A1) is preferably a quaternary alkylammonium compound with the total number of carbon atoms in the alkyl groups being 8 or more, since this has excellent selective solubility of silicon in silicon germanium. This total number of carbon atoms is more preferably 8 to 32, and even more preferably 12 to 24.
• the quaternary alkyl ammonium compound as component (A1) preferably has the same four alkyl groups, since this compound has excellent selective solubility of silicon relative to silicon germanium.
• component (A1) preferably contains 50% by mass or more of quaternary alkyl ammonium compounds having the same four alkyl groups, more preferably 70% by mass or more, and even more preferably 90% by mass or more, per 100% by mass of component (A1). It is most preferable that component (A1) contains 100% by mass of quaternary alkyl ammonium compounds having the same four alkyl groups.
• quaternary ammonium compounds (A1) may be used alone or in combination of two or more.
• quaternary ammonium compounds (A1) tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, benzyltrimethylammonium hydroxide, and tetrabutylammonium bromide are preferred because of their excellent selective solubility of silicon relative to silicon germanium, with tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide being more preferred, with tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide being even more preferred, and tetrabutylammonium
• component (A1) is preferably a semi-clathrate hydrate-forming compound because it has excellent selective solubility of silicon in silicon germanium.
• the semi-clathrate hydrate-forming compound refers to a compound that becomes a guest molecule that stabilizes the clathrate hydrate by participating in a hydrogen bond network.
• the semi-clathrate hydrate-forming compound it is preferable that the compound has a melting point of 5° C.
• melting point of the clathrate hydrate since the compound has excellent control over the reactivity of water molecules by hydration in a temperature range in which the etching rate is high.
• component (A1) that satisfies the above preferred conditions include quaternary alkyl ammonium compounds such as tetrabutylammonium hydroxide (melting point of clathrate hydrate: 26°C) and tetrabutylammonium bromide (melting point of clathrate hydrate: 15°C).
• quaternary alkyl ammonium compounds such as tetrabutylammonium hydroxide (melting point of clathrate hydrate: 26°C) and tetrabutylammonium bromide (melting point of clathrate hydrate: 15°C).
• the component (A2) is an inorganic alkali compound (A2).
• the etching composition of the present invention promotes dissolution of silicon and exhibits excellent selective solubility of silicon relative to silicon germanium.
• component (A2) examples include metal hydroxides of alkali metals or alkaline earth metals, such as sodium hydroxide, potassium hydroxide, and calcium hydroxide. These components (A2) may be used alone or in combination of two or more.
• metal hydroxides are preferred because they have excellent silicon solubility, with sodium hydroxide, potassium hydroxide, and calcium hydroxide being more preferred, and potassium hydroxide being even more preferred.
• the content of component (A) in the composition of the present invention is preferably 0.1 mass% or more, more preferably 1 mass% or more, and even more preferably 2.5 mass% or more, based on 100 mass% of the composition of the present invention, because the composition has excellent selective solubility of silicon in silicon germanium.
• the content of component (A) in the composition of the present invention is preferably 39.99 mass% or less, more preferably 35 mass% or less, and even more preferably 30 mass% or less, because component (A) inhibits dissolution of silicon germanium and provides excellent selective solubility of silicon relative to silicon germanium.
• the content of the component (A1) is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 15 mass% or more, in 100 mass% of the etching composition of the present invention, because the component (A1) promotes dissolution of silicon and has excellent selective solubility of silicon relative to silicon germanium.
• the content of the component (A1) is preferably 39.99 mass% or less, more preferably 35 mass% or less, and even more preferably 30 mass% or less, in 100 mass% of the etching composition of the present invention, because the component (A1) inhibits dissolution of silicon germanium and has excellent selective solubility of silicon relative to silicon germanium.
• the content of component (A2) is preferably 0.5 mass% or more, more preferably 2 mass% or more, and even more preferably 5 mass% or more, based on 100 mass% of the composition of the present invention, because component (A2) promotes dissolution of silicon and has excellent selective solubility of silicon relative to silicon germanium.
• the content of component (A2) is preferably 39.99 mass% or less, more preferably 35 mass% or less, and even more preferably 30 mass% or less, based on 100 mass% of the composition of the present invention, because component (A2) inhibits dissolution of silicon germanium and has excellent selective solubility of silicon relative to silicon germanium.
• Component (B) is a thiol compound (B).
• the thiol compound (B) is adsorbed onto the surface of silicon germanium due to the interaction between the thiol group and germanium, thereby exerting the effect of protecting silicon germanium.
• the thiol compound (B) in the present invention may be one that decomposes in the composition to generate a thiol compound. Therefore, a compound that decomposes in the composition to generate a thiol compound, such as a disulfide compound, also falls under the component (B) of the present invention.
• the etching composition of the present invention may contain a disulfide compound as component (B).
• component (B) is preferably a compound having a hydrocarbon group and a thiol group, and more preferably a compound having a hydrophobic hydrocarbon group and a thiol group.
• Such thiol compounds (B) include thioglycerol, thioglycolic acid, ethanolamine thioglycolate, 8-mercaptooctanoic acid, 1-octanethiol, 1-undecanethiol, 1-dodecanethiol, 11-mercapto-1-undecanol, 11-mercaptoundecanoic acid, 16-mercaptohexadecanoic acid, 4,4'-dithiodibutyric acid, bis(2-hydroxyethyl) disulfide, and didodecane disulfide.
• thioglycerol, thioglycolic acid, ethanolamine thioglycolate, 1-octanethiol, 1-undecanethiol, 1-dodecanethiol, 11-mercapto-1-undecanol, 11-mercaptoundecanoic acid, and 16-mercaptohexadecanoic acid are preferred from the viewpoints of easy availability, low volatility, odor suppression, and ease of handling, and thioglycerol, thioglycolic acid, ethanolamine thioglycolate, 11-mercaptoundecanoic acid, and 16-mercaptohexadecanoic acid are more preferred.
• the thiol compound (B) may be used alone or in combination of two or more types.
• the content of component (B) is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and even more preferably 0.08 mass% or more, based on 100 mass% of the etching composition of the present invention, because component (B) inhibits dissolution of silicon germanium and has excellent selective solubility of silicon relative to silicon germanium.
• the content of component (B) is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1 mass% or less, in 100 mass% of the etching composition of the present invention, because component (B) promotes dissolution of silicon and has excellent selective solubility of silicon relative to silicon germanium.
• the etching composition of the present invention preferably contains a glycerol compound in an amount of 5 mass % or less.
• Glycerol compounds are capable of making hydrophobic substances that are not miscible with water miscible with water.
• the inclusion of a glycerol compound reduces the components in the composition that contribute to etching, thereby hindering the etching of silicon. For this reason, when the composition of the present invention contains a glycerol compound, the selective solubility of silicon relative to silicon germanium is impaired.
• the content of glycerol compounds in 100% by mass of the etching composition of the present invention is preferably 5% by mass or less, more preferably 1% by mass or less, and most preferably contains no glycerol compounds (0% by mass of glycerol compounds).
• this glycerol compound does not include thiol compounds (B) such as thioglycerol.
• the etching composition of the present invention preferably contains water (component (C)) in addition to the components (A) and (B).
• the content of component (C) is preferably 60% by mass or more, more preferably 65% by mass or more, and even more preferably 70% by mass or more, based on 100% by mass of the etching composition of the present invention, because the composition is easy to manufacture, the dissolution of silicon is promoted, and the selective solubility of silicon relative to silicon germanium is excellent.
• component (C) is preferably 94.99 mass% or less, more preferably 89 mass% or less, and even more preferably 84 mass% or less, based on 100 mass% of the etching composition of the present invention, since component (C) suppresses dissolution of silicon germanium and has excellent selective solubility of silicon relative to silicon germanium.
• component (C) is preferably 99.49 mass% or less, more preferably 98 mass% or less, and even more preferably 95 mass% or less, based on 100 mass% of the etching composition of the present invention, since component (C) suppresses dissolution of silicon germanium and provides excellent selective solubility of silicon relative to silicon germanium.
• the etching composition of the present invention may contain other components in addition to the above-mentioned components (A), (B) and (C).
• the etching composition of the present invention contains a chelating agent, and thus exerts an effect of protecting silicon germanium.
• chelating agents examples include amine compounds, amino acids, and organic acids. These chelating agents may be used alone or in combination of two or more. Among these chelating agents, amine compounds, amino acids, and organic acids are preferred, and amine compounds are more preferred, because they have excellent selective solubility of silicon relative to silicon germanium.
• amine compounds include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, diethylenetriaminepentakis(methylphosphonic acid), ethylenediamine-N,N'-bis[2-(2-hydroxyphenyl)acetic acid], N,N'-bis(3-aminopropane)ethylenediamine, N-methyl-1,3-diaminopropane, 2-aminoethanol, N-methyldiethanolamine, 2-amino-2-methyl-1-propanol, etc. These amine compounds may be used alone or in combination of two or more.
• amino acids examples include glycine, arginine, histidine, (2-dihydroxyethyl)glycine, etc. These amino acids may be used alone or in combination of two or more.
• glycine, arginine, histidine, and (2-dihydroxyethyl)glycine are preferred, with (2-dihydroxyethyl)glycine being more preferred, due to their excellent selective solubility of silicon relative to silicon germanium.
• organic acids examples include oxalic acid, citric acid, tartaric acid, malic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid. These organic acids may be used alone or in combination of two or more.
• oxalic acid citric acid, tartaric acid, malic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid are preferred because they have excellent selective solubility of silicon in silicon germanium, with citric acid and 2-phosphonobutane-1,2,4-tricarboxylic acid being more preferred.
• the content of the chelating agent is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, and even more preferably 0.01 mass% or more, based on 100 mass% of the etching composition of the present invention, because the chelating agent has excellent selective solubility of silicon relative to silicon germanium.
• the content of the chelating agent is preferably 25 mass % or less, more preferably 10 mass % or less, and even more preferably 6 mass % or less, in 100 mass % of the etching composition of the present invention, since the chelating agent has excellent selective solubility of silicon in silicon germanium.
• the etching composition of the present invention may contain a water-miscible solvent.
• a water-miscible solvent By containing a water-miscible solvent, hydrophobic substances that are not miscible with water can be made miscible with water.
• containing a water-miscible solvent reduces the amount of etchable components in the composition, which hinders etching of silicon. For this reason, it is preferable that the etching composition of the present invention does not contain a water-miscible solvent.
• a water-miscible solvent may be any solvent that has excellent solubility in water, and a solvent with a solubility parameter (SP value) of 7.0 or more is preferred, and a solvent with a solubility parameter of 9.0 or more is even more preferred.
• SP value solubility parameter
• water-miscible solvents examples include polar protic solvents such as isopropanol, ethylene glycol, propylene glycol, methanol, ethanol, propanol, butanol, glycerol, and 2-(2-aminoethoxyethanol); polar aprotic solvents such as acetone, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and acetonitrile; and non-polar solvents such as hexane, benzene, toluene, and diethyl ether. These water-miscible solvents may be used alone or in combination of two or more.
• polar protic solvents such as isopropanol, ethylene glycol, propylene glycol, methanol, ethanol, propanol, butanol, glycerol, and 2-(2-aminoethoxyethanol)
• polar aprotic solvents such as acetone, di
• the content of the water-miscible solvent is preferably 5 mass% or less, more preferably 1 mass% or less, based on 100 mass% of the etching composition of the present invention, and most preferably does not contain any water-miscible solvents.
• etching composition of the present invention include, for example, surfactants such as anionic surfactants, nonionic surfactants, and cationic surfactants; water-soluble polymers such as polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyethyleneimine, polypropyleneimine, and polyacrylic acid; oxidizing agents such as hydrogen peroxide, perchloric acid, and periodic acid; and reducing agents such as ascorbic acid, gallic acid, pyrogallol, pyrocatechol, resorcinol, hydroquinone, and 8-hydroxyquinoline.
• surfactants such as anionic surfactants, nonionic surfactants, and cationic surfactants
• water-soluble polymers such as polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyethyleneimine, polypropyleneimine, and polyacrylic acid
• oxidizing agents such as hydrogen peroxide, perchloric acid, and periodic acid
• reducing agents such as ascorbic acid
• the mass ratio of component (B) to component (A) in the etching composition of the present invention is preferably 0.001 to 2, and more preferably 0.003 to 1.5, because the selective solubility of silicon in silicon germanium is excellent.
• the mass ratio of component (B) to component (A1) in the etching composition of the present invention is preferably 0.001 to 0.1, and more preferably 0.002 to 0.05, since this provides excellent selective solubility of silicon in silicon germanium.
• the mass ratio of component (B) to component (A2) in the etching composition of the present invention is preferably 0.001 to 2, and more preferably 0.1 to 1.5, since this provides excellent selective solubility of silicon in silicon germanium.
• the mass ratio of component (A) to component (C) is preferably 0.01 to 0.55, and more preferably 0.03 to 0.45, since this provides excellent selective solubility of silicon in silicon germanium.
• the mass ratio of component (A1) to component (C) is preferably 0.06 to 0.6, and more preferably 0.08 to 0.5, since this provides excellent selective solubility of silicon in silicon germanium.
• the mass ratio of component (A2) to component (C) is preferably 0.001 to 0.6, and more preferably 0.005 to 0.1, since this provides excellent selective solubility of silicon in silicon germanium.
• the mass ratio of component (B) to component (C) is preferably 0.0005 to 0.05, and more preferably 0.001 to 0.02, since this provides excellent selective solubility of silicon in silicon germanium.
• composition of the present invention is not particularly limited, and the composition can be produced by mixing components (A) and (B), and, if necessary, component (C) and other components.
• the order of mixing is not particularly limited, and all of the components may be mixed at once, or some of the components may be mixed in advance and then the remaining components may be mixed.
• the pH of the composition of the present invention is preferably from 8 to 14, more preferably from 9 to 14, and even more preferably from 10 to 14, because this provides an excellent silicon etching rate.
• the silicon etching rate ER Si of the composition of the present invention in a structure in which silicon germanium having a thickness of 10 nm and silicon having a thickness of 10 nm are laminated is preferably 5 nm/min or more, and more preferably 10 nm/min or more, since the composition has excellent selective solubility of silicon in silicon germanium.
• the etching rate ER SiGe of silicon germanium of the composition of the present invention in a structure in which silicon germanium having a thickness of 10 nm and silicon having a thickness of 10 nm are laminated is preferably 4 nm/min or less, and more preferably 2 nm/min or less, since the composition has excellent selective solubility of silicon in silicon germanium.
• the etching rate ratio (ER Si /ER SiGe ), which corresponds to the dissolution selectivity ratio of silicon germanium to silicon of the etching composition of the present invention in a structure in which silicon germanium having a thickness of 10 nm and single crystal silicon having a thickness of 10 nm are stacked, is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more, because the selective solubility of single crystal silicon relative to silicon germanium is excellent.
• the etching rate ER Si , the etching rate ER SiGe , and the dissolution selectivity ratio (ER Si /ER SiGe ) are measured and calculated by the method described in the Examples section below.
• the etching composition of the present invention suppresses the dissolution of silicon germanium, promotes the dissolution of silicon, and has excellent selective solubility of silicon relative to silicon germanium, and is therefore suitable for an etching solution, more suitable for an etching solution that dissolves silicon, and particularly suitable for an etching solution that suppresses the dissolution of silicon germanium and dissolves silicon.
• the etching composition of the present invention is suitable for etching structures containing silicon, more suitable for structures containing silicon and silicon germanium, and particularly suitable for structures in which silicon and silicon germanium are alternately stacked, which are necessary for forming a GAA type FET.
• Structures containing silicon, structures containing silicon and silicon germanium, and structures in which silicon and silicon germanium are alternately stacked, which are necessary for forming GAA type FETs, are used in semiconductor devices.
• the silicon to be etched is preferably single-crystal silicon, since single-crystal silicon germanium has excellent characteristics for gate-all-around transistors, and single-crystal silicon germanium is less likely to have defects when grown epitaxially on single-crystal silicon germanium.
• the silicon content in the silicon germanium to be etched is preferably 10 mass % or more, and more preferably 20 mass % or more, based on 100 mass % of silicon germanium, in order to be suitable for etching with the etching composition of the present invention.
• the silicon content in the silicon germanium to be etched is preferably 95 mass % or less, and more preferably 85 mass % or less, based on 100 mass % of silicon germanium, in order to be suitable for etching with the etching composition of the present invention.
• the germanium content in the silicon germanium to be etched is preferably 5 mass % or more, and more preferably 15 mass % or more, based on 100 mass % of silicon germanium, since this is suitable for etching with the etching composition of the present invention.
• the germanium content in the silicon germanium to be etched is preferably 90 mass % or less, and more preferably 80 mass % or less, based on 100 mass % of silicon germanium, in order to be suitable for etching with the etching composition of the present invention.
• the silicon germanium alloy film may be produced by deposition using known methods, but it is preferable to produce it by deposition using a crystal growth method, as this provides excellent mobility of electrons and holes after transistor formation.
• silicon oxide, silicon nitride, silicon carbonitride, etc. may be exposed.
• the etching method of the present invention is a method for etching a structure containing silicon and silicon germanium using the etching composition of the present invention.
• the silicon to be etched is preferably single crystal silicon, since single crystal silicon germanium has excellent characteristics for gate-all-around transistors, and single crystal silicon germanium is less likely to have defects when epitaxially grown on single crystal silicon germanium.
• a known etching method can be used, such as a batch method or a single wafer method.
• the temperature during etching is preferably 15° C. or higher, and more preferably 20° C. or higher, since this allows the etching rate to be improved.
• the temperature during etching is preferably 100° C. or less, and more preferably 80° C. or less, from the viewpoints of reducing damage to the substrate and ensuring etching stability.
• the temperature during etching corresponds to the temperature of the etching composition during etching.
• the etching composition of the present invention suppresses the dissolution of silicon germanium, promotes the dissolution of silicon, and has excellent selective solubility of silicon relative to silicon germanium, and is therefore suitable for an etching solution, more suitable for an etching solution that dissolves silicon, and particularly suitable for an etching solution that suppresses the dissolution of silicon germanium and dissolves silicon.
• the etching composition and etching method of the present invention can be suitably used in the manufacture of semiconductor devices, which includes a step of etching a structure containing silicon and silicon germanium, and suppresses the dissolution of silicon germanium, promotes the dissolution of silicon, and has excellent selective solubility of silicon relative to silicon germanium. Therefore, the etching composition and etching method of the present invention can be particularly suitably used in the manufacture of GAA type FETs, which includes a step of etching a structure containing silicon and silicon germanium. In particular, they are suitable for structures in which silicon and silicon germanium are alternately stacked, which are necessary for the formation of GAA type FETs.
• ER Si [nm/min] (width of silicon layer before immersion [nm] ⁇ width of silicon layer after immersion [nm]) ⁇ (immersion time [min]) ⁇ 2 (1)
• ER SiGe [nm/min] (width of silicon germanium layer before immersion [nm] ⁇ width of silicon germanium layer after immersion [nm]) ⁇ (immersion time [min]) ⁇ 2 (2)
• Dissolution selectivity ER Si [nm/min] ⁇ ER SiGe [nm/min] (3)
• Example 1 The components were mixed so that, based on 100% by mass of the composition, the component (A1-1) was 26.0% by mass, the component (B-1) was 0.1% by mass, and water was the balance, to obtain a composition.
• the evaluation results of the obtained compositions are shown in Table 1.
• Examples 2 and 10 Comparative Examples 1, 7, and 8
• Compositions were obtained in the same manner as in Example 1, except that the type and/or content of each component in the composition was changed as shown in Table 1.
• Examples 3 to 9, 11, Comparative Examples 2 to 5 Compositions were obtained in the same manner as in Example 1, except that the type and/or content of each component in the composition was changed as shown in Table 1 and nitrogen gas was bubbled for 5 minutes. In addition, evaluations were performed in the same manner as in Example 1, except that bubbling was performed when the substrate was immersed.
• Example 12 The components were mixed so that, based on 100% by mass of the composition, the component (A2-1) was 5.6% by mass, the component (B-1) was 1.0% by mass, and water was the remainder, and then bubbled with nitrogen gas for 5 minutes to obtain a composition. In addition, except that bubbling was also performed when the substrate was immersed, the same operation as in Example 1 was performed and evaluation was performed.
• Examples 13 to 14, Comparative Example 6 Compositions were obtained in the same manner as in Example 12, except that the type and/or content of each component in the composition was changed as shown in Table 1. The evaluation results of the obtained compositions are shown in Table 1.
• compositions of Examples 1 to 14 containing component (A) and component (B) suppress the dissolution of silicon germanium, promote the dissolution of silicon, and are excellent in the selective solubility of silicon relative to silicon germanium.
• compositions of Comparative Examples 1 to 6, which do not contain component (B) are inferior in the selective solubility of silicon in silicon germanium.
• Comparative Examples 7 and 8 which do not contain component (A), neither silicon nor silicon germanium can be dissolved.
• the etching composition of the present invention and the etching method of the present invention using this composition suppress the dissolution of silicon germanium, promote the dissolution of silicon, and have excellent selective solubility of silicon relative to silicon germanium. Therefore, the etching composition of the present invention and the etching method of the present invention using this etching composition are suitable for structures containing silicon as the etching target.
• the etching composition and etching method of the present invention can be suitably used in the manufacture of semiconductor devices, and in particular, can be suitably used in the manufacture of GAA type FETs.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Crystallography & Structural Chemistry (AREA)
• Metallurgy (AREA)
• Weting (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Insulated Gate Type Field-Effect Transistor (AREA)
• Thin Film Transistor (AREA)

Priority Applications (3)

Applications Claiming Priority (4)

Related Child Applications (1)

Publications (1)

Family

ID=92263061

Family Applications (1)

Country Status (5)

Citations (4)

Family Cites Families (1)

• 2024
  • 2024-02-08 JP JP2024576902A patent/JPWO2024166976A1/ja active Pending
  • 2024-02-08 WO PCT/JP2024/004306 patent/WO2024166976A1/ja not_active Ceased
  • 2024-02-08 KR KR1020257022727A patent/KR20250148703A/ko active Pending
  • 2024-02-15 TW TW113105219A patent/TW202440877A/zh unknown
• 2025
  • 2025-08-08 US US19/295,266 patent/US20250361441A1/en active Pending

Patent Citations (4)

Also Published As

Similar Documents

Legal Events