Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
  • C23F11/167—Phosphorus-containing compounds
  • C23F11/1676—Phosphonic acids
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
  • C23F11/12—Oxygen-containing compounds
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  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds
  • C11D7/04—Water-soluble compounds
  • C11D7/10—Salts
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/34—Organic compounds containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/36—Organic compounds containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
  • C23F11/16—Sulfur-containing compounds
  • C23F11/163—Sulfonic acids
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
  • H10D64/00—Electrodes of devices having potential barriers
  • H10D64/01—Manufacture or treatment
  • H10D64/011—Manufacture or treatment of electrodes ohmically coupled to a semiconductor
• • 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
  • H10P70/00—Cleaning of wafers, substrates or parts of devices
  • H10P70/20—Cleaning during device manufacture
  • H10P70/27—Cleaning during device manufacture during, before or after processing of conductive materials, e.g. polysilicon or amorphous silicon layers
• • 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
  • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/01—Manufacture or treatment
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W90/00—Package configurations
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/01—Manufacture or treatment
  • H10W72/019—Manufacture or treatment of bond pads
  • H10W72/01931—Manufacture or treatment of bond pads using blanket deposition
  • H10W72/01938—Manufacture or treatment of bond pads using blanket deposition in gaseous form, e.g. by CVD or PVD
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/01—Manufacture or treatment
  • H10W72/019—Manufacture or treatment of bond pads
  • H10W72/01971—Cleaning, e.g. oxide removal
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/90—Bond pads, in general
  • H10W72/921—Structures or relative sizes of bond pads
  • H10W72/923—Bond pads having multiple stacked layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/90—Bond pads, in general
  • H10W72/951—Materials of bond pads
  • H10W72/952—Materials of bond pads comprising metals or metalloids, e.g. PbSn, Ag or Cu
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W80/00—Direct bonding of chips, wafers or substrates
  • H10W80/211—Direct bonding of chips, wafers or substrates using auxiliary members, e.g. aids for protecting the bonding area
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W80/00—Direct bonding of chips, wafers or substrates
  • H10W80/301—Bonding techniques, e.g. hybrid bonding
  • H10W80/312—Bonding techniques, e.g. hybrid bonding characterised by the direct bonding of electrically conductive pads

Definitions

• the present invention relates to a composition for protecting a copper surface, and a semiconductor intermediate and a method for manufacturing a semiconductor using the composition.
• 3D integration technology is attracting attention as a method to meet the demands for smaller size and higher functionality of semiconductors.
• 3D integration technology involves stacking multiple semiconductor chips or semiconductor wafers by interconnecting them, and known stacking formats include Chip to Chip (C2C), Chip to Wafer (C2W), and Wafer to Wafer (W2W). ing.
• C2C Chip to Chip
• C2W Chip to Wafer
• W2W Wafer to Wafer
• Patent Document 1 describes a semiconductor layer, an adhesive layer disposed above the semiconductor layer, an anode metal layer disposed above the adhesive layer, and a semiconductor layer disposed above the semiconductor layer.
• An invention is described that relates to a semiconductor structure comprising a cathode metal layer disposed above an anode metal layer.
• Patent Document 1 describes that rapid oxide formation on the Cu surface, which inhibits sufficient interconnection, is a serious problem in interconnection by Cu--Cu bonding.
• Patent Document 1 describes that as a method of inhibiting Cu oxidation, by using a metal (such as Mg) having an oxidation potential higher than the Cu oxidation potential, a galvanic pair is formed and Mg itself is sacrificed. It has been described that Cu oxide growth is inhibited or reduced.
• the present invention includes, for example, the following aspects.
• R is a substituted or unsubstituted alkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms] At least one copper surface protective agent selected from the group consisting of a compound represented by and a salt thereof; a solvent; A composition for protecting copper surfaces.
• the copper surface protection agent contains a compound represented by formula (1) and/or a salt thereof.
• R is a substituted or unsubstituted alkyl group having 3 to 30 carbon atoms.
• the pH adjuster contains at least one selected from the group consisting of sodium hydroxide and potassium hydroxide.
• a method for producing a first semiconductor intermediate comprising a copper-containing layer and a copper surface protection layer laminated on the copper-containing layer, A step of contacting the copper surface protection composition according to any one of [1] to [7] above on the copper-containing layer of the first semiconductor having the copper-containing layer to form a copper surface protection layer.
• a method for manufacturing a first semiconductor intermediate comprising (1).
• the method for producing the first semiconductor intermediate according to [8] above including a step of cleaning the copper-containing layer with a cleaning liquid before the step (1).
• the cleaning liquid contains at least one selected from the group consisting of hydrofluoric acid, sulfuric acid, nitric acid, and ammonia.
• a method for manufacturing a semiconductor including a copper-containing bonding layer, removing the copper surface protective layer of the first semiconductor intermediate produced by the method according to any one of [8] to [10] above to expose the copper-containing layer;
• a method for manufacturing a semiconductor comprising the step of bonding the exposed copper-containing layer with the metal-containing layer in a second semiconductor intermediate including the metal-containing layer to form a copper-containing bonding layer.
• a composition for protecting a copper surface, etc. that can prevent oxidation of the copper surface is provided.
• a composition for protecting a copper surface, etc. that can prevent oxidation of the copper surface.
• the composition for protecting a copper surface includes at least one copper surface protecting agent selected from the group consisting of compounds represented by formulas (1) to (3) and salts thereof, and a solvent.
• the copper surface protection composition may further contain a pH adjuster, a surfactant, a viscosity adjuster, a chelating agent, a reducing agent, an antifoaming agent, and the like.
• the copper surface protection composition is preferably used in the manufacture of semiconductors.
• a copper surface protection layer can be formed by bringing a copper surface protection composition into contact with a copper surface (for example, a copper-containing layer included in a semiconductor). Since the copper surface protective layer is a dense layer, it can prevent oxygen from permeating. As a result, contact between the copper surface and oxygen can be prevented, and oxidation of the copper surface can be prevented.
• a copper surface protection layer can be formed by bringing a copper surface protection composition into contact with a copper surface (for example, a copper-containing layer included in a semiconductor). Since the copper surface protective layer is a dense layer, it can prevent oxygen from permeating. As a result, contact between the copper surface and oxygen can be prevented, and oxidation of the copper surface can be prevented.
• the copper surface protection layer formed on the copper-containing layer can be stably maintained for a long period of time, so that the semiconductor intermediate having the copper surface protection layer can be maintained for a long time. Can be stored for a period of time.
• the copper surface protection composition has excellent usability because the formed copper surface protection layer has high removability. Since a covalent bond between the copper and copper surface protective layers is not necessarily required, the copper surface protective layer can be easily removed by heating, hydrogen ashing, ion irradiation with an inert gas, etc., for example. Therefore, the copper surface protection composition has excellent usability.
• the copper surface protective agent is selected from the group consisting of compounds represented by formulas (1) to (3) and salts thereof.
• R is a substituted or unsubstituted alkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
• alkyl group having 3 to 30 carbon atoms examples include, but are not limited to, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, heptyl group, heptyl group, octyl group, Examples include nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, octadecyl group, and icosyl group.
• the substituent is not particularly limited, but includes an alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, and propyloxy; a hydroxy group; a cyano group; Nitro group; halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. There may be one substituent or a combination of two or more.
• Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, and the like.
• the substituent is not particularly limited, but alkyl groups having 1 to 30 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc. ; alkoxy groups having 1 to 30 carbon atoms such as methoxy, ethoxy, and propyloxy groups; hydroxy groups; cyano groups; nitro groups; halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), and the like.
• the number of substituents may be one, and may have two or more in combination.
• R is the same as in formulas (1) to (3).
• X + can each independently be a monovalent cation.
• two X + between the compounds of the compounds of formulas (1-1) to (3-1), and two X + within the compounds of the compounds of formulas (1-2) and (2-2). may be one divalent cation.
• two compounds of formula (1-1) may have the following structure containing a divalent cation.
• the monovalent cation is not particularly limited, but includes sodium cation, potassium cation, ammonium cation, quaternary ammonium cation (methylammonium cation, ethylammonium cation, dimethylammonium cation, trimethylammonium cation, tetramethylammonium cation), etc. can be mentioned. These monovalent cations may be contained alone or in combination of two or more.
• the divalent cations include, but are not particularly limited to, magnesium cations, calcium cations, strontium cations, barium cations, and the like.
• copper surface protective agents include, but are not limited to, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, nonylphosphonic acid, decylphosphonic acid, undecylphosphonic acid.
• Compounds represented by formula (1) such as acids, dodecylphosphonic acid, phenylphosphonic acid, 4-methylphenylphosphonic acid, naphthylphosphonic acid; propyl phosphoric acid, butyl phosphoric acid, pentyl phosphoric acid, hexyl phosphoric acid, heptyl phosphonic acid, octyl phosphonic acid
• Compounds represented by formula (2) such as acids, nonyl phosphoric acid, decyl phosphoric acid, undecyl phosphoric acid, dodecyl phosphoric acid, phenyl phosphoric acid, 4-nitrophenyl phosphoric acid; propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid , hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenz
• the copper surface protective agent preferably contains at least one of the compound represented by formula (1) and a salt thereof, and includes propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, and heptylphosphonic acid. More preferably, it contains at least one selected from the group consisting of phosphonic acid, octylphosphonic acid, nonylphosphonic acid, decylphosphonic acid, undecylphosphonic acid, dodecylphosphonic acid, and salts thereof, and heptylphosphonic acid, octylphosphonic acid, and salts thereof.
• the said copper surface protection agent may be used individually, or may be used in combination of 2 or more types.
• the content of the copper surface protective agent is preferably 0.00001 to 1% by mass, more preferably 0.0001 to 1% by mass, based on the total mass of the composition for copper surface protection. It is more preferably .001 to 0.5% by weight, particularly preferably 0.005 to 0.1% by weight. It is preferable that the content of the copper surface protective agent is 0.00001% by mass or more because a dense copper surface protective layer can be formed. On the other hand, it is preferable that the content of the copper surface protective agent is 1% by mass or less because it is easy to prepare a uniform composition.
• solvent The solvent is not particularly limited, and examples include water and organic solvents.
• the water is not particularly limited, but it is preferably water from which metal ions, organic impurities, particles, etc. have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc., and pure water is preferable. More preferred is ultrapure water.
• the organic solvent is not particularly limited, but includes alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and tert-butanol; ethylene glycol, propylene glycol, neopentyl glycol, and 1,2-hexanediol.
• glycol ethers such as -butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, and propylene glycol phenyl
• the solvent is water.
• the said solvent may be used individually or may be used in combination of 2 or more types.
• the addition rate of the solvent, especially water is preferably 50% by mass or more, more preferably 80% by mass or more, and 90% by mass or more based on the total mass of the copper surface protection composition. It is more preferable that the amount is 95% by mass or more, and particularly preferably 95% by mass or more.
• the pH adjuster has a function of adjusting the pH of the copper surface protection composition.
• Examples of the pH adjuster include acidic compounds and basic compounds.
• the acidic compounds are not particularly limited, but include strong inorganic acid compounds such as hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, and nitric acid; strong organic acid compounds such as methanesulfonic acid and benzenesulfonic acid; weak inorganic acids such as phosphoric acid.
• strong inorganic acid compounds such as hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, and nitric acid
• strong organic acid compounds such as methanesulfonic acid and benzenesulfonic acid
• weak inorganic acids such as phosphoric acid.
• Compounds include organic weak acid compounds such as acetic acid and citric acid.
• the basic compound is not particularly limited, but includes strong inorganic basic compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide; tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH).
• Inorganic weak base compounds such as sodium carbonate and ammonia;
• Organic weak base compounds such as diazabicycloundecene (DBU) and diazabicyclononene (DBU).
• the pH adjuster preferably contains at least one selected from the group consisting of a strong inorganic acid compound, a strong inorganic base compound, and a weak inorganic base compound, including sulfuric acid, nitric acid, sodium hydroxide, and potassium hydroxide. , calcium hydroxide, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), and ammonia.
• TMAH tetramethylammonium hydroxide
• TEAH tetraethylammonium hydroxide
• ammonia ammonia.
• At least one selected from the group consisting of calcium oxide, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), and ammonia is included, and sodium hydroxide, potassium hydroxide, and hydroxide It is particularly preferable that at least one member selected from the group consisting of calcium is included.
• the above-mentioned pH adjuster may be used individually or may be used in combination of 2 or more types.
• the content of the pH adjuster is not particularly limited, and it is preferably an amount that makes the pH of the copper surface protection composition a desired pH.
• the pH of the copper surface protection composition is preferably 0.1 to 13, more preferably 1 to 12.5, even more preferably 2 to 12, and even more preferably 2.5 to 5.5. It is particularly preferable that By adjusting the pH of the copper surface protection composition, a suitable copper surface protection layer can be formed on the copper surface.
• a change in the surface potential ( ⁇ potential) of copper due to pH may be cited.
• the pH of the copper surface protection composition is acidic (pH less than 7.0)
• the copper surface has many positive charges
• the pH is basic (pH greater than 7.0).
• copper surfaces tend to have many negative charges. It is thought that such a change in the surface potential ( ⁇ potential) of copper allows the copper surface protecting agent contained in the copper surface protecting composition to interact favorably with the copper surface.
• the semiconductor intermediate includes a copper-containing layer and a copper surface protection layer laminated on the copper-containing layer.
• the method for manufacturing the semiconductor intermediate includes the step of contacting the copper surface protection composition described above on the copper-containing layer of the first semiconductor having the copper-containing layer to form a copper surface protection layer. 1).
• the semiconductor intermediate may include a step (cleaning step) of cleaning the copper-containing layer with a cleaning liquid before the step (1).
• cleaning step and step (1) will be explained in this order.
• the term "copper-containing layer” refers to a layer in which at least metal copper is present on the surface of the layer, and the copper-containing layer is preferably a layer made of copper.
• a washing step is performed before step (1).
• the cleaning step is a step of cleaning the copper-containing layer in the first semiconductor having the copper-containing layer with a cleaning liquid.
• the first semiconductor includes a copper-containing layer.
• the first semiconductor is not particularly limited, but includes a semiconductor chip or a semiconductor wafer.
• the cleaning liquid has a function of cleaning the surface of the copper-containing layer, for example, a function of removing copper oxide formed on the exposed surface of the copper-containing layer.
• the cleaning liquid includes a cleaning agent and a solvent.
• the cleaning agent is not particularly limited, but includes at least one selected from the group consisting of acids and alkalis.
• the acids include, but are not particularly limited to, inorganic acids such as hydrofluoric acid, hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, and phosphoric acid; acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and benzenesulfone.
• inorganic acids such as hydrofluoric acid, hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, and phosphoric acid
• acetic acid methanesulfonic acid, trifluoromethanesulfonic acid, and benzenesulfone.
• organic acids such as p-toluenesulfonic acid and 10-camphorsulfonic acid.
• the alkali is not particularly limited, but includes ammonia and ammonium salts.
• the ammonium salt is not particularly limited, but includes ammonium fluoride (NH 4 F); ammonium hydrogen fluoride (NH 4 F.HF); tetraethylammonium hydroxide (TEAH), tetramethylammonium hydroxide (TMAH), and ethyl fluoride.
• NH 4 F ammonium fluoride
• NH 4 F.HF ammonium hydrogen fluoride
• TEAH tetraethylammonium hydroxide
• TMAH tetramethylammonium hydroxide
• ethyl fluoride ethyl fluoride
• Tetraalkylammonium hydroxides such as trimethylammonium hydroxide, diethyldimethylammonium hydroxide, triethylmethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide; Aryls such as benzyltrimethylammonium hydroxide and benzyltriethylammonium hydroxide Group-containing ammonium hydroxide; trimethyl (2-hydroxyethyl) ammonium hydroxide, triethyl (2-hydroxyethyl) ammonium hydroxide, tripropyl (2-hydroxyethyl) ammonium hydroxide, trimethyl (1-hydroxypropyl) ammonium hydroxide Examples include hydroxy group-containing ammonium hydroxide such as.
• the cleaning agent preferably contains at least one selected from the group consisting of acid and ammonia, and includes hydrofluoric acid, hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, and ammonia. More preferably at least one selected from the group consisting of hydrofluoric acid, sulfuric acid, nitric acid, and ammonia; more preferably at least one selected from the group consisting of hydrofluoric acid, sulfuric acid, nitric acid, and ammonia; It is particularly preferable that at least one selected from the group consisting of: sulfuric acid is included, and sulfuric acid is most preferably included. Note that the cleaning agents may be used alone or in combination of two or more.
• the content of the cleaning agent is preferably 0.001 to 50% by mass, more preferably 0.01 to 10% by mass, and 0.03 to 3% by mass based on the total mass of the cleaning liquid. It is more preferable that the amount is 0.05 to 2% by mass, and particularly preferably 0.05 to 2% by mass.
• the solvent is not particularly limited, but examples include those similar to those used in the copper surface protection composition. Among these, the solvent is preferably water. In addition, the said solvent may be used individually or may be used in combination of 2 or more types.
• the addition rate of the solvent, especially water is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, based on the total mass of the cleaning liquid.95 It is particularly preferable that the amount is at least % by mass.
• the cleaning liquid may further contain a pH adjuster.
• the pH adjuster is not particularly limited, but examples include those similar to the pH adjusters used in copper surface protection compositions. These pH adjusters may be used alone or in combination of two or more.
• the pH of the cleaning solution is not particularly limited, but is preferably from 0.1 to 13, more preferably from 0.5 to 10, even more preferably from 0.5 to 5, and even more preferably from 0.4 to 2. 5 is particularly preferred.
• the cleaning method is not particularly limited, and known techniques can be employed as appropriate.
• the first semiconductor may be immersed in a cleaning liquid, the cleaning liquid may be sprayed onto the surface of the copper-containing layer of the first semiconductor, or the cleaning liquid may be dropped (by single-wafer spin treatment, etc.). good.
• the dipping may be repeated two or more times, the spraying may be repeated two or more times, the dropping may be repeated two or more times, or dipping, spraying, and dropping may be combined.
• the washing temperature is not particularly limited, but is preferably 0 to 90°C, more preferably 5 to 70°C, and even more preferably 10 to 50°C.
• the washing time is not particularly limited, but is preferably 10 seconds to 3 hours, more preferably 10 seconds to 1 hour, even more preferably 15 seconds to 45 minutes, and even more preferably 30 seconds to 20 minutes. It is particularly preferable that there be.
• Step (1) is a step of bringing the above-described copper surface protection composition into contact with the copper-containing layer of the first semiconductor having the copper-containing layer to form a copper surface protection layer.
• First semiconductor As the first semiconductor, the one described above is used. At this time, the first semiconductor is preferably subjected to the above-mentioned cleaning process to remove copper oxide that the copper-containing layer may have.
• Copper surface protection composition As the copper surface protection composition, the one described above is used.
• the contact method is not particularly limited, and known techniques can be employed as appropriate.
• the first semiconductor may be immersed in the copper surface protection composition, the copper surface protection composition may be sprayed onto the surface of the copper-containing layer of the first semiconductor, or the copper surface protection composition may be dropped. (Single wafer spin processing, etc.) may be performed. At this time, the dipping may be repeated two or more times, the spraying may be repeated two or more times, the dropping may be repeated two or more times, or dipping, spraying, and dropping may be combined.
• the contact temperature is not particularly limited, but is preferably 0 to 90°C, more preferably 5 to 70°C, and even more preferably 10 to 65°C.
• the contact time is not particularly limited, but is preferably 10 seconds to 3 hours, more preferably 10 seconds to 1 hour, even more preferably 1 to 45 minutes, and 3 to 20 minutes. is particularly preferred.
• excess copper surface protection composition, etc. is appropriately washed with water, isopropyl alcohol, etc., and the solvent contained in the copper surface protection composition adhered to the surface of the copper-containing layer is removed, thereby removing the copper surface protection layer. can be formed.
• the copper surface protection layer contains a copper surface protection agent. Since the copper surface protective layer is a dense layer, it is difficult for oxygen to permeate through it. As a result, contact of oxygen to the copper-containing layer can be prevented, and oxidation of the surface of the copper-containing layer can be prevented.
• the thickness of the copper surface protective layer is not particularly limited, but is preferably 0.1 to 50 nm, more preferably 0.2 to 10 nm, even more preferably 0.3 to 2 nm, and A range of .4 to 1 nm is particularly preferred.
• the thickness of the "copper surface protective layer” means the maximum thickness of the copper surface protective layer in the direction perpendicular to the contact surface between the copper-containing layer and the copper surface protective layer.
• the first semiconductor intermediate includes a copper-containing layer and a copper surface protection layer laminated on the copper-containing layer.
• the copper surface protective layer may cover part or all of other layers such as an insulating layer and a silicon substrate layer in addition to the copper-containing layer.
• the copper surface protective layer is formed on the copper-containing layer, so that oxidation of the surface of the copper-containing layer can be prevented. Therefore, the first semiconductor intermediate can be stored for a long period of time.
• a method for manufacturing a semiconductor includes a copper-containing bonding layer.
• the semiconductor manufacturing method includes a step (exposure step) of removing the copper surface protective layer of the first semiconductor intermediate manufactured by the above method to expose the copper-containing layer, and removing the exposed copper-containing layer. , a step of forming a copper-containing bonding layer by bonding with the metal-containing layer in the second semiconductor intermediate including the metal-containing layer (bonding step).
• a "metal-containing layer” means a layer in which at least a metal is present on the surface of the layer, and the metal-containing layer is preferably a layer made of metal.
• the "metal” is a metal that can be bonded to copper, preferably copper or tin, and more preferably copper.
• the exposing step is a step of removing the copper surface protective layer of the first semiconductor intermediate to expose the copper-containing layer.
• the method for removing the copper surface protective layer of the first semiconductor intermediate is not particularly limited, but heating, hydrogen ashing, and inert gas ion irradiation are preferable, and heating is more preferable. Further, heating may be performed under an inert gas atmosphere. Examples of the inert gas include nitrogen and argon.
• the heating temperature is not particularly limited, but is preferably 100 to 300°C, more preferably 150 to 250°C.
• the heating time is not particularly limited, but is preferably from 0.1 seconds to 3 hours, more preferably from 1 second to 1 hour, even more preferably from 10 seconds to 15 minutes, and even more preferably from 1 minute to 15 minutes. Particularly preferred is minutes.
• the copper-containing layer By removing the copper surface protective layer of the first semiconductor, the copper-containing layer can be exposed. That is, a first semiconductor having a copper-containing layer is obtained.
• the bonding step is a step of bonding the exposed copper-containing layer with the metal-containing layer in the second semiconductor intermediate including the metal-containing layer to form a copper-containing bonding layer.
• the second semiconductor intermediate includes a metal-containing layer.
• the second semiconductor intermediate is not particularly limited, but examples include a semiconductor chip or a semiconductor wafer. Note that when the metal-containing layer is a copper-containing layer, the second semiconductor intermediate may be manufactured by the same method as the first semiconductor intermediate. In this case, it is used in the bonding process after the above-mentioned exposure process.
• Bonding can interconnect the copper-containing layer and the metal-containing layer to obtain a three-dimensional (3D) integrated semiconductor.
• the joining method is not particularly limited, but thermocompression bonding is preferable.
• the bonding temperature is not particularly limited, but is preferably 80 to 500°C, more preferably 90 to 300°C, even more preferably 100 to 250°C, particularly 120 to 200°C. preferable.
• the bonding time is not particularly limited, and is preferably 0.01 to 600 seconds, more preferably 0.1 to 60 seconds.
• a copper surface protection composition was prepared by mixing butylphosphonic acid, which is a copper surface protection agent, and water, which is a solvent. At this time, the content of butylphosphonic acid was 0.01% by mass based on the total mass of the copper surface protection composition.
• the pH of the copper surface protection composition was measured and found to be 3.2. Note that pH was measured at 23° C. using a tabletop pH meter (F-71) (manufactured by Horiba, Ltd.) and a pH electrode (9615S-10D) (manufactured by Horiba, Ltd.).
• Example 2 A copper surface protection composition was produced in the same manner as in Example 1, except that hexylphosphonic acid was used as the copper surface protection agent. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 3.3.
• Example 3 A copper surface protection composition was produced in the same manner as in Example 1, except that octylphosphonic acid was used as the copper surface protection agent. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 3.4.
• Example 4 A composition for protecting a copper surface was produced in the same manner as in Example 1, except that dodecyl phosphoric acid was used as a copper surface protecting agent so that the content was 0.001% by mass. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 4.5.
• Example 5 A copper surface protection composition was produced in the same manner as in Example 1, except that phenylphosphonic acid was used as the copper surface protection agent. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 3.2.
• Example 6 A copper surface protection composition was produced in the same manner as in Example 1, except that 4-dodecylbenzenesulfonic acid was used as a copper surface protection agent at a content of 0.05% by mass. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 2.9.
• Example 7 A copper surface protection composition was produced in the same manner as in Example 3, except that sulfuric acid was further added as a pH adjuster so that the content was 1% by mass. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 1.2.
• Example 8 A copper surface protection composition was produced in the same manner as in Example 3, except that sulfuric acid was further added as a pH adjuster so that the content was 0.05% by mass. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 2.1.
• Example 9 A copper surface protection composition was produced in the same manner as in Example 3, except that ammonia was further added as a pH adjuster so that the content was 0.0006% by mass. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 4.0.
• Example 10 A copper surface protection composition was produced in the same manner as in Example 3, except that ammonia was further added as a pH adjuster so that the content was 0.0007% by mass. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 5.0.
• Example 11 A copper surface protection composition was produced in the same manner as in Example 3, except that ammonia was further added as a pH adjuster so that the content was 0.0012% by mass. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 6.0.
• Example 12 A copper surface protection composition was produced in the same manner as in Example 3, except that ammonia was further added as a pH adjuster so that the content was 0.0014% by mass. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 7.0.
• Example 13 A copper surface protection composition was produced in the same manner as in Example 3, except that ammonia was further added as a pH adjuster so that the content was 0.0016% by mass. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 8.0.
• Example 14 A copper surface protection composition was produced in the same manner as in Example 3, except that ammonia was further added as a pH adjuster so that the content was 0.0031% by mass. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 9.0.
• Example 15 A copper surface protection composition was produced in the same manner as in Example 3, except that ammonia was further added as a pH adjuster so that the content was 0.013% by mass. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 10.0.
• Example 16 A copper surface protection composition was prepared in the same manner as in Example 3, except that tetramethylammonium hydroxide (TMAH) was further added as a pH adjuster so that the content was 0.018% by mass. Manufactured. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 11.0.
• TMAH tetramethylammonium hydroxide
• Example 17 A copper surface protection composition was prepared in the same manner as in Example 3, except that tetramethylammonium hydroxide (TMAH) was further added as a pH adjuster so that the content was 0.075% by mass. Manufactured. In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 12.0.
• TMAH tetramethylammonium hydroxide
• Example 18 A copper surface protection composition was produced in the same manner as in Example 3, except that sodium hydroxide (NaOH) was further added as a pH adjuster so that the content was 0.0026% by mass. . In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 5.0.
• NaOH sodium hydroxide
• Example 19 A copper surface protection composition was produced in the same manner as in Example 3, except that potassium hydroxide (KOH) was further added as a pH adjuster so that the content was 0.0029% by mass. . In addition, when the pH of the copper surface protection composition was measured in the same manner as in Example 1, it was found to be 5.0.
• KOH potassium hydroxide
• Example 1 A composition was produced in the same manner as in Example 1, except that benzotriazole was used in place of the copper surface protective agent so that the content was 0.05% by mass. In addition, when the pH of the composition was measured in the same manner as in Example 1, it was 5.2.
• composition was produced in the same manner as in Example 1, except that dodecylpyridinium chloride was used in place of the copper surface protective agent so that the content was 0.05% by mass.
• pH of the composition was measured in the same manner as in Example 1, it was found to be 4.7.
• Example 3 A composition was prepared in the same manner as in Example 1, except that 1-hydroxyethane-1,1-diphosphonic acid was used in a content of 0.5% by mass instead of the copper surface protective agent. was manufactured. In addition, when the pH of the composition was measured in the same manner as in Example 1, it was found to be 1.7.
• Table 1 below shows the copper surface protection compositions produced in Examples 1 to 19 and Comparative Examples 1 to 4.
• the copper oxidation rate in the plated Cu sample having the copper surface protective layer after storage was measured. Specifically, a plated Cu sample having a copper surface protective layer after storage was analyzed by X-ray photoelectron spectroscopy (XPS; PHI Quantera II manufactured by ULVAC-PHI Inc.) to obtain a narrow scan spectrum of Cu2p. The obtained narrow scan spectrum of Cu2p was analyzed by curve fitting, and the peak area of Cu 2+ alone and the sum of the peak areas of Cu + and Cu were calculated. Using the obtained peak area, the copper oxidation rate (the value obtained by dividing the peak area of Cu 2+ by the sum of the peak areas of Cu + and Cu) was determined.
• XPS X-ray photoelectron spectroscopy
• the contact angle of water on the surface of the Cu sample before and after standing on a hot plate was measured and evaluated based on the following criteria. Note that when the copper surface protective layer is removed by heating, the copper surface with high surface free energy is exposed, and the contact angle tends to become small. The results obtained are shown in Table 2 below.
• Example 3 (1) 1% hydrofluoric acid (DHF) Using the copper surface protection composition of Example 3, the copper oxidation rate and removability were evaluated in the same manner as above.
• This example uses 1% hydrofluoric acid (DHF) as a pretreatment agent.

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