WO2009133793A1 - 化学機械研磨用水系分散体および該化学機械研磨用水系分散体を調製するためのキット、ならびに化学機械研磨方法 - Google Patents
化学機械研磨用水系分散体および該化学機械研磨用水系分散体を調製するためのキット、ならびに化学機械研磨方法 Download PDFInfo
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- WO2009133793A1 WO2009133793A1 PCT/JP2009/057957 JP2009057957W WO2009133793A1 WO 2009133793 A1 WO2009133793 A1 WO 2009133793A1 JP 2009057957 W JP2009057957 W JP 2009057957W WO 2009133793 A1 WO2009133793 A1 WO 2009133793A1
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- WIPO (PCT)
- Prior art keywords
- chemical mechanical
- mechanical polishing
- aqueous dispersion
- composition
- acid
- Prior art date
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- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 5
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Images
Classifications
-
- 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
- C09K3/1409—Abrasive particles per se
-
- 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
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
Definitions
- the present invention relates to a chemical mechanical polishing aqueous dispersion, a kit for preparing the chemical mechanical polishing aqueous dispersion, and a chemical mechanical polishing method using the chemical mechanical polishing aqueous dispersion.
- LCD liquid crystal display
- PDP plasma display device
- ECD electrochromic display device
- ELD electroluminescent display device
- FEM Electro Luminescent Display
- FED Field Emission Display
- a flat panel display is usually configured by a method in which a display material such as liquid crystal is sandwiched between a pair of substrates and a voltage is applied to the display material. At this time, it is necessary to arrange electrical wiring made of a conductive material on at least one of the substrates.
- a wiring structure in which the conductive wiring is ultra-fine and highly integrated is essential.
- a wiring material such as copper or copper alloy
- only a dry film forming method such as a conventional sputtering method, a vapor deposition method, or a CVD method, or a wet film forming method such as an electroless plating method or a thermal decomposition method can be used. Therefore, there is a limit in forming an ultra-fine and highly integrated wiring structure.
- a chemical mechanical polishing technique As a technique capable of forming such a wiring structure, a chemical mechanical polishing technique, a so-called damascene method, has attracted attention.
- a desired wiring is formed by removing excess wiring material by chemical mechanical polishing.
- the size of a substrate used for manufacturing a conventional semiconductor device is about 50 to 300 mm, whereas it is used for manufacturing an electro-optical display device.
- the substrate (hereinafter referred to as “electro-optical display device substrate”) may have a maximum size of about 1500 to 3000 mm, the size of the substrate may vary depending on the chemical mechanical polishing technique. New problems have arisen due to it. Specifically, for example, there is a problem that the uniformity of the polishing amount per unit time (hereinafter also referred to as “polishing rate”) on the surface to be polished cannot be maintained.
- the amount of the substance to be removed varies within the surface to be polished, and flatness cannot be obtained.
- the area of the surface to be polished is not so large as to impair the in-plane flatness, but is within an acceptable range in quality control, and has not been a significant problem.
- polishing a substrate for an electro-optic display device having a surface to be polished that is much larger than the substrate for a semiconductor device it is a non-negligible problem that the uniformity of the polishing rate cannot be maintained.
- Chemical mechanical polishing is a method of polishing a substrate to be polished by filling a chemical mechanical polishing aqueous dispersion between the substrate to be polished and a polishing pad.
- this method as the size of the substrate to be polished increases, the amount of the chemical mechanical polishing aqueous dispersion in the substrate surface becomes non-uniform. Therefore, it is considered that the uniformity of the polishing rate cannot be ensured and the above problem occurs.
- the chemical mechanical polishing aqueous dispersion is theoretically squared according to the distance from the center of rotation to the outer periphery. It is necessary to increase the supply in proportion to (area equivalent).
- the chemical mechanical polishing aqueous dispersion is supplied as described above between the polishing target substrate and the polishing pad that is pressed against the polishing pad with a certain pressure. Is technically difficult.
- the electro-optical display substrate is subjected to chemical mechanical polishing, it is required to polish different materials at the same polishing rate as possible.
- the polishing rate of glass and the polishing rate of copper may be different, and the phenomenon of dishing in which the polished surface of the copper wiring becomes concave or the glass dissolves.
- a phenomenon called erosion occurs.
- such a phenomenon may occur in a semiconductor device substrate, it may also occur in an electro-optical display substrate, and a chemical mechanical polishing aqueous dispersion capable of suppressing this phenomenon is desired. ing.
- the performance of the chemical mechanical polishing aqueous dispersion used for polishing a substrate for an electro-optical display device and the like includes not only improving the flatness of the surface to be polished, suppressing dishing, but also the polishing rate. It is requested at the same time.
- the present invention solves the above-mentioned problems, and the object is to provide a high polishing rate in the process of chemical mechanical polishing a wiring layer made of copper or a copper alloy, in-plane uniformity of the polishing rate and the surface to be polished.
- a chemical mechanical polishing aqueous dispersion that can ensure the inner flatness and hardly cause problems such as dishing, a kit for preparing the chemical mechanical polishing aqueous dispersion, and the chemical mechanical polishing aqueous dispersion were used. It is to provide a chemical mechanical polishing method.
- the chemical mechanical polishing aqueous dispersion according to the present invention comprises: (A) a compound represented by the following general formula (1), (B) a surfactant that is at least one selected from alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, ⁇ -olefinsulfonic acid, and salts thereof; (C) abrasive grains, (D) an amino acid, including.
- R 1 and R 2 each independently represents a hydrogen atom, a metal atom, or a substituted or unsubstituted alkyl group
- R 3 represents a substituted or unsubstituted alkenyl group or sulfone.
- the surfactant (B) is at least one selected from alkylbenzenesulfonic acid, potassium alkylbenzenesulfonate, and ammonium alkylbenzenesulfonate, and the alkyl group of the surfactant has a substituted or unsubstituted carbon number. There can be 10 to 20 alkyl groups.
- the (B) surfactant may be at least one selected from dodecylbenzenesulfonic acid, potassium dodecylbenzenesulfonate, and ammonium dodecylbenzenesulfonate.
- the (C) abrasive grains may be at least one selected from silica and organic-inorganic composite particles.
- the (E) oxidizing agent may be hydrogen peroxide.
- (F) acid ammonium salt can be included.
- the (F) acid ammonium salt may be ammonium amidosulfate.
- the chemical mechanical polishing aqueous dispersion can be used for polishing a wiring layer made of copper or a copper alloy provided on a substrate for an electro-optical display device.
- the chemical mechanical polishing method according to the present invention comprises: The above-described chemical mechanical polishing aqueous dispersion is used to polish a wiring layer made of copper or copper alloy provided on an electro-optical display device substrate.
- the chemical mechanical polishing aqueous dispersion preparation kit comprises: A kit for preparing an aqueous dispersion for chemical mechanical polishing composed of a first composition and a second composition,
- the first composition comprises: (A) a compound represented by the following general formula (1), (B) a surfactant, (C) abrasive grains, (D) an amino acid, Including
- the second composition includes (E) an oxidizing agent.
- R 1 and R 2 each independently represents a hydrogen atom, a metal atom, or a substituted or unsubstituted alkyl group
- R 3 represents a substituted or unsubstituted alkenyl group or sulfone.
- the first composition may further include (F) an ammonium salt of acid.
- the chemical mechanical polishing aqueous dispersion preparation kit comprises: A kit for preparing an aqueous dispersion for chemical mechanical polishing composed of a third composition and a fourth composition,
- the third composition includes (C) abrasive grains,
- the fourth composition comprises (D) an amino acid; At least one of the third composition and the fourth composition is: (A) a compound represented by the following general formula (1), (B) a surfactant, Including At least one of the third composition and the fourth composition contains (E) an oxidizing agent.
- R 1 and R 2 each independently represents a hydrogen atom, a metal atom, or a substituted or unsubstituted alkyl group
- R 3 represents a substituted or unsubstituted alkenyl group or sulfone.
- At least one of the third composition and the fourth composition may further contain (F) an ammonium salt of acid.
- the chemical mechanical polishing aqueous dispersion preparation kit comprises: A kit for preparing a chemical mechanical polishing aqueous dispersion composed of a fifth composition, a sixth composition, and a seventh composition,
- the fifth composition includes (E) an oxidizing agent
- the sixth composition includes (C) abrasive grains
- the seventh composition comprises (D) an amino acid;
- At least one selected from the fifth composition, the sixth composition, and the seventh composition is: (A) a compound represented by the following general formula (1), (B) a surfactant, including.
- R 1 and R 2 each independently represents a hydrogen atom, a metal atom, or a substituted or unsubstituted alkyl group
- R 3 represents a substituted or unsubstituted alkenyl group or sulfone.
- At least one selected from the fifth composition, the sixth composition, and the seventh composition can further include (F) an ammonium salt of acid.
- the method for preparing a chemical mechanical polishing aqueous dispersion according to the present invention includes a step of mixing each composition of the chemical mechanical polishing aqueous dispersion preparation kit described above.
- the wiring layer made of copper or a copper alloy provided on the electro-optic display substrate having a maximum dimension of the polished surface of about 1500 to 3000 mm is uniformly and over the entire substrate. It can be polished flat. Moreover, according to the said chemical mechanical polishing aqueous dispersion, dishing of the surface to be polished can be suppressed. Moreover, according to the chemical mechanical polishing aqueous dispersion, the wiring layer can be polished at high speed. As a result, for example, a highly miniaturized and highly integrated wiring structure can be easily provided on an electro-optic display device substrate or a semiconductor device substrate. Further, according to the chemical mechanical polishing method, since the chemical mechanical polishing aqueous dispersion is used, for example, the flat panel display can be increased in area and definition.
- a good chemical mechanical polishing aqueous dispersion can be obtained even after long-term storage. That is, according to the chemical mechanical polishing aqueous dispersion preparation kit, the storage stability of the chemical mechanical polishing aqueous dispersion can be enhanced.
- FIG. 1 is a cross-sectional view schematically showing a part of a process of the method for manufacturing a substrate for an electro-optical device according to this embodiment.
- FIG. 2 is a cross-sectional view schematically illustrating a part of the process of the method for manufacturing the substrate for an electro-optical device according to the present embodiment.
- FIG. 3 is a cross-sectional view schematically showing a part of the process of the method for manufacturing the substrate for an electro-optical device of the present embodiment.
- FIG. 4 is a cross-sectional view schematically showing a part of the process of the method for manufacturing the substrate for an electro-optical device of the present embodiment.
- FIG. 5 is a cross-sectional view schematically illustrating an example of an electro-optical device substrate manufactured by the electro-optical device substrate manufacturing method of the present embodiment.
- Chemical mechanical polishing aqueous dispersion includes (A) a compound represented by the following general formula (1), (B) an alkylbenzenesulfonic acid, an alkylnaphthalenesulfonic acid, and an ⁇ -olefin. Surfactant which is at least 1 sort (s) chosen from sulfonic acid and those salts, (C) Abrasive grain, (D) Amino acid is included.
- R 1 and R 2 each independently represents a hydrogen atom, a metal atom, or a substituted or unsubstituted alkyl group
- R 3 represents a substituted or unsubstituted alkenyl group or sulfone.
- the compounds (A) to (F) may be abbreviated as components (A) to (F), respectively.
- the chemical mechanical polishing aqueous dispersion according to this embodiment contains (A) a compound represented by general formula (1).
- A) One of the functions of the compound represented by the general formula (1) is that the compound is adsorbed on the copper surface and protects the copper surface from excessive etching and corrosion. Thereby, a smooth to-be-polished surface can be obtained.
- R 1 and R 2 are preferably each independently a hydrogen atom, a metal atom, or a substituted or unsubstituted alkyl group.
- R 1 and R 2 are alkyl groups, it is more preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.
- R 1 and R 2 are metal atoms, they are preferably alkali metal atoms, and most preferably sodium or potassium.
- R 3 represents a substituted or unsubstituted alkenyl group or sulfonic acid group (—SO 3 X).
- X represents a hydrogen ion, an ammonium ion, or a metal ion.
- R 3 is an alkenyl group, it is preferably a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms.
- R 3 is a sulfonic acid group (—SO 3 X)
- X is preferably a hydrogen ion, a sodium ion, a potassium ion, or an ammonium ion. Since the compound represented by the general formula (1) having such a structure is adsorbed on the surface of the copper film and protects the copper film surface, it is possible to prevent copper from being excessively polished.
- a trade name “Newcol 291-M” having a sulfonic acid group (—SO 3 X) at R 3 in the formula of the general formula (1) (Available from Nippon Emulsifier Co., Ltd.), having the sulfonic acid group (—SO 3 X) in R 3 with the trade name “New Coal 292-PG” (available from Nippon Emulsifier Co., Ltd.), dipotassium alkenyl succinate A trade name “Latemul ASK” (available from Kao Corporation) and a trade name “Perex TA” (available from Kao Corporation) having a sulfonic acid group (—SO 3 X) in R 3 Is mentioned.
- the amount of the component (A) added to the chemical mechanical polishing aqueous dispersion according to the present embodiment is such that when the wiring layer provided on the electro-optical display substrate is polished, the chemical mechanical polishing aqueous dispersion in use is used.
- the amount is preferably 0.0005 to 1% by mass, more preferably 0.001 to 0.5% by mass, and particularly preferably 0.01 to 0.2% by mass based on the mass of the body. Further, when polishing the wiring layer provided on the semiconductor substrate, it is preferably 0.00005 to 0.2% by mass, more preferably 0.0001 to 0.1% by mass, particularly preferably 0. .0003 to 0.05 mass%.
- the addition amount of the component (A) is less than the above range, the protection of the copper surface is weakened, and corrosion or excessive etching proceeds, and a smooth surface may not be obtained.
- the addition amount exceeds the above range the protection of the copper surface is too strong and a sufficient polishing rate may not be obtained.
- the reason why the optimum concentration differs between the electro-optic display substrate and the semiconductor substrate is that the required polishing rate is different, and thus it is necessary to adjust the protection strength by changing the concentration.
- the chemical mechanical polishing aqueous dispersion according to this embodiment contains (B) a surfactant.
- One function of the component (B) is to impart viscosity to the chemical mechanical polishing aqueous dispersion. That is, the viscosity of the chemical mechanical polishing aqueous dispersion can be controlled by the amount of component (B) added. If the viscosity of the chemical mechanical polishing aqueous dispersion is controlled, the polishing performance of the chemical mechanical polishing aqueous dispersion can be controlled.
- an anionic surfactant is preferable, and sulfonic acids such as alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, ⁇ -olefin sulfonic acid, And their salts are more preferred.
- alkylbenzenesulfonic acid dodecylbenzenesulfonic acid is particularly preferable.
- ammonium salt, potassium salt, and sodium salt are preferable.
- the alkylbenzene sulfonate include ammonium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate.
- the amount of the (B) surfactant added to the chemical mechanical polishing aqueous dispersion according to this embodiment is preferably 0.005 to 1% by mass with respect to the mass of the chemical mechanical polishing aqueous dispersion in use. More preferably, the content is 0.01 to 0.5% by mass, and particularly preferably 0.02 to 0.15% by mass. If the addition amount of the surfactant is less than the above range, the viscosity of the chemical mechanical polishing aqueous dispersion is too low, so that the pressure applied to the polishing pad can be efficiently and uniformly transmitted to the surface to be polished. First, it causes variation in the polishing performance of the chemical mechanical polishing aqueous dispersion in the surface to be polished.
- the chemical mechanical polishing aqueous dispersion flows out from between the substrate to be polished and the polishing pad, and particularly the chemical mechanical polishing aqueous dispersion in the outer peripheral portion within the surface to be polished. May cause variation in abundance.
- the addition amount of the surfactant exceeds the above range, not only the flatness improvement effect with respect to the addition amount becomes dull and the flatness improvement effect cannot be obtained, but also the polishing rate is reduced or the chemical mechanical polishing water is used. In some cases, the viscosity of the system dispersion becomes too high, so that the frictional heat of friction rises and the in-plane uniformity is deteriorated.
- the chemical mechanical polishing aqueous dispersion according to this embodiment includes (C) abrasive grains.
- C As an abrasive grain, at least 1 sort (s) chosen from an inorganic particle, an organic particle, and an organic inorganic composite particle is mentioned. Examples of the inorganic particles include silica, alumina, titania, zirconia, and ceria.
- Organic particles include polyolefins and olefins such as polyvinyl chloride, polystyrene and styrene copolymers, polyacetals, saturated polyesters, polyamides, polycarbonates, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, etc.
- examples thereof include (meth) acrylic resins such as methacrylic copolymers, phenoxy resins, and polymethyl methacrylate, and acrylic copolymers.
- the organic / inorganic composite particles can be composed of the organic particles and the inorganic particles.
- the abrasive grains used in the chemical mechanical polishing aqueous dispersion according to this embodiment are preferably at least one selected from silica and organic-inorganic composite particles.
- Examples of the silica that can be used in the chemical mechanical polishing aqueous dispersion according to this embodiment include silica and metal alkoxide synthesized by the fumed method in which silicon chloride, aluminum chloride, titanium chloride, and the like are reacted with oxygen and hydrogen in the gas phase.
- Examples thereof include silica synthesized by a sol-gel method synthesized by hydrolysis condensation, colloidal silica synthesized by an inorganic colloid method in which impurities are removed by purification, and the like.
- colloidal silica synthesized by an inorganic colloid method in which impurities are removed by purification is particularly preferable.
- the colloidal silica those having an average particle diameter of 100 nm or less can be suitably used from the viewpoint of ensuring the flatness of the surface to be polished.
- the organic-inorganic composite particles that can be used in the chemical mechanical polishing aqueous dispersion according to the present embodiment are integrally formed to such an extent that the organic particles and inorganic particles are not easily separated during the chemical mechanical polishing step.
- the type, configuration, etc. are not particularly limited.
- Examples of the organic / inorganic composite particles include polycondensation of alkoxysilane, aluminum alkoxide, titanium alkoxide and the like in the presence of polymer particles such as polystyrene and polymethyl methacrylate, and polysiloxane or the like is formed on at least the surface of the polymer particles. What is combined can be used.
- the produced polycondensate may be directly bonded to the functional group of the polymer particles, or may be bonded via a silane coupling agent or the like. Further, silica particles, alumina particles, or the like can be used instead of alkoxysilane or the like. These may be held in entanglement with polysiloxane or the like, or may be chemically bonded to the polymer particles by a functional group such as a hydroxyl group which they have.
- organic-inorganic composite particles that can be used in the chemical mechanical polishing aqueous dispersion according to the present embodiment, in an aqueous dispersion containing organic particles and inorganic particles having zeta potentials having different signs, these particles are generated by electrostatic force.
- the thing formed by combining is also mentioned.
- the zeta potential of organic particles is often negative over the entire pH range or a wide range excluding a low pH range, but it is more reliable by using organic particles having a carboxyl group, a sulfonic acid group, etc. Organic particles having a negative zeta potential can be obtained.
- the organic particle which has a positive zeta potential in a specific pH range can also be set as the organic particle which has an amino group etc.
- the zeta potential of inorganic particles is highly pH-dependent and has an isoelectric point at which this potential becomes 0, and the sign of the zeta potential is reversed before and after that. Therefore, by combining specific organic particles and inorganic particles and mixing them in a pH range in which the zeta potential has an opposite sign, the organic particles and the inorganic particles can be integrally combined by electrostatic force. Further, even when the zeta potential has the same sign during mixing, the organic particles and the inorganic particles can be integrated by changing the pH and changing the zeta potential to the opposite sign.
- alkoxysilane, aluminum alkoxide, titanium alkoxide and the like are polycondensed as described above in the presence of particles integrally combined by electrostatic force, and at least on the surface of the particles, Further, a compound obtained by combining polysiloxane or the like can also be used.
- the average particle diameter of the organic-inorganic composite particles used in the chemical mechanical polishing aqueous dispersion according to this embodiment is preferably 50 to 500 nm. If the average particle size is less than 50 nm, a sufficient polishing rate may not be exhibited. Moreover, when it exceeds 500 nm, aggregation and sedimentation of particles are likely to occur.
- the average particle diameter of the abrasive grains can be measured with a laser scattering diffraction measuring machine, and can be calculated from the cumulative particle diameter and number by observing individual particles with a transmission electron microscope.
- the amount of (C) abrasive grains used in the chemical mechanical polishing aqueous dispersion according to this embodiment is preferably 0.01 to 10% by mass with respect to the mass of the chemical mechanical polishing aqueous dispersion in use. More preferably, it is 0.02 to 5% by mass. If the added amount of abrasive grains is less than the above range, a sufficient polishing rate may not be obtained, and it may take a long time to complete the polishing step. On the other hand, when the addition amount of the abrasive grains exceeds the above range, the cost may increase and a stable chemical mechanical polishing aqueous dispersion may not be obtained.
- the chemical mechanical polishing aqueous dispersion according to this embodiment contains (D) an amino acid.
- One of the functions of the amino acid is to improve the polishing rate when the chemical mechanical polishing aqueous dispersion is applied to the polishing of the electro-optical display substrate or the semiconductor substrate.
- Amino acids can accelerate the polishing rate especially for wiring materials made of copper or copper alloys.
- the amino acid (D) that can be used in the chemical mechanical polishing aqueous dispersion according to this embodiment is preferably an ion comprising a wiring material element or an amino acid having a coordination ability with respect to the surface of the wiring material. More preferably, it is an amino acid having a chelate coordination ability with respect to the surface of the ion or the wiring material element composed of the wiring material element, specifically, glycine, alanine, aspartic acid, glutamic acid, lysine, arginine, aromatic amino acid, complex Examples include cyclic amino acids. As the amino acid (D) used in the present embodiment, glycine is particularly preferable among the amino acids because it has a high effect of improving the polishing rate.
- the amount of the amino acid (D) added to the chemical mechanical polishing aqueous dispersion according to this embodiment is preferably 0.05 to 5% by mass with respect to the mass of the chemical mechanical polishing aqueous dispersion in use.
- the amount is preferably 0.1 to 4% by mass, particularly preferably 0.2 to 3% by mass.
- (D) If the amount of amino acid added is less than the above range, a sufficient polishing rate may not be obtained, and it may take a long time to complete the polishing step. On the other hand, when the amount of amino acid (D) added exceeds the above range, the chemical etching effect increases and the flatness of the surface to be polished may be impaired.
- the chemical mechanical polishing aqueous dispersion according to this embodiment may contain (E) an oxidizing agent as necessary.
- E) One of the functions of the oxidizing agent is to improve the polishing rate when the chemical mechanical polishing aqueous dispersion is applied to the polishing of the electro-optical display substrate or the semiconductor substrate. The reason for this is that (E) the oxidizing agent oxidizes the surface of the copper film and promotes a complexing reaction with the components of the chemical mechanical polishing aqueous dispersion, thereby forming a fragile modified layer on the surface of the copper film. This is considered to be easy to form and polish the copper film.
- Examples of the (E) oxidizing agent used in the chemical mechanical polishing aqueous dispersion according to this embodiment include hydrogen peroxide, peracetic acid, perbenzoic acid, organic peroxides such as tert-butyl hydroperoxide, and potassium permanganate.
- Permanganate compounds such as potassium dichromate, dichromate compounds such as potassium dichromate, halogen acid compounds such as potassium iodate, nitrate compounds such as nitric acid and iron nitrate, perhalogenate compounds such as perchloric acid, ammonium persulfate, etc. Examples thereof include persulfates and heteropolyacids.
- organic peroxides such as hydrogen peroxide or persulfates such as ammonium persulfate, which are harmless to decomposition products, are more preferred, and hydrogen peroxide is particularly preferred.
- the amount of the (E) oxidizing agent added to the chemical mechanical polishing aqueous dispersion according to this embodiment is preferably 0.005 to 5% by mass with respect to the mass of the chemical mechanical polishing aqueous dispersion in use. More preferably, the content is 0.01 to 3% by mass, and particularly preferably 0.05 to 1% by mass.
- the addition amount of the oxidizing agent is less than the above range, the chemical etching effect may not be sufficiently obtained. Therefore, a sufficient polishing rate cannot be obtained, and the polishing process is terminated. It may take a lot of time. On the other hand, if the amount of (E) the oxidizing agent exceeds the above range, the surface to be polished may be corroded.
- the chemical mechanical polishing aqueous dispersion according to this embodiment may contain (F) an ammonium acid salt, if necessary.
- (F) One of the functions of the acid ammonium salt is to improve the polishing rate when the chemical mechanical polishing aqueous dispersion is applied to the polishing of the electro-optical display substrate or the semiconductor substrate.
- Examples of the (F) ammonium salt that can be used in the chemical mechanical polishing aqueous dispersion according to this embodiment include ammonium sulfate, ammonium chloride, ammonium nitrate, and organic acid ammonium.
- Examples of the organic acid ammonium include ammonium amidosulfate, ammonium formate, ammonium acetate, ammonium propionate, ammonium butyrate, ammonium lactate, ammonium succinate, ammonium malonate, ammonium maleate, ammonium fumarate, ammonium quinaldate, and ammonium quinolinate. Can be mentioned. Of these, ammonium amidosulfate is particularly preferred.
- (F) component means the acid ammonium salt different from this compound, when at least one compound of (A) component and (B) component is acid ammonium salt.
- the amount of addition of the ammonium salt (F) to the chemical mechanical polishing aqueous dispersion according to this embodiment is preferably 0. 0 relative to the mass of the chemical mechanical polishing aqueous dispersion in use. 05 to 5% by mass, more preferably 0.1 to 3% by mass, and particularly preferably 0.2 to 2% by mass. (F) When the addition amount of acid ammonium salt is less than the said range, the improvement effect of a polishing rate may not be acquired. On the other hand, if the amount of (F) acid ammonium salt added exceeds the above range, the flatness of the surface to be polished may be impaired.
- the chemical mechanical polishing aqueous dispersion according to this embodiment may contain various additives as necessary in addition to the above components.
- the chemical mechanical polishing aqueous dispersion according to this embodiment can increase the dispersion stability of abrasive grains by adding an organic acid or an inorganic acid.
- organic acid include formic acid, acetic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, and compounds having a heterocyclic ring such as quinaldic acid and quinolinic acid.
- inorganic acid include nitric acid, sulfuric acid, and phosphoric acid. Of these, organic acids are particularly preferred.
- the chemical mechanical polishing aqueous dispersion according to this embodiment can be adjusted to a desired pH by adding the above acid or alkali.
- the alkali include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, or ammonia.
- the polishing rate can be controlled by adjusting the pH of the chemical mechanical polishing aqueous dispersion.
- the pH can be set by appropriately adding acid or alkali while taking into consideration factors such as electrochemical properties of the surface to be polished and dispersion stability of the abrasive grains. Among these, ammonia is particularly preferable from the viewpoint of improving the polishing rate.
- the chemical mechanical polishing aqueous dispersion can be supplied in a state where it can be used as a polishing composition as it is after the preparation.
- a polishing composition that is, a concentrated polishing composition
- containing each component of the chemical mechanical polishing aqueous dispersion at a high concentration is prepared, and the concentrated polishing composition is used at the time of use. It may be diluted to obtain a desired chemical mechanical polishing aqueous dispersion.
- a plurality of compositions (for example, two or three compositions) containing any of the above components can be prepared and used by mixing them at the time of use.
- this may be supplied to the chemical mechanical polishing apparatus, or a plurality of liquids may be supplied individually to the chemical mechanical polishing apparatus.
- a chemical mechanical polishing aqueous dispersion may be prepared on a surface plate.
- the chemical mechanical polishing aqueous dispersion can be prepared, for example, by mixing a plurality of liquids using the following first to third kits.
- the first kit is a kit for obtaining the chemical mechanical polishing aqueous dispersion by mixing the first composition and the second composition.
- the first composition is an aqueous dispersion containing (A) a compound represented by the general formula (1), (B) a surfactant, (C) abrasive grains, and (D) an amino acid.
- the second composition is (E) an aqueous solution containing an oxidizing agent.
- (F) acid ammonium salt can also be added to a said 1st composition.
- the components (A) to (F) are the same as those described in the section “1. Chemical mechanical polishing aqueous dispersion”.
- each of the above-described aqueous dispersions is obtained by mixing the first composition and the second composition. It is necessary to determine the concentration of each component contained in the first composition and the second composition so that the components are included in the concentration range described above.
- the first composition and the second composition may contain each component at a high concentration (that is, may be concentrated). In this case, the first composition is diluted at the time of use. And a second composition can be obtained.
- the storage stability of the (E) oxidizing agent contained in the second composition can be improved by separating the first composition and the second composition. it can.
- the mixing method and timing are not particularly limited.
- the first composition and the second composition containing each component at a high concentration are prepared, and the first composition and the second composition are diluted at the time of use, and these are mixed,
- a chemical mechanical polishing aqueous dispersion in which the concentration of is within the above range is prepared.
- the concentration of each component of the chemical mechanical polishing aqueous dispersion actually used is 2 What is necessary is just to prepare the 1st composition and 2nd composition which were concentrated twice.
- concentration of 2 times or more and mixing these by the weight ratio of 1: 1 it dilutes with water so that each component may become the said range. Also good.
- the chemical mechanical polishing aqueous dispersion is prepared at the time of polishing.
- the first composition and the second composition may be mixed to prepare the chemical mechanical polishing aqueous dispersion, which may then be supplied to a chemical mechanical polishing apparatus, or the first composition And the second composition may be separately supplied to the chemical mechanical polishing apparatus and mixed on a surface plate.
- the first composition and the second composition may be separately supplied to the chemical mechanical polishing apparatus and line mixed in the apparatus, or the chemical mechanical polishing apparatus may be provided with a mixing tank, May be mixed. In line mixing, a line mixer or the like may be used in order to obtain a more uniform aqueous dispersion.
- the second kit is a kit for preparing the chemical mechanical polishing aqueous dispersion by mixing the third composition and the fourth composition.
- the third composition is (C) an aqueous dispersion containing abrasive grains
- the fourth composition is (D) an aqueous solution containing an amino acid.
- At least one of the third composition and the fourth composition contains (A) a compound represented by the general formula (1) and (B) a surfactant.
- At least one of the third composition and the fourth composition contains (E) an oxidizing agent.
- (F) an ammonium salt can be included in at least one of the third composition and the fourth composition.
- the components (A) to (F) are the same as those described in the section “1. Chemical mechanical polishing aqueous dispersion”.
- the third composition and the fourth composition may contain each component at a high concentration (that is, may be concentrated). In this case, the third composition is diluted at the time of use. And a fourth composition can be obtained.
- the storage stability of the (C) abrasive grains contained in the third composition can be improved by separating the third composition and the fourth composition. it can.
- the third composition and the fourth composition are separately prepared and supplied, and are integrated during polishing.
- the mixing method and timing are not particularly limited.
- the 3rd composition and the 4th composition which contain each ingredient in high concentration are prepared, the 3rd composition and the 4th composition are diluted at the time of use, these are mixed, A chemical mechanical polishing aqueous dispersion in which the concentration of is within the above range is prepared.
- the concentration of each component of the chemical mechanical polishing aqueous dispersion actually used is 2 What is necessary is just to prepare the 3rd composition and 4th composition which were concentrated twice.
- concentration of 2 times or more and mixing these by the weight ratio of 1: 1 it dilutes with water so that each component may become the said range. Also good.
- the chemical mechanical polishing aqueous dispersion may be prepared at the time of polishing.
- this may be supplied to a chemical mechanical polishing apparatus, or the third composition And the fourth composition may be separately supplied to the chemical mechanical polishing apparatus and mixed on a surface plate.
- the third composition and the fourth composition may be separately supplied to the chemical mechanical polishing apparatus and line mixed in the apparatus, or a mixing tank may be provided in the chemical mechanical polishing apparatus, May be mixed.
- a line mixer or the like may be used in order to obtain a more uniform aqueous dispersion.
- the third kit is a kit for preparing the chemical mechanical polishing aqueous dispersion by mixing the fifth composition, the sixth composition, and the seventh composition.
- the fifth composition is (E) an aqueous solution containing an oxidizing agent
- the sixth composition is (C) an aqueous dispersion containing abrasive grains
- the composition is (D) an aqueous solution containing an amino acid.
- at least 1 sort (s) chosen from the said 5th composition, the said 6th composition, and the said 7th composition is (A) the compound shown by the said General formula (1), and (B) Surface activity Agent.
- (F) acid ammonium salt can be added to at least one selected from the fifth to seventh compositions.
- the components (A) to (F) are the same as those described in the section “1. Chemical mechanical polishing aqueous dispersion”.
- the above-mentioned components are in the concentration ranges described above in the aqueous dispersion obtained by mixing the fifth to seventh compositions. It is necessary to determine the concentration of each component contained in the fifth to seventh compositions so as to be included in the composition.
- the fifth to seventh compositions may contain each component at a high concentration (that is, may be concentrated). In this case, the fifth to seventh compositions are diluted at the time of use. It is possible to obtain According to the third kit, by separating the fifth to seventh compositions, (E) the oxidizing agent contained in the fifth composition and (C) the abrasive grains contained in the sixth composition The storage stability of can be improved.
- the fifth to seventh compositions are separately prepared and supplied, and integrated during polishing.
- the mixing method and timing are not particularly limited.
- the fifth to seventh compositions containing each component at a high concentration are prepared, and the fifth to seventh compositions are diluted at the time of use and mixed, and the concentration of each component is within the above range.
- a chemical mechanical polishing aqueous dispersion is prepared. Specifically, when the fifth to seventh compositions are mixed at a weight ratio of 1: 1: 1, the concentration of each component of the chemical mechanical polishing aqueous dispersion actually used is three times higher. Concentrated fifth to seventh compositions may be prepared. Further, after preparing the fifth to seventh compositions having a concentration of 3 times or more, mixing them at a weight ratio of 1: 1: 1, and then diluting with water so that each component is in the above range. Good.
- the chemical mechanical polishing aqueous dispersion may be prepared at the time of polishing.
- this may be supplied to a chemical mechanical polishing apparatus, or the fifth to seventh compositions may be supplied.
- You may supply separately to a chemical mechanical polishing apparatus, and may mix on a surface plate.
- the fifth to seventh compositions may be separately supplied to the chemical mechanical polishing apparatus and line mixed in the apparatus, or the chemical mechanical polishing apparatus may be provided with a mixing tank and mixed in the mixing tank. Also good. In line mixing, a line mixer or the like may be used in order to obtain a more uniform aqueous dispersion.
- an appropriate chemical mechanical polishing aqueous dispersion can be selected according to the purpose depending on the polishing target.
- the chemical mechanical polishing step in the method for manufacturing the substrate for an electro-optic display device according to the present embodiment is divided into a first step for mainly polishing the wiring layer and a second step for mainly polishing the barrier metal film. Can do.
- the chemical mechanical polishing aqueous dispersion according to this embodiment can be applied to a first stage process for polishing a wiring layer made of copper or a copper alloy.
- FIG. 1 to 5 are cross-sectional views of the substrate for an electro-optic display device showing the chemical mechanical polishing process according to this embodiment.
- a glass substrate, a film substrate, or a plastic substrate can be used as the substrate used in the method for manufacturing the substrate for an electro-optic display device according to the present embodiment.
- the substrate having a diagonal dimension of 1500 mm to 3000 mm can be used.
- the substrate may be a single layer or a laminate in which an insulating film such as silicon oxide is formed on the substrate.
- a glass substrate 10 is prepared.
- the glass substrate 10 has a wiring recess 12 for forming a wiring.
- dry etching is used as a method for forming the wiring recess 12 on the glass substrate 10. Dry etching is a method of physically processing a glass substrate by irradiating accelerated ions. Fine pattern processing can be performed by precisely controlling the irradiation beam.
- the glass substrate 10 can be made of a material such as soda-lime glass, borosilicate glass, aluminosilicate glass, or quartz glass.
- a barrier metal film 20 is formed so as to cover the surface of the glass substrate 10 and the bottom and inner wall surface of the wiring recess 12.
- the barrier metal film 20 can be made of a material such as tantalum or tantalum nitride, for example.
- CVD chemical vapor deposition
- a metal for wiring is deposited so as to cover the surface of the barrier metal film 20 to form a metal film 30.
- the metal film 30 can be made of copper or a copper alloy.
- PVD physical vapor deposition
- the excess metal film 30 other than the portion buried in the wiring recess 12 is removed by chemical mechanical polishing using the chemical mechanical polishing aqueous dispersion according to this embodiment. Further, the above method is repeated until the barrier metal film 20 is exposed. After chemical mechanical polishing, it is preferable to remove abrasive grains remaining on the surface to be polished. The removal of the abrasive grains can be performed by a normal cleaning method.
- the surface of the barrier metal film 20 and the glass substrate 10 other than the wiring recess 12 is subjected to chemical mechanical polishing using a chemical mechanical polishing aqueous dispersion for the barrier metal film. To remove.
- the metal film 30 is removed using the chemical mechanical polishing aqueous dispersion according to the present embodiment. Therefore, the polishing rate is high, the in-plane flatness of the polishing is good, and dishing or the like is performed. Less prone to polishing defects. Therefore, according to the present method, a substrate for an electro-optic display device or a semiconductor substrate having a wiring metal, highly miniaturized, and excellent in in-plane flatness can be manufactured with high throughput.
- Substrate used for evaluation of flatness (dishing) A barrier metal film made of tantalum nitride having a thickness of 30 nm is formed on the surface of a glass substrate having a diagonal dimension of 2000 mm provided with a wiring pattern having a width of 300 ⁇ m formed by a recess having a depth of 3 ⁇ m. Filmed. Thereafter, copper was deposited to a thickness of 6 ⁇ m on the barrier metal film and in the recess by sputtering.
- substrate a the substrate thus obtained is referred to as “substrate a”.
- Substrate used for in-plane uniformity evaluation A barrier metal film made of tantalum nitride having a thickness of 30 nm is formed on the surface of a glass substrate having a diagonal dimension of 2000 mm. Thereafter, copper was deposited on the barrier metal film to a thickness of 6 ⁇ m by sputtering.
- substrate b the substrate thus obtained is referred to as “substrate b”.
- a silicon substrate with an 8-inch thermal oxide film (hereinafter referred to as “substrate c”) on which a substrate and a copper film with a film thickness of 15,000 angstroms are used for the evaluation of the polishing rate.
- a silicon substrate with an 8-inch thermal oxide film on which a tantalum film having a thickness of 2,000 angstroms is stacked (hereinafter referred to as “substrate d”).
- a patterned substrate (a silicon nitride film of 1,000 angstroms is deposited on the silicon substrate and low A dielectric insulating film (Black Diamond film) is sequentially deposited to 4,500 angstroms, and then a PETEOS film is sequentially deposited to 500 angstroms, followed by mask pattern processing of “SEMATECH 854”, and 250 angstrom tantalum film and 1000 angstrom copper seed on it.
- the test was performed using a test substrate on which a film and a 10,000 angstrom copper plating film were sequentially laminated (hereinafter referred to as “substrate e”).
- aqueous dispersion containing abrasive grains composed of inorganic abrasive grains or composite grains 4.2.1. Preparation of Aqueous Dispersion Containing Inorganic Abrasive Grains (a) Preparation of Aqueous Dispersion Containing Fumed Method Silica Particles 2 kg of fumed silica particles (trade name “Aerosil # 90” manufactured by Nippon Aerosil Co., Ltd.) An aqueous dispersion containing fumed silica was prepared by dispersing to 7 kg using an ultrasonic disperser and filtering through a filter having a pore size of 5 ⁇ m.
- the alcohol in the dispersion is removed by repeating the operation of removing the alcohol content with an evaporator while adding ion-exchanged water to the dispersion at 80 ° C., and the solid content concentration is 8% by mass.
- the alcohol in the dispersion is removed by repeating the operation of removing the alcohol content with an evaporator while adding ion-exchanged water to the dispersion at 80 ° C., and the solid content concentration is 8% by mass.
- the dispersion aqueous solution containing the silica particles is concentrated under reduced pressure (boiling point 78 ° C.), and the silica concentration is 32.0 mass%, the average particle diameter of silica is 26 nm, and the pH is 9.8. Got.
- This silica particle dispersion is again passed through the hydrogen-type cation exchange resin layer to remove most of sodium, and then 10% by mass of potassium hydroxide aqueous solution is added, and the silica particle concentration: 28.0% by mass, pH A silica particle dispersion of 10.0 was obtained.
- aqueous dispersion containing abrasive grains composed of composite particles (d) Preparation of aqueous dispersion containing polymer particles 90 parts by mass of methyl methacrylate, methoxypolyethylene glycol methacrylate (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) “NK Ester M-90G”, # 400) 5 parts by mass, 4-vinylpyridine 5 parts by mass, azo polymerization initiator (trade name “V50” manufactured by Wako Pure Chemical Industries, Ltd.) 2 parts by mass, and ion-exchanged water 400 parts by mass was put into a flask having a capacity of 2000 cm 3 , heated to 70 ° C.
- an aqueous dispersion containing 10% by mass of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name “Snowtex O”) was adjusted to 8 with potassium hydroxide to obtain an aqueous dispersion (g).
- the zeta potential of the polymethyl methacrylate-based particles contained in the aqueous dispersion (f) was +17 mV
- the zeta potential of the silica particles contained in the aqueous dispersion (g) was ⁇ 40 mV.
- aqueous dispersion (g) 50 parts by mass of the aqueous dispersion (g) was gradually added to 100 parts by mass of the aqueous dispersion (f), mixed and stirred for 2 hours, and silica particles adhered to the polymethyl methacrylate particles.
- An aqueous dispersion containing particles was obtained.
- 2 parts of vinyltriethoxysilane was added to this aqueous dispersion and stirred for 1 hour, then 1 part by weight of tetraethoxysilane was added, the temperature was raised to 60 ° C., and stirring was continued for 3 hours, followed by cooling.
- an aqueous dispersion (e) containing composite particles was obtained.
- the average particle diameter of the composite particles was 180 nm, and silica particles were attached to 80% of the surface of the polymethyl methacrylate particles.
- a surfactant having a group represented by -SO 3 X in the formula, R 3 in the general formula (1) (Trade name “New Coal 292-PG” manufactured by Nippon Emulsifier Co., Ltd.) is used as a compound (c), a surfactant (trade name “Latemul ASK” manufactured by Kao Corporation) that is dipotassium alkenyl succinate, and a compound ( D)
- a surfactant (trade name “Perex TA” manufactured by Kao Corporation) having a group represented by —SO 3 X in R 3 in the general formula (1) was used.
- amino acid (D) any one of glycine, alanine and aspartic acid was used.
- Ammonium amidosulfate was used as the acid ammonium salt.
- the (B) surfactant used here is any one of dodecylbenzenesulfonic acid, potassium dodecylbenzenesulfonate, and ammonium dodecylbenzenesulfonate
- the oxidizing agent is any one of hydrogen peroxide and ammonium persulfate. Or a kind.
- Second composition B1 The concentration was adjusted with ion-exchanged water so that the hydrogen peroxide concentration was 5% by mass to obtain a second composition B1.
- the kit for preparing the chemical mechanical polishing aqueous dispersion composed of the first composition A1 and the second composition B1 was prepared by the above steps.
- aqueous dispersion containing colloidal silica prepared in the above "4.2.1.
- B) Preparation of aqueous dispersion containing colloidal silica a is 6.0 mass in terms of silica. % In a polyethylene bottle, converted to 0.24% by mass of dipotassium alkenyl succinate, 0.24% by mass of dodecylbenzenesulfonic acid and 35% by mass of hydrogen peroxide in hydrogen peroxide solution. An amount corresponding to 8% by mass was sequentially added, and the pH was adjusted with ammonia, followed by stirring for 15 minutes.
- 3rd composition A2 which is an aqueous dispersion was obtained by filtering with a filter with a hole diameter of 5 micrometers.
- composition A3 that is an aqueous dispersion.
- Polishing evaluation test 4.7.1. Polishing a substrate with a copper film 4.7.1a. Evaluation of Polishing Rate Using the chemical mechanical polishing aqueous dispersions of Examples 1 to 11, Comparative Examples 1 to 3 and Reference Example 1, a copper film-coated substrate was polished under the following conditions. This evaluation was performed using the substrate b described above.
- ⁇ Polishing device Chemical mechanical polishing machine for display substrate
- Polishing pad Urethane foam material chemical mechanical polishing pad with groove
- Carrier head load 200 g / cm 2 -Head rotation speed: 60 rpm ⁇ Table rotation speed: 65pm ⁇
- Abrasive supply amount 150 cm 3 / min ⁇ Polishing time: 30 seconds
- the chemical mechanical polishing machine for display substrate is an existing chemical mechanical polishing device (model “EPO-112” manufactured by Ebara Corporation) so that a display substrate having a diagonal size of 2000 mm can be subjected to chemical mechanical polishing. It is a modified one.
- polishing rate (nm / min) (Thickness of copper film before polishing-thickness of copper film after polishing) / polishing time (2)
- the dishing was evaluated by measuring a 300 ⁇ m wiring on the substrate a using a surface roughness meter (model “P-10” manufactured by KLA Tencor).
- the polishing time in the dishing evaluation is the polishing rate V (nm / min) obtained by “4.7.1 Polishing the substrate with a copper film” of the initial excess copper film having a thickness T (nm).
- the divided value (T / V) (min) was multiplied by 1.5 (min).
- the amount of depression of the copper wiring measured by the surface roughness meter is described as a dishing value ( ⁇ m).
- the dishing value is 1 ( ⁇ m) or less, it can be said that dishing is suppressed.
- polishing amount Film thickness before polishing-Film thickness after polishing (4)
- Polishing speed ⁇ (polishing amount) / polishing time (5)
- In-plane uniformity (Standard deviation of polishing amount / Average value of polishing amount) ⁇ 100 (%) (6)
- the in-plane uniformity is good when the in-plane uniformity is 10% or less.
- the polishing rate is sufficiently high at 1710 nm / min or more, the dishing of 300 ⁇ m wiring is as small as 0.82 ⁇ m or less, and the in-plane uniformity is 8.6% or less. is there. From the above, the chemical mechanical polishing aqueous dispersions of Examples 1 to 8 have a high polishing rate and ensure in-plane uniformity in chemical mechanical polishing for a substrate (display substrate) having a large surface area to be polished. It was also found that dishing can be suppressed.
- Example 1 Although the polishing rate was very high at 2980 nm / min, the dishing of the 300 ⁇ m wiring was as small as 0.77 ⁇ m, and the in-plane uniformity was as low as 8.0%, and very good results were obtained. Has been obtained.
- Examples 9 to 11 have almost the same results as Example 5. That is, it was found that even when the chemical mechanical polishing aqueous dispersion was prepared using a kit stored at room temperature for 6 months, it had almost the same performance as that immediately after the preparation. From this result, it was found that the storage stability of each component contained in the chemical mechanical polishing aqueous dispersion can be ensured by storing at least as a kit. On the other hand, the chemical mechanical polishing aqueous dispersion of Example 5 stored at room temperature for 6 months showed enlargement of abrasive grains, and required redispersion such as ultrasonic treatment when used.
- Comparative Example 1 is an example in which (D) amino acid is not contained, the polishing rate is not sufficient, and high throughput is realized when used for manufacturing a large area substrate such as a substrate for an electro-optical display device. Is difficult.
- Comparative Example 2 is an example in which the compound represented by (A) the chemical formula (1) is not included, and although the polishing rate is not poor, dishing and in-plane uniformity are too large, so the electro-optical display device It cannot be said that it is suitable for manufacturing a manufacturing substrate.
- Comparative Example 3 is an example in which (B) the surfactant is not included, and although the polishing rate is not poor, the dishing and in-plane uniformity are too large, so that the substrate such as a substrate for an electro-optical display device It is not suitable for the production of
- Reference Example 1 is an example in which (E) an oxidizing agent is not included, and the polishing rate is very low, and when used for manufacturing a large area substrate such as a substrate for an electro-optical display device, a high throughput is realized. Is difficult. In this example, since the polishing rate was too low, it was impossible to evaluate dishing and in-plane uniformity.
- polishing speed (1) Polishing conditions and head rotation speed: 70 rpm Head load: 200 gf / cm 2 ⁇ Table rotation speed: 70rpm -Supply speed of chemical mechanical polishing aqueous dispersion: 200 mL / min
- the supply speed of the chemical mechanical polishing aqueous dispersion refers to a value obtained by assigning the total supply amount of all supply liquids per unit time.
- polishing rate calculation method For copper film and tantalum film, polishing of each film on the substrate c and the substrate d using an electroconductive film thickness measuring device (model “Omnimap RS75” manufactured by KLA Tencor). The film thickness after the treatment was measured, and the polishing rate was calculated from the film thickness decreased by chemical mechanical polishing and the polishing time.
- polishing Conditions in Polishing Process / Aqueous Dispersion for Polishing Process Steps Examples 12 to 18 and Comparative Examples 4 to 7 and Reference Example 2 Aqueous dispersion for chemical mechanical polishing Using the body.
- the supply speed of the chemical mechanical polishing aqueous dispersion refers to a value obtained by assigning the total supply amount of all supply liquids per unit time.
- Polishing time After the copper film was removed from the surface to be polished and the barrier metal film was exposed, the point of polishing for 30 seconds was taken as the polishing end point.
- the amount of erosion (nm) in a portion where the fine wiring length in a pattern of copper wiring width (line, L) / insulating film width (space, S) of 9 ⁇ m / 1 ⁇ m was continuously 1000 ⁇ m was measured.
- the results are shown in Table 2.
- the erosion amount is preferably 30 nm or less, and more preferably 20 nm or less.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Rehabilitation Tools (AREA)
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WO2013177110A1 (en) | 2012-05-22 | 2013-11-28 | Cabot Microelectronics Corporation | Cmp composition containing zirconia particles and method of use |
WO2021130947A1 (ja) * | 2019-12-26 | 2021-07-01 | ニッタ・デュポン株式会社 | 研磨用スラリー |
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US10479911B1 (en) * | 2018-06-05 | 2019-11-19 | Cabot Microelectronics Corporation | Composition and method for polishing memory hard disks exhibiting reduced edge roll off |
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KR20110102774A (ko) | 2011-09-19 |
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JP5782257B2 (ja) | 2015-09-24 |
JPWO2009133793A1 (ja) | 2011-09-01 |
TW201000614A (en) | 2010-01-01 |
KR101126100B1 (ko) | 2012-03-29 |
KR101610976B1 (ko) | 2016-04-08 |
JP2014159587A (ja) | 2014-09-04 |
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