WO2016132951A1 - Composition de polissage - Google Patents

Composition de polissage Download PDF

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Publication number
WO2016132951A1
WO2016132951A1 PCT/JP2016/053718 JP2016053718W WO2016132951A1 WO 2016132951 A1 WO2016132951 A1 WO 2016132951A1 JP 2016053718 W JP2016053718 W JP 2016053718W WO 2016132951 A1 WO2016132951 A1 WO 2016132951A1
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WIPO (PCT)
Prior art keywords
polishing
site
silicon
polishing composition
group
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PCT/JP2016/053718
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English (en)
Japanese (ja)
Inventor
晃仁 安井
Original Assignee
株式会社フジミインコーポレーテッド
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Publication of WO2016132951A1 publication Critical patent/WO2016132951A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • 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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a polishing composition.
  • CMP chemical mechanical polishing
  • LSI manufacturing process particularly shallow trench isolation (STI), planarization of interlayer insulating film (ILD film), tungsten plug formation
  • CMP is used in processes such as the formation of multilayer wiring composed of copper and a low dielectric constant film.
  • polishing a polishing object such as polysilicon, silicon oxide, silicon nitride, or a composite material thereof at high speed.
  • the particle diameter, shape and concentration of the abrasive grains are generally improved by surface modification with a coupling agent or the like.
  • Patent Document 1 cannot sufficiently control the polishing rate of a polishing object having a silicon-oxygen bond such as a silicon oxide film, and further improvement has been desired.
  • An object of the present invention is to provide a polishing composition capable of sufficiently controlling the polishing rate of a polishing object having a silicon-oxygen bond such as a silicon oxide film.
  • the present inventor has intensively studied to solve the above problems.
  • a polishing composition capable of sufficiently controlling the polishing rate of a polishing object having a silicon-oxygen bond such as a silicon oxide film in at least one of acidic, neutral and basic regions. Can be provided.
  • X to Y indicating a range means “X or more and Y or less”.
  • operations and physical properties are measured under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.
  • the present invention includes (1) an action site that interacts with a polishing object having a silicon-oxygen bond, and a suppression part that suppresses a polishing component that polishes the polishing object from approaching the polishing object; And (2) abrasive grains; and (3) a dispersion medium, wherein the polishing object having the silicon-oxygen bond in at least one of acidic, neutral, and basic regions.
  • a polishing composition that suppresses the polishing rate is also referred to as “polishing composition of the present invention”.
  • the organic compound of the present invention polishes the polishing object with an action site that interacts with a polishing object having a silicon-oxygen bond (hereinafter, also simply referred to as “polishing object”).
  • a polishing component that suppresses the approach of the polishing component to the polishing object also referred to as “organic compound of the present invention” in the present specification.
  • the organic compound of the present invention suppresses the action site that interacts with the polishing object having a silicon-oxygen bond in one molecule and the polishing component that polishes the polishing object from approaching the polishing object. And having a suppression site at the same time. Therefore, the site of action in the organic compound interacts with the object to be polished, and on the other hand, the suppression site prevents the polishing component that polishes the object to be polished from approaching the object to be polished. Therefore, a polishing composition containing such an organic compound sufficiently controls a polishing object having a silicon-oxygen bond, such as a silicon oxide film, in at least one of acidic, neutral and basic regions. In other words, a compound that does not have an action site and a suppression site simultaneously in one molecule is distinguished from the organic compound of the present invention.
  • polishing the polishing rate of the polishing object having a silicon-oxygen bond in at least one of acidic, neutral or basic regions as shown in the examples, A polishing object having a silicon-oxygen bond such as a silicon oxide film in any region as compared with the case where no additives (that is, components other than “abrasive grains, dispersion medium, and pH adjuster as necessary”) are added at all. This means that the polishing rate is suppressed.
  • the “polishing component” is a component capable of polishing an object to be polished, and means, for example, abrasive grains.
  • the organic compound of the present invention has an action site that interacts with a polishing object having a silicon-oxygen bond.
  • the “action site” may have any structure as long as it is a site that interacts with an object to be polished having a silicon-oxygen bond, preferably a nitrogen atom, an oxygen atom, It has at least one selected from the group consisting of a sulfur atom and a phosphorus atom. By having such a structure, it is possible to interact with a polishing object having a silicon-oxygen bond.
  • the action site may be in the form of a salt, and a sodium salt, potassium salt, ammonium salt, amine salt or the like is preferable as the salt.
  • the number of action sites is not particularly limited as long as it is 1 or more per molecule, and may be 2 or more, or 3 or more.
  • the action site has at least a nitrogen atom and an oxygen atom.
  • the site of action includes a sulfide group, an amino group, a phosphonic acid group or a salt group thereof, an N-oxide structure, a carboxyl group or a salt group thereof, a phenol structure, an alkylene oxide structure (a diether structure). And at least one selected from the group consisting of betaine structures.
  • the alkylene oxide is preferably methylene oxide.
  • a plurality of alkylene oxide structures may be contained in one molecule.
  • the “amino group” means a group having the structure of —NH 2 .
  • the action site has a structure in which a nitrogen atom and an oxygen atom are directly bonded, or a divalent organic group having 3 or less carbon atoms between the nitrogen atom and the oxygen atom. Is intervening.
  • a structure in which a nitrogen atom and an oxygen atom are directly bonded, or a divalent organic group having 3 or less carbon atoms between the nitrogen atom and the oxygen atom. Is intervening.
  • This relationship is determined based on the relationship between the electronegativity of the elements, which tends to be positively charged or easily negatively charged.
  • the interaction of electrons in the molecule of the same organic compound influences each other as the distance between the atoms becomes shorter. Therefore, the charge intensity of each atom becomes stronger. . From such a theory, it is inferred that the range of strength that can sufficiently act on the oxygen-silicon structure at the site of action is 3 or less in terms of carbon number.
  • the mechanism of action of the structures having the respective electron densities is such that the nitrogen atoms in a state where the electron density is low become oxygen atoms on the surface of the film having an oxygen-silicon structure, and the state where the electron density is high It is considered that the site of action of the organic compound is chemically adsorbed on the surface of the film having an oxygen-silicon structure because each oxygen atom acts on a silicon atom.
  • the action site is preferably at least one of an N-oxide structure and a betaine structure.
  • the organic group of the suppression site is particularly preferably a site having an alkyl group having 8 or more carbon atoms.
  • the functional site when the functional site has an N-oxide structure, it is preferable that the functional site does not have a carboxyl group at the same time.
  • the organic compound is preferably a tertiary amine oxide.
  • the oxidizing agents enumerated below such as hydrogen peroxide.
  • the action site is an N-oxide structure
  • the suppression site is an alkyl group or an acyl group having 8 or more carbon atoms.
  • the N-oxide structure has a strong chemisorption action on the surface of the object to be polished having a silicon-oxygen bond
  • the alkyl group or acyl group having 8 or more carbon atoms is a three-dimensional structure. It has a function of obstructing the action of the polishing component.
  • the above mechanism is only speculation and does not limit the technical scope of the present invention.
  • the carbon number of the alkyl group or acyl group may be 9 or more, 10 or more, and the upper limit may be 20 or less, or 15 or less.
  • the alkyl group those listed below are suitable.
  • the acyl group preferably has a “—COR” structure, and R is preferably a similar alkyl group.
  • the action site when an action site has a nitrogen atom and the N-oxide structure and the betaine structure are not adopted, the action site is bonded to a hydrogen atom without a carbon atom. It is preferable.
  • an aromatic substance such as benzene or naphthalene is used. It is preferably bonded to a group ring.
  • an oxygen atom when used as an action site, when the N-oxide structure and the betaine structure are not adopted, when there are three oxygen atoms, a phosphorus atom is contained. Preferably it is.
  • the organic compound of the present invention has a suppression site for suppressing the polishing component that polishes the polishing object from approaching the polishing object.
  • the “suppressed part” may have any structure as long as the polishing component for polishing the polishing object has an action of suppressing the approach to the polishing object.
  • the number of suppression sites is not particularly limited as long as it is 1 or more per molecule, and may be 2 or more, or 3 or more.
  • the suppression site is preferably a site having a total of 3 or more carbon atoms. In one embodiment of the present invention, the suppression sites have a total of 4 or more carbon atoms. In one embodiment of the present invention, the suppression sites have a total of 6 or more carbon atoms. In one embodiment of the present invention, the suppression sites have a total of 8 or more carbon atoms.
  • the total number of carbon atoms is 3 or more, it is easy to produce a molecular arrangement film that is a suppression film by suppressing a decrease in hydrophobicity at the suppression site. Further, when the total number of carbon atoms is 3 or more, the polishing component is further prevented from approaching the surface of the object to be polished (substrate), so that the suppression effect is improved.
  • total means that, for example, when the organic compound is “laurylphosphonic acid”, “action site” is “phosphonic acid group” and “suppression site” is “lauryl group”.
  • the carbon number of the “suppression site” is 12.
  • the organic compound is “betaine”
  • the “action site” is “betaine structure”
  • the “action site” is three “methyl groups”, so the total number of carbon atoms is 3.
  • the suppression sites have a total of 20 or less carbon atoms. On the other hand, in one embodiment of the present invention, the suppression sites have a total of 18 or less carbon atoms. On the other hand, in one embodiment of the present invention, the suppression sites have a total of 16 or less carbon atoms. If the organic chain (carbon number) of the suppression site is too large, the solubility in the slurry (polishing composition) will be low, so an amount of inhibitor (organic compound of the present invention) sufficient to suppress can be added. There is a risk of disappearing.
  • the suppression site tends to bend (a state where it is bent not in a straight line), and the density of the suppression film and the generation rate of the molecular arrangement film decrease, resulting in a suppression effect. There is also a risk of lowering.
  • part is a site
  • the suppression site is a site having an alkyl group having 4 or more carbon atoms.
  • the suppression site is a site having an alkyl group having 7 or more carbon atoms.
  • the site of action when the suppression site is a relatively short alkyl group having 1 to 6 carbon atoms, the site of action has a betaine structure.
  • the suppression site is a site having an alkyl group having 8 or more carbon atoms.
  • the polishing component for polishing the object to be polished has the action of suppressing the approach to the object to be polished more reliably.
  • part is a site
  • the organic compound of the present invention is important in that the action site and the suppression site coexist in one molecule.
  • the suppression site is a site having an alkyl group having 11 or more carbon atoms, and according to a further preferred embodiment of the present invention, the suppression site is an alkyl group having 12 or more carbon atoms. It is a site
  • the alkyl group may be linear or branched, but in the case of branching, the number of organic molecules that can act on the same area decreases (the density of organic molecules decreases). There is a possibility that the suppression ability may be reduced. Moreover, in the case of a branched alkyl group, it is conceivable that the molecular arrangement speed of the suppression film composed of an organic compound (an organic molecule of the inhibitor) decreases due to the complexity of the structure. Therefore, it is preferably linear.
  • alkyl group may be substituted with a hydroxyl group, a halogen atom, or the like.
  • alkyl group having 1 to 20 carbon atoms are not particularly limited, but are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl.
  • the number of suppression sites is not particularly limited, but the number of alkyl groups having 4 or more carbon atoms in the suppression sites in the organic compound of the present invention is 1 to 3. It is preferable that there is one, and more preferably one from the viewpoint of ease of molecular alignment film of the inhibitor organic molecule (organic compound of the present invention). Further, according to a more preferred embodiment of the present invention, the number of alkyl groups having 10 or more carbon atoms in the suppression site in the organic compound of the present invention is preferably 1 to 3, and the inhibitor organic molecule (present From the viewpoint of easiness of the molecular alignment film of the organic compound) of the invention, it is more preferably one.
  • examples of the organic compound of the present invention include lauryl betaine, 4-laurylpyridine N-oxide, N, N-dimethyldodecylamine N-oxide, N, N-dihydroxyethyllaurylamine N-oxide, 4-heptylphenol, n-octylamine, nonanoic acid, laurylphosphonic acid, betaine, 4-n-octylbenzenecarboxylic acid, ethylene glycol dibutyl ether, heptylmethyl sulfide, 4-octylpyridine N-oxide, 4-hexylpyridine N-oxide, 4- Butylpyridine N-oxide, 4-ethylpyridine N-oxide, carboxylatomethyloctyldimethylammonium, carboxylatomethylhexyldimethylammonium, carboxylatomethylbutyldimethylammonium N, N-dimethyl Silamine N-oxide, N, N-dimethyl
  • the interaction is due to a chemical bond selected from at least one of an ionic bond, a covalent bond and a hydrogen bond.
  • a chemical bond selected from at least one of an ionic bond, a covalent bond and a hydrogen bond.
  • the interaction is due to, for example, a hydrophobic interaction or an intermolecular force (van der Waals force)
  • the interaction is not firmly adsorbed to the polishing object having a silicon-oxygen bond, and the effect of the present invention is achieved. May not.
  • the organic compound (polishing rate inhibitor) of the present invention adsorbed on the surface of the polishing object (substrate) to be removed from the surface of the polishing object (substrate) by abrasive grains or a polishing pad.
  • at least one of strong bonds such as covalent bonds.
  • the polishing rate of the polishing object having a silicon-oxygen bond can be suppressed in any of acidic, neutral and basic regions.
  • the polishing object having the silicon-oxygen bond in all the acidic, neutral or basic regions It is preferable to suppress the polishing rate.
  • the content of the organic compound in the polishing composition of the present invention is not particularly limited, but is preferably 0.01 mM or more, more preferably 0.1 mM or more, and even more preferably 0.5 mM or more from the viewpoint of controlling polishing efficiency.
  • it is 1.0 mM or more, more preferably 1.5 mM or more, still more preferably 2.0 mM or more, and particularly preferably 2.5 mM or more.
  • 100 mM or less is preferable, 50 mM or less is more preferable, 30 mM or less is more preferable, 20 mM or less is further more preferable, 15 mM or less is even more preferable, and 10 mM. More preferably, it is more preferably 5 mM or less.
  • the action site of the present invention can be chemically bonded to the surface of the polishing object having a silicon-oxygen bond, while the suppression site of the organic compound is the polishing object.
  • a molecular alignment film is formed so as to face the liquid contact side from the surface of the object, or to cover the surface, thereby inhibiting the action of the polishing component for polishing the object to be polished. Since the suppression part of the organic compound is highly hydrophobic, organic compounds having the same action part and the suppression part are aggregated by hydrophobic interaction, so that the surface of the polishing object having a silicon-oxygen bond is collected. A suppression film is formed.
  • polishing of an object to be polished having a silicon-oxygen bond such as a silicon oxide film, in at least one region (preferably in two or more regions) of acidic, neutral or basic.
  • a polishing composition capable of sufficiently controlling the speed can be provided.
  • a polishing composition capable of sufficiently controlling the polishing rate of an object to be polished having a silicon-oxygen bond such as a silicon oxide film can be provided.
  • a silicon-oxygen bond such as a silicon oxide film
  • the polishing composition of the present invention contains abrasive grains.
  • the abrasive used may be any of inorganic particles, organic particles, and organic-inorganic composite particles.
  • the inorganic particles include particles made of metal oxides such as silica, alumina, ceria, titania, silicon nitride particles, silicon carbide particles, and boron nitride particles.
  • Specific examples of the organic particles include latex particles, polystyrene particles, and polymethyl methacrylate (PMMA) particles.
  • PMMA polymethyl methacrylate
  • the object to be polished is removed by mechanical action by scraping the object to be polished with abrasive grains, but this mechanical action is dependent on the material, shape and particle diameter of the abrasive grains. , The particle size distribution has a great influence. With abrasive grains having a low Mohs hardness or a material that is easily crushed, the mechanical action is weakened, and the polishing rate of a polishing object having a silicon-oxygen bond such as a silicon oxide film can be suppressed.
  • the trapping with the object to be polished is weakened, so that the polishing rate of the object to be polished having a silicon-oxygen bond such as a silicon oxide film can be suppressed.
  • Abrasive grains having a small particle diameter can reduce the strain applied to the surface of the object to be polished, so that the polishing rate of an object to be polished having a silicon-oxygen bond such as a silicon oxide film can be suppressed.
  • Abrasive grains having a narrower particle size distribution can reduce the force applied to each particle, so that the polishing rate of a polishing object having a silicon-oxygen bond such as a silicon oxide film can be suppressed.
  • the electrostatic repulsive force acting between the particle and the substrate surface increases or the electrostatic attractive force decreases.
  • the polishing rate of a polishing object having a silicon-oxygen bond such as a silicon oxide film can be suppressed.
  • the mechanical action is adjusted by these methods to suppress the polishing rate of the silicon oxide film, the polishing efficiency of other film types is often also suppressed, so that polishing is performed by the effect of the additive. It is desirable to control efficiency.
  • silica is preferable, and colloidal silica is particularly preferable from the viewpoint of suppressing generation of polishing flaws.
  • colloidal silica that can be used is not particularly limited, and for example, surface-modified colloidal silica can be used.
  • Surface modification of colloidal silica (supported colloidal silica) can be performed, for example, by mixing a metal such as aluminum, titanium or zirconium, or an oxide thereof with colloidal silica and doping the surface of silica particles.
  • it can be carried out by chemically bonding the functional group of the organic acid to the surface of the silica particles, that is, by immobilizing the organic acid.
  • the immobilization of the organic acid on the colloidal silica is not achieved simply by the coexistence of the colloidal silica and the organic acid.
  • sulfonic acid which is a kind of organic acid
  • colloidal silica see, for example, “Sulphonic acid-functionalized silica through of thiol groups”, Chem. Commun. 246-247 (2003).
  • a silane coupling agent having a thiol group such as 3-mercaptopropyltrimethoxysilane is coupled to colloidal silica and then oxidized with hydrogen peroxide to fix the sulfonic acid on the surface.
  • the colloidal silica thus obtained can be obtained.
  • the colloidal silica used in the examples is also modified with sulfonic acid groups in this way.
  • colloidal silica which is a kind of organic acid
  • carboxylic acid which is a kind of organic acid
  • colloidal silica for example, “Novel Silane Coupling Agents Containing a Photobolizable 2-Nitrobenzoyl Sterfotrophic Induction of CarbodisulfideCarbon Letters, 3, 228-229 (2000).
  • colloidal silica having a carboxylic acid immobilized on the surface can be obtained by irradiating light after coupling a silane coupling agent containing a photoreactive 2-nitrobenzyl ester to colloidal silica.
  • colloidal silica to which sulfonic acid is fixed is particularly preferable from the viewpoint of easy production. Further, in the form in which sulfonic acid is immobilized on colloidal silica, the polishing rate of a polishing object having a silicon-oxygen bond such as a silicon oxide film can be suppressed by the following mechanism.
  • the surface of a polishing object having a silicon-oxygen bond such as a general silicon oxide film, has an isoelectric point where the surface zeta potential is zero near pH 2, and is negatively charged at a pH higher than that.
  • the absolute value of the value increases as the pH increases. Although it is slightly positively charged at a lower pH, it takes a value almost equal to the isoelectric point.
  • the surface of an object to be polished having a silicon-oxygen bond such as a general silicon oxide film is negatively charged in a wide pH range.
  • it is effective to use abrasive grains having a negative zeta potential in a wide range.
  • abrasive grains having a negative zeta potential in a wide range As particles having a negative zeta potential in such a wide pH range, it is effective to modify acid groups having a low functional group pKa on the surface of the abrasive grains.
  • a general acid group having a low pKa a sulfonic acid group is preferable. The reason for this is that a general sulfonic acid group has a pKa value of 1 or less.
  • a negative abrasive grain having a pH of 1 or more is obtained. It is done.
  • a polishing object having a silicon-oxygen bond such as a silicon oxide film
  • an electrical connection between the abrasive grains and the substrate is possible in a wide pH range. Since a repulsive force is generated, it is an effective means for suppressing the polishing efficiency of the object to be polished.
  • an abrasive produced by a method for producing a cation sol may be used.
  • composite abrasive grains and abrasive grains having a core-shell structure can also be used.
  • the lower limit of the average primary particle diameter of the abrasive grains in the polishing composition is preferably 5 nm or more, more preferably 7 nm or more, further preferably 10 nm or more, and more preferably 15 nm or more. More preferably, it is particularly preferably 25 nm or more.
  • the upper limit of the average primary particle diameter of the abrasive grains is preferably 200 nm or less, more preferably 150 nm or less, further preferably 100 nm or less, still more preferably 70 nm or less, and 60 nm. More preferably, it is more preferably 50 nm or less.
  • the average primary particle diameter of an abrasive grain is calculated based on the specific surface area of the abrasive grain measured by BET method, for example. This is also calculated in the embodiment of the present invention.
  • the lower limit of the average secondary particle diameter of the abrasive grains in the polishing composition is preferably 5 nm or more, more preferably 7 nm or more, further preferably 10 nm or more, and preferably 26 nm or more. Still more preferably, it is more preferably 36 nm or more, still more preferably 45 nm or more, and particularly preferably 55 nm or more.
  • the upper limit of the average secondary particle diameter of the abrasive grains is preferably 300 nm or less, more preferably 260 nm or less, further preferably 220 nm or less, still more preferably 150 nm or less, It is more preferably 120 nm or less, still more preferably 100 nm or less, and particularly preferably 80 nm or less. If it is such a range, it can suppress more that a surface defect arises on the surface of the grinding
  • the secondary particles refer to particles formed by association of abrasive grains in the polishing composition
  • the average secondary particle diameter of the secondary particles is represented by, for example, a laser diffraction scattering method. It can be measured by a dynamic light scattering method. This is also calculated in the embodiment of the present invention.
  • the lower limit of the ratio with the diameter D10 of the particles when reaching 10% is preferably 1.1 or more, and preferably 1.2 or more. More preferably, it is more preferably 1.3 or more, and particularly preferably 1.4 or more.
  • the upper limit of D90 / D10 is not particularly limited, but is preferably 5.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less, and 2.0 or less.
  • the lower limit of the content of abrasive grains in the polishing composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. More preferably, it is more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. When the lower limit is such, it is preferable for obtaining sufficient polishing efficiency for a polishing object other than a polishing object having a silicon-oxygen bond such as a silicon oxide film.
  • the upper limit of the content of the abrasive grains in the polishing composition is preferably 50% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and 8 More preferably, it is more preferably 6% by mass or less, and particularly preferably 4% by mass or less.
  • the cost of the polishing composition can be suppressed, and the occurrence of surface defects on the surface of the object to be polished after polishing using the polishing composition can be further suppressed.
  • Dispersion medium In the polishing composition of the present invention, a dispersion medium is used for dispersing each component.
  • a dispersion medium an organic solvent and water are conceivable.
  • water containing as little impurities as possible is preferable. Specifically, pure water, ultrapure water, or distilled water from which foreign ions are removed through a filter after removing impurity ions with an ion exchange resin is preferable.
  • the present invention provides a polishing composition capable of sufficiently controlling a polishing object having a silicon-oxygen bond in at least one of acidic, neutral and basic regions.
  • polishing objects having a silicon-oxygen bond examples include silicon oxide films, BD (black diamond: SiOCH), FSG (fluorosilicate glass), HSQ (hydrogen silsesquioxane), CYCLOTENE, SiLK, MSQ (Methyl silsesquioxane), and the like. Is mentioned.
  • the polishing composition of the present invention may further contain other components such as a pH adjuster, an oxidizing agent, a reducing agent, a surfactant, a water-soluble polymer, and an antifungal agent, if necessary.
  • a compound having an action site that interacts with a polishing object having a silicon-oxygen bond, and a suppression part that suppresses a polishing component that polishes the polishing object from approaching the polishing object when it can also act as “another component”, the present invention classifies it as an organic compound of the present invention.
  • the polishing composition of the present invention suppresses the polishing rate of the polishing object having a silicon-oxygen bond in at least one of acidic, neutral and basic regions. Therefore, the pH adjuster is preferably used for adjusting to an acidic or basic region.
  • the acidic region means that the pH is less than 7, and preferably 1 to 4.
  • the neutral region means pH 7.
  • the basic region means a pH of more than 7, preferably a pH of 8-13.
  • the value of pH in this invention shall say the value measured on the conditions as described in an Example.
  • pH adjusting agent for adjusting to the acidic region may be any of an inorganic compound and an organic compound.
  • sulfuric acid H 2 SO 4
  • nitric acid nitric acid
  • boric acid carbonic acid
  • hypoxia Inorganic acids such as phosphoric acid, phosphorous acid and phosphoric acid
  • citric acid formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, maleic acid, phthalic acid, malic acid
  • carboxylic acids such as tartaric acid and lactic acid
  • organic acids such as organic sulfuric acid such as methanesulfonic acid, ethanesulfonic acid and isethionic acid.
  • the above acid is a divalent or higher acid (for example, sulfuric acid, carbonic acid, phosphoric acid, oxalic acid, etc.), it may be in a salt state as long as one or more protons (H + ) can be released.
  • a divalent or higher acid for example, sulfuric acid, carbonic acid, phosphoric acid, oxalic acid, etc.
  • protons H +
  • ammonium hydrogen carbonate, ammonium hydrogen phosphate the type of the cation species of the counter is basically arbitrary, but a weak base cation (ammonium, triethanolamine, etc.) is preferred).
  • the salt concentration (the conductivity of the slurry) increases, and the thickness of the electric double layer on the abrasive grain surface decreases. Therefore, since the electrostatic repulsive force of the abrasive grains is weakened, there is a concern that the polishing rate of a polishing object having a silicon-oxygen bond such as a silicon oxide film may be improved. For this reason, in the polishing composition of the present invention, it is more preferable that the pH adjuster for adjusting to the acidic region does not contain a salt.
  • salts include halogen acids such as hydrochloric acid, ammonium salts of inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, and carbonic acid, potassium salts, amine salts, acetic acid, citric acid, oxalic acid, maleic acid, and other organic acids. Ammonium salt, potassium salt, amine salt.
  • pH adjusting agent for adjusting to the basic region may be any of an inorganic compound and an organic compound, but alkali metal hydroxides or salts thereof, quaternary ammonium, hydroxide hydroxide Quaternary ammonium or a salt thereof, ammonia, amine and the like can be mentioned.
  • alkali metal examples include potassium and sodium.
  • Specific examples of the salt include carbonate, hydrogen carbonate, sulfate, acetate, and the like.
  • quaternary ammonium examples include tetramethylammonium, tetraethylammonium, tetrabutylammonium and the like.
  • quaternary ammonium hydroxide or a salt thereof examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and the like.
  • the polishing composition contains ammonia, amine, or potassium as a base from the viewpoint of prevention of metal contamination and ease of diffusion of metal ions into the semiconductor device structure.
  • Specific examples include potassium hydroxide (KOH), potassium carbonate, potassium hydrogen carbonate, potassium sulfate, potassium acetate, and potassium chloride.
  • oxidizing agent examples include hydrogen peroxide, peracetic acid, percarbonate, urea peroxide, perchloric acid; sodium persulfate, potassium persulfate, ammonium persulfate, potassium monopersulfate, oxone (2KHSO 5 ⁇ KHSO 4 ⁇ Persulfates such as double salts with peroxides such as K 2 SO 4 ), hypochlorite, chlorite, chlorate, perchlorate, hypobromite, bromite Halogen-based oxidants such as salts, bromate, perbromate, hypoiodite, iodate, iodate, periodate, cerium ammonium nitrate, potassium permanganate, potassium chromate, etc. And compounds of metal elements that can take a wide range of oxidation numbers. These oxidizing agents may be used alone or in combination of two or more.
  • the lower limit of the content (concentration) of the oxidizing agent in the polishing composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more.
  • the material cost of the polishing composition can be suppressed, and in addition, there is an advantage that the load of the treatment of the polishing composition after polishing use, that is, the waste liquid treatment can be reduced. . In addition, there is an advantage that excessive oxidation of the surface of the object to be polished by the oxidizing agent hardly occurs.
  • the polishing composition of the present invention may contain a reducing agent.
  • a reducing agent conventionally known ones used in polishing compositions can be included.
  • organic substances hydrazine, formic acid, oxalic acid, formaldehyde aqueous solution, ascorbic acid, glucose and other reducing sugars, inorganic substances In, nitrous acid or its salt, phosphorous acid or its salt, hypophosphorous acid or its salt, sulfurous acid or its salt, thiosulfuric acid or its salt, lithium aluminum hydride, sodium borohydride, multiple stable valences Metal and its compounds.
  • the lower limit of the content (concentration) of the reducing agent in the polishing composition is preferably 0.001% by mass or more, and more preferably 0.01% by mass or more.
  • polishing target other than the polishing target having a silicon-oxygen bond is polished such that the polishing efficiency is improved by adding a reducing agent by making the lower limit in this way, polishing is performed without increasing the abrasive concentration.
  • the efficiency can be increased.
  • the upper limit of content (concentration) of the reducing agent in polishing composition is 30 mass% or less, More preferably, it is 10 mass% or less.
  • a surfactant may be contained in the polishing composition.
  • the surfactant improves the cleaning efficiency after polishing by imparting hydrophilicity to the polished surface after polishing, and can prevent the adhesion of dirt.
  • step performance such as dishing can be improved by selecting an appropriate surfactant.
  • the surfactant may be any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.
  • One of these surfactants may be used alone, or two or more thereof may be used in combination.
  • the content of the surfactant in the polishing composition is preferably 0.001 g / L or more, more preferably 0.005 g / L or more. By setting it as such a lower limit, the cleaning efficiency after polishing is further improved. Further, by selecting an appropriate surfactant, step performance such as dishing can be improved.
  • the water-soluble polymer is a temperature at which the water-soluble polymer is most dissolved and when it is dissolved in water at a concentration of 0.5% by mass and filtered through a G2 glass filter (maximum pores 40 to 50 ⁇ m). The mass of the insoluble matter to be filtered out is within 50 mass% of the added water-soluble polymer.
  • a water-soluble polymer When a water-soluble polymer is added to the polishing composition, the surface roughness of the polishing object after polishing using the polishing composition is further reduced.
  • One of these water-soluble polymers may be used alone, or two or more thereof may be used in combination.
  • the content of the water-soluble polymer in the polishing composition is preferably 0.01 g / L or more, more preferably 0.05 g / L or more. By setting it as such a lower limit, the surface roughness of the polishing surface by the polishing composition is further reduced.
  • the content of the water-soluble polymer in the polishing composition is preferably 100 g / L or less, more preferably 50 g / L or less. By setting such an upper limit, the remaining amount of the water-soluble polymer on the polishing surface is reduced, and the cleaning efficiency is further improved.
  • antiseptic and fungicide examples include 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one. And the like, isothiazoline-based preservatives such as paraoxybenzoates, and phenoxyethanol. These antiseptics and fungicides may be used alone or in combination of two or more.
  • the polishing rate of a polishing object having a silicon-oxygen bond can be sufficiently controlled.
  • the polishing environment is appropriately adjusted depending on the polishing application or the like. That is, polishing may be performed in an acidic environment, polishing may be performed in a neutral environment, and polishing may be performed in a basic environment.
  • polishing rate of the polishing object having a silicon-oxygen bond is suppressed in at least one of the acidic, neutral or basic regions of the present invention, a specific pH region is selected depending on the polishing application and the like.
  • a polishing composition capable of sufficiently controlling the polishing rate of a polishing object having a silicon-oxygen bond such as a silicon oxide film may be appropriately selected and used. Therefore, from another point of view, it is added that it is not meaningful to compare the polishing rate between different pH ranges.
  • the polishing rate of a polishing object having a silicon-oxygen bond such as a silicon oxide film in an acidic environment is preferably less than 155 [55 / min], and more preferably 150 [ ⁇ / min] or less. More preferably 135 [ ⁇ / min] or less, still more preferably 100 [ ⁇ / min] or less, still more preferably 80 [ ⁇ / min] or less, and even more preferably 70 [[/ min] or less. ⁇ / min] or less, more preferably 50 [ ⁇ / min] or less, and particularly preferably 30 [ ⁇ / min] or less.
  • the lower limit is not particularly limited, but is substantially 0 [ ⁇ ⁇ / min] or more.
  • the colloidal silica of the abrasive grains used in the verification experiment of the example / comparative example has a negative charge on the acidic side of the zeta potential.
  • colloidal silica when colloidal silica is used as the abrasive grains, it is difficult to suppress the polishing rate in an acidic environment, but the point to which the present invention should be focused is that it is suppressed even in acidic conditions.
  • the polishing rate of a polishing object having a silicon-oxygen bond such as a silicon oxide film in a neutral environment is preferably less than 15 [ ⁇ / min], more preferably 14 [14 / min] or less. More preferably, it is 13 [ ⁇ / min] or less.
  • the lower limit is not particularly limited, but is substantially 0 [ ⁇ ⁇ / min] or more.
  • the polishing rate of an object to be polished having a silicon-oxygen bond such as a silicon oxide film in a basic environment is preferably less than 10 [ ⁇ / min], more preferably 9 [ ⁇ / min] or less. More preferably, it is 8 [ ⁇ / min] or less.
  • the lower limit is not particularly limited, but is substantially 0 [ ⁇ ⁇ / min] or more.
  • the polishing rate means a value measured by the method described in the examples.
  • the polishing target having a silicon-oxygen bond such as a silicon oxide film
  • the polishing target includes polysilicon
  • the polishing rate of a polishing object having a silicon-oxygen bond can be suppressed while maintaining the same polishing rate.
  • a method for producing a polishing composition that suppresses the polishing rate of the polishing object having a silicon-oxygen bond in at least one of acidic, neutral and basic regions, An organic compound; (2) abrasive grains; and (3) a dispersion medium, wherein the organic compound interacts with a polishing object having a silicon-oxygen bond, and the polishing.
  • a method for producing a polishing composition comprising: a suppression part that suppresses a polishing component that polishes an object from approaching the polishing object.
  • polishing composition is not restrict
  • the temperature at the time of mixing each component is not particularly limited, but is preferably 10 to 40 ° C., and may be heated to increase the dissolution rate. Further, the mixing time is not particularly limited.
  • ⁇ Polishing method> there is provided a polishing method in which a polishing object having a silicon-oxygen bond is polished with the above polishing composition or the polishing composition obtained by the above production method.
  • a polishing apparatus As a polishing apparatus, a general holder having a polishing surface plate on which a holder for holding a substrate having a polishing object and a motor capable of changing the number of rotations are attached and a polishing pad (polishing cloth) can be attached A polishing apparatus can be used.
  • polishing pad a general nonwoven fabric, polyurethane, porous fluororesin, or the like can be used without particular limitation. It is preferable that the polishing pad is grooved so that the polishing composition accumulates.
  • the polishing conditions are not particularly limited.
  • the rotation speed of the polishing surface plate is preferably 10 to 500 rpm
  • the rotation speed of the head (carrier) is preferably 10 to 500 rpm
  • the pressure applied to the substrate having the object to be polished is preferably 0.1 to 10 psi.
  • the method of supplying the polishing composition to the polishing pad is not particularly limited, and for example, a method of continuously supplying with a pump or the like is employed. Although the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with the polishing composition of the present invention. Also, the polishing time is not particularly limited.
  • ⁇ Method for suppressing polishing rate of polishing object having silicon-oxygen bond (1) an action site that interacts with a polishing object having a silicon-oxygen bond, and a suppression part that suppresses a polishing component that polishes the polishing object from approaching the polishing object. And (2) abrasive grains; (3) a dispersion medium; and polishing the object to be polished with an abrasive, an acidic, neutral or basic There is also provided a method for suppressing the polishing rate of a polishing object having a silicon-oxygen bond in at least one region.
  • Polishing compositions of Examples and Comparative Examples were prepared by using 2% by mass of abrasive grains (sulfonic acid group-modified colloidal silica; average primary particle size: 35 nm, average secondary particle size: 65 nm D90 / D10: 1.6), pH adjuster.
  • the organic compound 3 mM shown in Table 1 was prepared by mixing in pure water (mixing temperature: about 25 ° C., mixing time: about 10 minutes).
  • the concentration of the tertiary amine of the following raw materials was 3 mM.
  • N-lauroylsarcosine N-oxide, N, N-dimethyllaurylamine N-oxide (N, N-dimethyldodecylamine N-oxide) and N, N of Examples 13 to 15 -Dihydroxyethyllaurylamine N-oxide was prepared as follows.
  • the pH of the polishing composition was adjusted to 2, 7, and 10 by adding appropriate amounts of H 2 SO 4 and KOH.
  • the pH of the polishing composition (liquid temperature: 25 ° C.) was confirmed by a pH meter (manufactured by Horiba, Ltd., model number: LAQUA).
  • polishing performance evaluation Using the obtained polishing compositions of Examples and Comparative Examples, the polishing rate when the polishing object (wafer with a silicon oxide film) was polished under the following polishing conditions was measured.
  • Polishing machine Single-side CMP polishing machine (ENGIS) Polishing pad: Polyurethane pad (IC1010: manufactured by Rohm and Haas) Pressure: 3.04 psi Platen (surface plate) rotation speed: 90rpm Head (carrier) rotation speed: 40 rpm Flow rate of polishing composition: 100 ml / min Polishing time: 60 sec ⁇ Polishing speed> The polishing rate (polishing rate) was calculated by the following formula.
  • the film thickness was evaluated by obtaining by a light interference type film thickness measuring device (model number: Lambda Ace manufactured by Dainippon Screen Mfg. Co., Ltd.) and dividing the difference by the polishing time.
  • the polishing composition of the comparative example does not have an action site on the surface of the polishing object having a silicon-oxygen structure, suggesting that the polishing rate of the silicon oxide film cannot be suppressed. .
  • these organic compounds have a structure that improves the polishing rate of the silicon oxide film. Is suggested.
  • Comparative Example 10 and Comparative Example 11 are tertiary amines, they do not have an action site on the surface of the polishing object having a silicon-oxygen structure, and are comparative examples. However, these comparative organic compounds were converted to tertiary amine-N-oxides and N, N-dimethyldodecylamine N-oxide, N, N-dihydroxyethyl as shown in Examples 14 and 15, respectively. When laurylamine N-oxide is used, it is suggested that the polishing rate is suppressed. As for Example 14 and Example 15, the same organic compounds as in Examples 3 and 4 are used as the organic compounds. However, the former is an oxidant that has not reacted in the synthesis process ( Since H 2 O 2 ) is included, it is presumed that differences have been observed in the numerical values of the respective polishing rates.

Abstract

La présente invention a pour objet une composition de polissage à l'aide de laquelle il est possible, dans au moins l'une des plages acide, neutre et basique, de commander de façon suffisante le taux de polissage pour un objet à polir comprenant une liaison silicium-oxygène, tel qu'un film d'oxyde de silicium. À cet effet, la présente invention porte sur une composition de polissage comprenant (1) un composé organique comprenant un site actif qui entre en interaction avec un objet à polir comprenant une liaison silicium-oxygène, et un site de suppression qui supprime l'approche d'un constituant de polissage pour polir l'objet à polir vers l'objet à polir, (2) des particules abrasives, et (3) un milieu de dispersion, le taux de polissage pour l'objet à polir comprenant une liaison silicium-oxygène étant supprimé dans au moins l'une des plages acide, neutre et basique.
PCT/JP2016/053718 2015-02-19 2016-02-08 Composition de polissage WO2016132951A1 (fr)

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Cited By (1)

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WO2009096495A1 (fr) * 2008-02-01 2009-08-06 Fujimi Incorporated Composition de polissage et procédé de polissage l'utilisant
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WO2013138558A1 (fr) * 2012-03-14 2013-09-19 Cabot Microelectronics Corporation Compositions de polissage chimico-mécanique sélectives pour l'oxyde et le nitrure affichant un taux d'élimination élevé et une faible défectivité

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JP2004273547A (ja) * 2003-03-05 2004-09-30 Kao Corp 研磨速度選択比向上剤
WO2009096495A1 (fr) * 2008-02-01 2009-08-06 Fujimi Incorporated Composition de polissage et procédé de polissage l'utilisant
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WO2018193916A1 (fr) * 2017-04-17 2018-10-25 日産化学株式会社 Composition de polissage contenant un tensioactif amphotère
KR20190141132A (ko) * 2017-04-17 2019-12-23 닛산 가가쿠 가부시키가이샤 양성 계면활성제를 포함하는 연마용 조성물
JPWO2018193916A1 (ja) * 2017-04-17 2020-04-23 日産化学株式会社 両性界面活性剤を含む研磨用組成物
US11459486B2 (en) 2017-04-17 2022-10-04 Nissan Chemical Corporation Polishing composition containing amphoteric surfactant
JP7148849B2 (ja) 2017-04-17 2022-10-06 日産化学株式会社 両性界面活性剤を含む研磨用組成物
KR102634780B1 (ko) 2017-04-17 2024-02-07 닛산 가가쿠 가부시키가이샤 양성 계면활성제를 포함하는 연마용 조성물

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