WO2010052983A1 - 研磨用組成物および半導体集積回路装置の製造方法 - Google Patents
研磨用組成物および半導体集積回路装置の製造方法 Download PDFInfo
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- WO2010052983A1 WO2010052983A1 PCT/JP2009/067269 JP2009067269W WO2010052983A1 WO 2010052983 A1 WO2010052983 A1 WO 2010052983A1 JP 2009067269 W JP2009067269 W JP 2009067269W WO 2010052983 A1 WO2010052983 A1 WO 2010052983A1
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- 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
-
- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- H01L21/31—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]
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- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/7684—Smoothing; Planarisation
Definitions
- the present invention relates to a novel polishing composition suitably used for semiconductor integrated circuits and the like.
- CMP Chemical Mechanical Polishing
- Specific needs for new polishing compositions include prevention of surface irregularities.
- Multi-layered wiring is to form a new circuit using lithography etc. after forming the circuit, but if there is unevenness on the surface of the underlying circuit, a new circuit on it will be created. Since the surface to be formed also appears uneven and deviates from the depth of focus in lithography, it becomes impossible to form the wiring as designed. In recent semiconductor integrated circuit designs, the surface on which the circuit is formed is flattened with extremely high accuracy. Therefore, it is required not to affect the flatness of the surface of the upper layer.
- the unevenness on the surface affects the electrical characteristics of the wiring, so it should be suppressed as much as possible in order to suppress variations in quality.
- a wiring groove pattern is formed on the target surface of the semiconductor integrated circuit device, and aluminum or It is formed so as to embed a metal having a low specific resistance such as metallic copper.
- the metal is first formed as a film on the surface by a plating method or a sputtering method.
- the film is polished by a CMP technique, the metal other than the wiring portion is removed, and a wiring corresponding to the groove is formed. At this time, the polished surface is also flattened.
- the barrier layer adjacent to the copper layer is exposed.
- the problem of copper remaining on the barrier layer (copper residue) and the pits (dents) on the copper wiring become problems as surface irregularities.
- FIG. 1 is a cross-sectional view schematically showing a state in which a portion having a copper residue 21 is raised as compared with a portion 22 having no copper residue. Such a copper residue is likely to occur at a location where the wiring density is high. In that case, the copper wiring at the corresponding location may even be thicker than other locations.
- FIGS. FIG. 2 shows a state where there is a copper residue 21 at a portion 23 where the wiring density is high.
- the thickness of the copper wiring in the portion 23 tends to be thicker than the thickness of the copper wiring in the portion 22 where there is no copper remaining.
- the barrier layer is not shown.
- the pits on the copper wiring are probably a kind of copper corrosion and are fine enough to be finally seen at a magnification of about tens of thousands of times.
- polishing composition for CMP used for polishing copper an abrasive using rosin is disclosed.
- this polishing composition it has not been possible to completely cope with the copper residue or to sufficiently reduce the polishing rate of the barrier layer (see, for example, Patent Document 1).
- An object of the present invention is to provide a novel polishing composition that can solve the above-mentioned problems. Still other objects and advantages of the present invention will become apparent from the following description.
- the copper layer A polishing composition used in a step of polishing until the adjacent barrier layer is exposed (first polishing step), An alicyclic resin acid;
- the content in the polishing composition is 0.1 to 1.5% by mass, the average primary particle size is 10 to 40 nm, the average secondary particle size is 30 to 80 nm, and the average secondary particle size ⁇ Colloidal silica having a content in the range of 10 to 40;
- a polishing composition comprising tetramethylammonium ions is provided.
- the polishing composition according to the above aspect 1 which further contains potassium ions.
- the content of tetramethylammonium ions in the polishing composition is 0.1 to 1.4% by mass in terms of tetramethylammonium hydroxide.
- the described polishing composition is provided.
- the polishing composition of the said aspect 2 or 3 whose content in the polishing composition of potassium ion is 0.6 mass% or less in conversion of potassium hydroxide is provided. Is done.
- the polishing composition as described in 1. is provided.
- the polishing composition according to any one of the above aspects 1 to 5, wherein the alicyclic resin acid is rosin.
- the polishing composition according to any one of the above aspects 1 to 7, further comprising a complex-forming agent.
- a method of manufacturing a semiconductor integrated circuit device includes an insulating layer having a groove and a copper embedded wiring formed in the groove, A multilayer structure for a semiconductor integrated circuit device in which a barrier layer and a copper layer are formed in this order on the insulating layer is formed using the polishing composition according to any one of the above aspects 1 to 8, and the copper layer A method of manufacturing a semiconductor integrated circuit device is provided that includes polishing until the barrier layer adjacent to the substrate is exposed.
- the method for manufacturing a semiconductor integrated circuit device according to the ninth aspect, wherein the barrier layer includes at least one selected from the group consisting of Ta, TaN, Ti, TiN and Ru. Provided.
- the method for manufacturing a semiconductor integrated circuit device according to the ninth or tenth aspect, wherein the multilayer structure includes a cap layer between the insulating layer and the barrier layer. Is provided.
- the method for manufacturing a semiconductor integrated circuit device according to any one of the above aspects 9 to 11, wherein the insulating layer having the groove has a silicon dioxide film or a relative dielectric constant of 3 or less. Provided.
- a novel polishing composition for the first polishing step that can solve the problem of remaining copper and suppress the polishing rate of the barrier layer while improving the polishing rate of the copper wiring in the first polishing step. Things are obtained.
- FIG. 1 is a cross-sectional view schematically showing a state in which a portion having a copper residue is raised as compared with a portion having no copper residue.
- FIG. 2 is a cross-sectional view schematically showing a state in which there is a copper residue at a location where the wiring density is high.
- FIG. 3 is a cross-sectional view schematically showing a state after the cross section in the state of FIG. 2 is subjected to the second polishing step.
- 4A to 4C are schematic cross-sectional views of the patterned wafer before and after the CMP process in the copper buried wiring forming process.
- 4A is a cross-sectional view of the semiconductor integrated circuit before polishing, FIG.
- FIG. 4B is a cross-sectional view of the semiconductor integrated circuit in which dishing has occurred by polishing, and FIG. 4C is ideally polished.
- FIG. 6 is a cross-sectional view after polishing a semiconductor integrated circuit.
- FIG. 5 is a schematic cross-sectional view of a patterned wafer for explaining erosion.
- polishing composition according to the present invention will be described in the case of polishing a surface copper film having a groove for wiring of a semiconductor integrated circuit.
- the case where the polishing composition according to the present invention is used for polishing copper wiring will be described. It goes without saying that can also be used.
- the following description exemplifies the present invention, does not limit the scope of the present invention, and it goes without saying that other embodiments may also belong to the category of the present invention as long as they match the gist of the present invention. Yes.
- the polishing composition according to the present invention is adjacent to the copper layer in pattern formation in which the copper layer provided on the insulating layer via the barrier layer is polished to alternately form the copper embedded wiring and the insulating layer.
- the polishing composition until the barrier layer is exposed that is, the polishing composition for the first polishing step.
- the copper portion other than the copper wiring is removed in the first polishing step
- the barrier layer is removed in the second polishing step, and in most cases, the insulating layer and, if necessary, a part of the copper are extremely used.
- polishing slightly a flat surface composed of an insulating layer and a copper layer is formed.
- FIG. 4A A schematic cross section of the patterned wafer before polishing is shown in FIG. 4A.
- an insulating layer 2 a barrier layer 3, and a wiring metal layer (copper layer) 4 are formed on a Si substrate 1.
- insulating layer As the insulating layer, a SiO 2 film by plasma CVD using tetraethoxysilane, silane or the like, a low dielectric constant material film (SiOF film, organic SOG film, etc.), and a combination of these with a cap layer, All of these are possible.
- any known material may be used as the material constituting the insulating layer that is one of the objects to be polished by the polishing composition according to the present invention.
- An example of such a material is a silicon dioxide film.
- the silicon dioxide film a film having a crosslinked structure of Si and O and having a ratio of the number of atoms of Si and O of 1: 2 is generally used, but other films may be used.
- a silicon dioxide film a film deposited by plasma CVD using tetraethoxysilane (TEOS) or silane gas (SiH 4 ) is generally known.
- TEOS tetraethoxysilane
- SiH 4 silane gas
- a film made of a low dielectric constant material having a relative dielectric constant of 3 or less has been used as an insulating layer for the purpose of suppressing signal delay.
- a low dielectric constant material film include a film made of fluorine-added silicon oxide (SiOF), an organic SOG film (a film containing an organic component obtained by Spin on glass), a low dielectric constant material film such as a porous silica film, An organic silicon material (generally referred to as SiOC) film that is mainly composed of Si—O bonds and includes CH 3 bonds is known. These films can also be suitably used as an insulating layer to which the polishing composition according to the present invention is applied.
- Organic silicon materials are an extension of conventional technology as process technology, and mass production technology with a wide range of application has been achieved by performing appropriate process tuning. Therefore, a technique for flattening a film using this low dielectric constant material is desired, and the polishing composition according to the present invention can be suitably used.
- organic silicon material which is a low dielectric constant material
- trade name: Black Diamond (relative permittivity 2.7, Applied Materials technology), trade name Coral (relative permittivity 2.7, Novellus Systems technology), Aurora 2 7 (relative permittivity 2.7, Japan ASM Co., Ltd. technology) and the like trade name: Black Diamond (relative permittivity 2.7, Applied Materials technology), trade name Coral (relative permittivity 2.7, Novellus Systems technology), Aurora 2 7 (relative permittivity 2.7, Japan ASM Co., Ltd. technology) and the like, and a compound having a Si—CH 3 bond is particularly preferably used.
- the polishing composition according to the present invention is not shown in FIG. 4, it can also be suitably used when a cap layer is formed on an insulating layer.
- a cap layer is formed on an insulating layer.
- the cap layer is completely removed and then the insulating layer is shaved and flattened. it can.
- the cap layer is used to increase the adhesion between the insulating layer and the barrier layer when a low dielectric constant material is used for the insulating layer, or to embed a metal wiring layer in the low dielectric constant insulating layer that is chemically and mechanically fragile. It is a layer provided for the purpose of using as a mask material when the groove is formed by etching or for preventing deterioration of the low dielectric constant material.
- a film having silicon and oxygen as constituent elements is generally used.
- An example of such a film is a silicon dioxide film.
- the silicon dioxide film a film having a crosslinked structure of Si and O and having a ratio of the number of atoms of Si and O of 1: 2 is generally used, but other films may be used.
- a silicon dioxide film a film deposited by plasma CVD using tetraethoxysilane (TEOS) or silane gas (SiH 4 ) is generally known.
- the barrier layer is a layer containing at least one selected from the group consisting of Ta, TaN, Ti, TiN, Ru, and the like formed on the insulating layer by, for example, sputtering, and copper from the copper layer to the insulating layer.
- the polishing of the copper layer it also serves as a stopper for finding a point in time when the wiring portion appears.
- the copper layer is formed on the insulating layer via a barrier layer.
- the film forming method include a method of forming a Cu seed layer to a thickness of about 100 nm by sputtering after forming the barrier layer, and further forming a Cu layer on the Cu seed layer by electrolytic plating.
- the dishing amount at the time when the barrier layer is exposed is large, the dishing amount varies greatly after the first polishing step is completed and the excess copper layer is removed by overpolishing, and in some cases, the erosion Also occurred.
- the second polishing step after the barrier layer is shaved, it is necessary to further grind a part of the insulating layer and the copper wiring to finish the copper wiring and the insulating layer smoothly.
- the amount of polishing in the second polishing step is increased, there may be a portion where the depth of the wiring groove is insufficient due to the in-plane distribution of polishing, or dishing of the copper wiring may be newly generated. Note that erosion is likely to occur in thin wiring portions and dense wiring portions. As shown in FIG.
- the insulating layer in the wiring portion is excessively polished as compared with the insulating layer portion (Global portion) having no wiring pattern. This is a phenomenon in which the insulating layer is partially thinned. That is, an erosion portion 18 that is further polished than the global portion 20 is generated. In FIG. 5, the barrier layer is omitted.
- the polishing composition of the present invention when used, the copper wiring is not polished more than necessary by over-polishing, so that the first polishing step does not cause dishing and does not cause erosion. Can be polished.
- the amount of dishing at the time when the first polishing process is completed by removing the excess copper layer smoothly and uniformly over the entire wafer surface by over-polishing Has a remarkable effect that the thickness can be 55 nm or less.
- the trench processing amount (wiring groove cutting amount) is shallow, and the polishing amount is reduced. Can be reduced. As a result, the entire process can be performed in a short time, so that the cost can be reduced, and the effects of suppressing variations in the wiring groove depth and dishing of the copper wiring can also be obtained.
- the polishing composition may contain a complex forming agent.
- the complex forming agent means a substance that forms a complex with copper. Inclusion of the complexing agent increases the copper polishing rate, although the mechanism is not clear. Specifically, it is as follows.
- Carboxylic acid having a nitrogen-containing heterocyclic group (monocarboxylic acid, polycarboxylic acid): 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridine Dicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, 2-quinoline Carboxylic acid (quinaldic acid), 3-quinoline carboxylic acid, 4-quinoline carboxylic acid, 8-quinoline carboxylic acid.
- Carboxylic acid having amino group (amino acid etc.): alanine, glycine, proline, phenylalanine.
- Carboxylic acid having a hydroxyl group (such as hydroxycarboxylic acid): lactic acid, malic acid, citric acid, isocitric acid, tartaric acid, glycolic acid, gluconic acid, salicylic acid.
- Carboxylic acid having a thiol group thioglycolic acid, thiosalicylic acid.
- the complex-forming agent is particularly preferably a polycarboxylic acid or monocarboxylic acid having a nitrogen-containing heterocyclic group, or an aliphatic polycarboxylic acid such as oxalic acid, particularly 2-pyridinecarboxylic acid or 2,3-pyridinecarboxylic acid. preferable.
- a carboxylic acid having a nitrogen-containing heterocyclic group such as 2-pyridinecarboxylic acid, the polishing rate of copper is particularly increased, and adhesion and residue of a copper complex or the like on the polishing pad can be prevented. Demonstrated.
- the content of the complex-forming agent in the polishing composition of the present invention is 0.1 to 5% by mass, particularly 0.3 to 3% by mass, more preferably 0.5 to 1.5% by mass with respect to the polishing composition. It is preferable that it is mass%. If the amount is less than 0.1% by mass, the polishing rate of copper may decrease, and if it exceeds 5% by mass, corrosion or dishing of the copper surface may occur.
- the polishing composition contains an alicyclic resin acid.
- Resin acid is an organic acid (carboxylic acid) that is present as a free or ester in natural resin
- alicyclic resin acid is a compound having an alicyclic structure among the resin acids (published by Kyoritsu Shuppan Co., Ltd.) (See “Resin acid” in Chemical Dictionary 4).
- a natural resin containing an alicyclic resin acid a refined product mainly composed of an alicyclic resin acid purified from a natural resin (at the same time, isomerization or the like may occur). Examples thereof include resin acids, alicyclic resin acids which are single compounds extracted from natural resins, and mixtures of two or more thereof.
- the purified resin acid examples include rosin obtained from pine resin, tall oil, tall oil rosin and the like.
- a purified resin acid mainly composed of an alicyclic resin acid such as rosin, abietic acid or its isomer, pimaric acid or its isomer, or hydrogenated abietic acid is preferable.
- a commercially available rosin can be used.
- rosin is a compound whose composition ratio varies depending on the type of natural resin from which it is derived, but any type of rosin can be used as long as it has an alicyclic resin acid as a main component. Can be used.
- rosins contain a small amount of aliphatic resin acid.
- the aliphatic resin acid is mainly an unsaturated higher fatty acid such as oleic acid or linoleic acid, and its content is usually about 10% by mass relative to the whole rosin.
- alicyclic resin acids that are single compounds include abietic acid, isomers of abietic acid, neoabietic acid, parastrinic acid, levopimaric acid, and the like.
- dehydroabietic acid and secodehydroabietic acid which are dehydrogenated products of acids.
- two or more alicyclic resin acids may be contained.
- a purified resin acid such as rosin is originally a mixture of two or more alicyclic resin acids (single compound), but is regarded as one alicyclic resin acid in the present invention. Therefore, in the polishing composition, two or more kinds of rosins may be contained, or one or more kinds of alicyclic resin acids which are a single compound with rosin may be contained.
- the alicyclic resin acid may be a derivative of the above-described purified resin acid or a single compound alicyclic resin acid, which is a compound having at least one carboxy group or a mixture containing the same. Good.
- the derivatives include isomerized products, hydrides, dehydrogenated products, multimerized products, unsaturated compounds (eg, maleic anhydride, alicyclic resin acids) other than alicyclic resin acids extracted from natural resins.
- unsaturated compounds eg, maleic anhydride, alicyclic resin acids
- Maleic anhydride adduct maleic acid modified product
- fumaric acid adduct fumaric acid-modified product
- at least one selected from the group consisting of dehydrogenated products are preferable, and the dehydrogenated product includes those in which a part of the alicyclic ring is converted to an aromatic ring by dehydrogenation.
- the content of abietic acid (including neoabietic acid that is an isomer of abietic acid, dihydroabietic acid that is a hydride of abietic acid, tetrahydroabietic acid, dehydrogenated product of abietic acid, etc.) is an abrasive composition. 0.005 to 5% by mass, further 0.005 to 2% by mass, 0.01 to 0.5% by mass, and 0.01 to 0.1% by mass are effective for copper. It is preferable because the surface can be protected.
- Alicyclic resin acids include salts of alicyclic resin acids.
- alicyclic resin acid salt rosin alkali metal salt (particularly potassium salt), rosin ammonium salt, and rosin organic amine salt, also called rosin, are preferable.
- rosin alkali metal salt particularly potassium salt
- rosin ammonium salt rosin ammonium salt
- rosin organic amine salt also called rosin
- salts for example, these 2 or more types of mixtures can also be used.
- an effect of suppressing the amount of dishing can be obtained by including an alicyclic fatty acid.
- the mechanism for obtaining such an effect acts as a surface protective agent that forms a protective layer on the surface of the copper film by performing some chemical or physical action on the surface of the semiconductor integrated circuit copper film during polishing. It is thought that.
- This surface protective layer is not so strong as to completely hinder the polishing of the copper film, and in the copper film on the semiconductor integrated circuit substrate, the polishing progresses at the convex portion where the pressing pressure of the polishing pad is large, and the pressing pressure is small. Polishing does not proceed in the concave portion of the wiring portion. Thereby, it is considered that a highly smooth polished surface property is realized.
- the content of the alicyclic resin acid in the polishing composition is 0.005 to 5% by mass, more preferably 0.01% to 1% by mass, and 0.01% to 0.5% by mass. preferable.
- the amount is less than 0.005% by mass, it is considered that the protective action of the copper film surface is insufficient, and corrosion and dishing are likely to occur during polishing. On the other hand, if it exceeds 5% by mass, the polishing rate of copper may decrease.
- the content ratio (mass ratio) of the complex-forming agent and the alicyclic resin acid is 50: 1 to 10: 1, particularly 40: 1 to 10: 1 in that the polishing rate can be improved. preferable.
- the mechanism of the oxidizing agent plays a role of oxidizing a metal such as copper to form a metal ion or oxide. It is considered that the polishing proceeds when the copper ions generated by the reaction with the oxidizing agent and the complex forming agent form a complex.
- An oxidizing agent can be added to the polishing composition of the present invention.
- a peroxide having an oxygen-oxygen bond in which an oxygen-oxygen bond is dissociated by external energy such as heat or light to generate a radical is preferable because it exhibits a strong oxidizing power.
- peroxide-based oxidizing agents include inorganic peroxides such as hydrogen peroxide, persulfates, peroxocarbonates, peroxosulfates, peroxophosphates, benzoyl peroxide, t-butylhydro Examples thereof include organic peroxides such as peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, performic acid and peracetic acid.
- Preferred oxidizing agents are hydrogen peroxide, ammonium persulfate, or potassium persulfate.
- these oxidizing agents it is more preferable to use ammonium salts, particularly ammonium persulfate, because a high polishing rate can be obtained for the copper film.
- the preferred oxidizing agents are then hydrogen peroxide and potassium persulfate.
- the content of the oxidizing agent in the polishing composition is preferably 0.1 to 5% by mass, particularly 0.5 to 3% by mass. If it is less than 0.1% by mass, the copper polishing rate may decrease. If it exceeds 5% by mass, corrosion or dishing of the copper surface tends to occur.
- the main liquid medium in the polishing composition of the present invention is water, and preferably consists of water alone or a mixture of water and a water-soluble solvent.
- water it is preferable to use pure water which has been subjected to ion exchange and from which foreign substances have been removed.
- water-soluble solvent water-soluble alcohols, water-soluble polyols, water-soluble esters, water-soluble ethers, and the like can be used.
- the liquid medium in the polishing composition of the present invention is preferably water alone or a mixed solvent of water containing 80% by mass or more of water and a water-soluble organic solvent, and most preferably consists essentially of water.
- the proportion of the liquid medium in the polishing composition of the present invention is preferably 90% by mass or more, particularly 95% by mass or more.
- Substantially the total amount of the liquid medium is preferably composed of water.
- the water content in the polishing composition of the present invention is preferably 90% by mass or more, particularly preferably 95% by mass or more.
- the ratio of each component of the polishing composition of the present invention refers to the composition ratio when polishing is performed.
- the polishing composition is diluted prior to polishing and the diluted solution is used for polishing, the ratio of each component described above and below is a ratio in the diluted product.
- the polishing composition is usually diluted with a liquid medium (especially water), and in this case, the relative proportions of the components other than the liquid medium are usually not changed before and after the dilution.
- the polishing composition comprises an alicyclic resin acid, the content in the polishing composition is 0.1 to 1.5% by mass, the average primary particle size is 10 to 40 nm, and the average secondary particle size is Copper in the first polishing step contains colloidal silica having an average secondary particle size ⁇ content in the range of 10-40 (unit: nm ⁇ mass%) and tetramethylammonium ions in the range of 30-80 nm. It was found that the polishing rate of the barrier layer can be suppressed while improving the polishing rate of the wiring.
- the polishing rate (ratio) of the copper layer / barrier layer is preferably 150 or more.
- Tetramethylammonium ions can be obtained by adding tetramethylammonium hydroxide to the polishing composition.
- the counter ion of the tetramethylammonium ion is not particularly limited. However, since the tetramethylammonium compound itself can also function as a pH adjuster described later, it is preferable to select in consideration of the final pH. Examples of the tetramethylammonium compound generally include tetramethylammonium hydroxide (TMAH).
- the content of tetramethylammonium ions in the polishing composition is preferably 0.1 to 1.4% by mass, particularly preferably 0.2 to 1.2% by mass in terms of tetramethylammonium hydroxide. found. If it is less than 0.1% by mass, the polishing rate of the barrier layer with respect to copper increases due to an increase in the polishing rate of the barrier layer (copper polishing rate / barrier layer polishing rate). The layer is removed and the underlying insulating film layer is easily exposed. On the other hand, if it exceeds 1.4% by mass, the copper polishing rate decreases and the copper residue tends to be generated due to the occurrence of corrosion of the copper film due to the increase in pH of the polishing composition and the significant decrease in grinding power.
- the pH value of the polishing composition of the present invention is preferably 7.5 to 12, particularly 8 to 11, and more preferably 8.5 to 10.5. More preferably, it is 9-10.
- the pH value is lower than 7.5, the alicyclic resin acid contained in the polishing composition of the present invention may be separated in the polishing composition and become non-uniform.
- the pH value is preferably 8.0 or more.
- a pH value higher than 12 is not preferable because corrosion of the copper film is remarkable.
- the pH value is preferably 11 or less.
- a pH adjuster can be used.
- potassium hydroxide other potassium compounds, organic amines, or ammonia. Any of these may be used, but it is preferable to use an organic amine or ammonia that forms a complex ion with copper because a large polishing rate can be obtained with respect to the copper film.
- the pH may be adjusted to a desired pH value by adjusting the pH to the acidic side by adding nitric acid, sulfuric acid, phosphoric acid, etc. once the basic pH is set to the desired pH value.
- the order of the step of mixing the pH adjuster is not limited.
- a liquid medium is used.
- a liquid medium made basic by mixing with a pH adjuster (some or all of other components may already be contained) is prepared, dissolution and mixing of the alicyclic resin acid and the like are facilitated. It is preferable because it becomes difficult to separate.
- Potassium ions can be obtained by adding potassium hydroxide and other potassium compounds to the polishing composition.
- potassium hydroxide and other potassium compounds there is no restriction
- the potassium compounds that can be used are as described above. Needless to say, the potassium ion itself may not be attributed to the pH adjuster.
- the content of potassium ions in the polishing composition is preferably 0.6% by mass or less in terms of potassium hydroxide. When it exceeds 0.6%, the copper residue suppressing effect and the barrier film suppressing effect tend to be insufficient. In the case of 0.1% or less, the copper residue suppressing effect and the barrier suppressing effect are sufficiently obtained, but the concentration of the abrasive tends to be low. From the viewpoint of concentration of the abrasive, it is more preferably contained at 0.2% or more.
- the ratio of tetramethylammonium ion / potassium ion is preferably 0.3 or more, more preferably 3 or more, in terms of mass ratio in terms of tetramethylammonium hydroxide / potassium hydroxide. In the range of 0.3 or more, it is easy to obtain both a sufficient barrier layer polishing rate suppression effect and a sufficient copper residue elimination effect.
- the abrasive compounded in the polishing composition of the present invention is colloidal silica. Colloidal silica is more excellent than silica in terms of dispersibility, stability, polishing power and the like.
- the average primary particle diameter of colloidal silica is 10 to 40 nm, and the average secondary particle diameter is 30 to 80 nm. If the average secondary particle size exceeds 80 nm, the abrasive particle size is too large to increase the abrasive concentration, and if it is less than 30 nm, it is difficult to improve the polishing rate. Preferably, it is in the range of 30 to 70 nm.
- the specific surface area of the abrasive grains is preferably 30 to 300 m 2 / g. More preferably, it is in the range of 60 to 260 m 2 / g. When the specific surface area is less than 30 m 2 / g, the average primary particle diameter is too large, and when the specific surface area exceeds 300 m 2 / g, the primary particle diameter is too small. If the average primary particle size of the abrasive grains is not too small, a sufficient polishing rate can be obtained, and if the average primary particle size is not too large, a smooth and flat polished surface can be obtained.
- the content of the abrasive grains in the polishing composition of the present invention is such that the content in the polishing composition is 0.1 to 1 from the viewpoint that both the copper residue and the polishing rate can be achieved by the joint action with tetramethylammonium ions.
- the content of abrasive grains is more preferably 0.1 to 0.75% by mass.
- the average secondary particle size ⁇ content is more preferably in the range of 10 to 25 in particular.
- the polishing rate in contrast to copper, where the chemical action is dominant, in barrier layer polishing where the mechanical action is dominant, the polishing rate depends on the abrasive grain size, and the smaller the polishing rate, the slower the polishing rate. It seems that the speed tends to increase.
- the polishing residue of the copper layer depending on the average secondary particle size, the smaller one tends to remain, and the larger one tends to remain less likely to remain. Therefore, in order to maintain the copper layer polishing rate with no copper residue and to reduce the barrier layer polishing rate, the condition of average secondary particle size x content is necessary, probably because of the average secondary If the concentration is high even if the particle size is small, the same effect as when the average secondary particle size is larger appears.
- the concentration is low even if the average secondary particle size is large, the average secondary particle size is This is probably because the same effect as in the case of smaller size appears. Note that if the lower limit or upper limit of any of these ranges is exceeded, the polishing rate of the barrier layer will increase and the problem of copper residue may occur.
- the polishing composition preferably contains a rust inhibitor.
- the rust inhibitor is preferably an imidazole derivative, particularly in terms of preventing pits.
- the imidazole derivative specifically refers to imidazole and benzene in which 1 to 5 positions shown in the following formula may be substituted with a methyl group, and the 4 and 5 positions may be benzene which may have a substituent.
- the imidazole derivative examples include benzimidazole, imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1,2-dimethylimidazole, and the like. These may be used alone or in combination of two or more.
- the imidazole derivative is preferably contained in an amount of 0.001 to 0.5%, more preferably 0.003 to 0.3% based on the total mass of the polishing composition in terms of polishing characteristics.
- a reducing agent, a viscosity modifier, a dispersing agent, a preservative, and the like can be appropriately blended in addition to the above-described components as long as the gist of the present invention is not violated.
- these contents are generally 10% by mass or less in total, particularly 5% by mass or less, and more preferably 3% by mass or less.
- the polishing composition configured as described above can improve the polishing rate of the copper wiring in the first polishing step, can solve the problem of remaining copper, and can suppress the polishing rate of the barrier layer. Therefore, it is possible to obtain a semiconductor integrated circuit surface having an excellent flat surface state, which is extremely effective for multilayering and thinning of the semiconductor integrated circuit.
- This polishing composition is preferable in terms of low viscosity. Viscosity is a more important factor than expected in technical fields such as CMP. This is because it is generally very important to make the polishing conditions constant in order to perform stable polishing. However, when the viscosity of the polishing composition is too high, clogging may occur in the abrasive conveyance system or the abrasive may remain. Therefore, whether or not polishing can be performed under the same conditions during long-term polishing largely depends on the viscosity of the abrasive. In order to improve the viscosity, it is preferable not to contain a water-soluble polymer.
- the water-soluble polymer is a water-soluble polymer having a molecular weight of 5000 or more.
- the polishing composition according to the present invention is suitable for polishing a copper film formed on a surface having a groove for wiring as an abrasive.
- Other constituent components may be added to the polishing composition according to the present invention and used as an abrasive. More specifically, the problem of remaining copper can be solved while the copper wiring polishing rate is good, and the barrier layer polishing rate can be suppressed. Accordingly, for example, a semiconductor integrated circuit device for forming a copper wiring by a damascene method can be used. Since the progress of dishing and erosion is effectively suppressed in the manufacturing method, a semiconductor integrated circuit surface having an excellent flat surface state can be obtained.
- the polishing composition according to the present invention is a polishing method for pattern formation in which a copper layer provided on an insulating layer via a barrier layer is polished to alternately form copper embedded wiring and insulating layers.
- the second polishing step of polishing with the second polishing composition can be preferably used.
- the present polishing method that selectively uses these two types of polishing compositions can realize an excellent flat surface with little dishing and erosion with good in-plane uniformity when copper is used as a wiring metal. For this reason, it is extremely effective for multilayering and thinning of semiconductor integrated circuits.
- first polishing step and the second polishing step it is generally preferable to perform the second polishing step immediately after the first polishing step to complete the polishing, but the first polishing step and the second polishing step are performed as necessary.
- other steps may be included before the first polishing step or after the second polishing step.
- end time of the first polishing step and the start time and end time of the second polishing step which can be appropriately determined according to the actual situation of polishing, but usually, a barrier layer is interposed on the insulating layer.
- the first polishing process is stopped and the process proceeds to the second polishing process, and when the predetermined surface flatness is obtained, the second polishing process is stopped. That is, the copper portion other than the copper wiring is removed in the first polishing step, the barrier layer is removed in the second polishing step, and in most cases, the insulating layer and, if necessary, a part of the copper are extremely used. By polishing slightly, a flat surface composed of an insulating layer and a copper layer is formed.
- Examples 6 to 11, 13 to 15, 17 to 20, 26 to 29, 31 to 34 and 39 to 42 are examples, and examples 1 to 5, 12, 16, 21 to 25, 30 and 35 to 38 are comparative examples. is there.
- compositions of the polishing compositions in Examples 1 to 42 are summarized in Tables 1 to 4, respectively. Content of each component was described by the mass% with respect to the whole polishing composition mixed. The pH value was measured with a pH meter, pH 81-11, manufactured by Yokogawa Electric Corporation.
- the average primary particle size of the colloidal silica was determined by conversion from the specific surface area obtained by the BET method.
- the average secondary particle size of colloidal silica was measured by a dynamic light scattering method using a Microtrac UPA-ST150 particle size analyzer manufactured by NIKKISO.
- the measurement sample was measured by diluting with pure water in an appropriate concentration range determined by the apparatus, which can obtain appropriate scattering and reflected light intensity for measurement.
- the polishing composition is prepared by adding a predetermined amount of 2-pyridinecarboxylic acid, which is a complex forming agent, to ion-exchanged water, and then adjusting the pH as described in Tables 1 to 4 as necessary. Potassium hydroxide and tetramethylammonium hydroxide as pH adjusters were added and stirred sufficiently. While further stirring, the product name KR614 (rosin containing about 80% dehydroabietic acid), a flatness improver oleic acid, and an oxidizing agent APS (ammonium persulfate) were added with stirring. It was prepared by adding colloidal silica as abrasive grains. In addition, there was no supply source of potassium ions other than potassium hydroxide, and there was no supply source of tetramethylammonium ions other than tetramethylammonium hydroxide.
- polishing characteristics of the polishing composition were evaluated by the following methods.
- a blanket wafer and a patterned wafer were used as the objects to be polished.
- an 8-inch wafer (000CUR015 manufactured by Sematech Co., Ltd.) in which a copper film having a thickness of 1500 nm is formed on the Si substrate by wet plating is used. did.
- an 8-inch wafer manufactured by Yamaichi Co., Ltd. in which a tantalum film having a thickness of 300 nm was formed on a Si substrate by sputtering was used.
- An 8-inch wafer (trade name: 854CMP225) manufactured by Sematech was used as the wafer with a pattern.
- a schematic cross section of the patterned wafer before polishing is shown in FIG.
- This patterned wafer is a 25-nm-thick tantalum film formed by sputtering on an insulating layer 2 made of SiO 2 in which concave and convex portions in which embedded wirings formed on the Si substrate 1 are embedded are formed.
- Various width wiring patterns with a width of 100 ⁇ m to 180 nm are formed.
- polishing machine a fully automatic CMP apparatus MIRRA manufactured by APPLIED MATERIALS was used.
- a polishing pad XYK-groove (manufactured by Nitta Haas) having a two-layer pad IC1400 was used, and conditioning was performed using MEC100-PH3.5L (manufactured by Mitsubishi Materials Corporation).
- Polishing was performed at a supply rate of the polishing composition of 200 ml / min, a rotation speed of the polishing head (Head) and polishing platen (Platen) of 123 rpm and 117 rpm, respectively, and a polishing pressure of 1.5 psi, that is, 10.4 kPa. .
- polishing speed of solid film flat film not patterned
- the copper polishing speed and tantalum polishing speed using a blanket wafer were measured using a film thickness meter RS-75 (manufactured by KLA-Tencor). I did it. That is, for the copper blanket wafer and the tantalum blanket wafer, the film thickness before polishing and the film thickness after polishing for 1 minute were measured, and the copper polishing rate (nm / min) and the tantalum polishing rate (nm, respectively) / Min).
- the copper polishing rate is preferably 400 nm / min or more, and the tantalum polishing rate is preferably 5 nm / min or less.
- the acceleration voltage was set to 2 KV, and the entire surface was inspected at a magnification of 2000 times to determine whether copper remained in the portion between the copper lines having a line width of 0.18 ⁇ m.
- the case where no copper residue was observed was evaluated as “none”, and the case where any copper residue was observed was evaluated as “present”.
- the polishing rate of the barrier layer was all good at 5 nm / min or less. Further, the ratio of the polishing rate of the copper wiring / the polishing rate of the barrier layer was also good at 180 to 674.
- the ratio of speed / barrier layer polishing speed was 179 or less.
- Example 12 in which the amount of colloidal silica and the average secondary particle diameter ⁇ content deviate from the lower limit, the ratio of the polishing rate of the copper wiring / polishing rate of the barrier layer was increased, but a copper residue was generated.
- Example 30 where the average secondary particle diameter x content of colloidal silica deviates from the lower limit without adding potassium hydroxide, the ratio of the polishing rate of the copper wiring / the polishing rate of the barrier layer was increased, but the copper remaining Produced.
- the dicing was 55 nm or less in all of the examples and the comparative examples.
- the colloidal silica has a content in the polishing composition of 0.1 to 1.5% by mass, an average primary particle size of 10 to 40 nm, an average secondary particle size of 30 to 80, and an average of 2
- the secondary particle size ⁇ content was in the range of 10 to 40, the polishing rate of the barrier layer was suppressed while the polishing rate of the copper wiring in the first polishing step was good.
- a novel polishing composition for the first polishing step that can solve the problem of remaining copper and suppress the polishing rate of the barrier layer while improving the polishing rate of the copper wiring in the first polishing step. Things are obtained.
Abstract
Description
脂環族樹脂酸と、
研磨用組成物中における含有量が0.1~1.5質量%で、かつ平均一次粒子径が10~40nmで、平均二次粒子径が30~80nmであり、かつ平均二次粒子径×含有量が10~40の範囲にあるコロイダルシリカと、
テトラメチルアンモニウムイオンと
を含む、研磨用組成物が提供される。
当該半導体集積回路装置が、溝を有する絶縁層と、当該溝に形成された銅埋め込み配線とを備えており、
当該絶縁層上にバリア層と銅層とがこの順に形成された当該半導体集積回路装置用の多層構造体を上記態様1~8のいずれかに記載の研磨用組成物を用いて、前記銅層に隣接した前記バリア層が露出するまで研磨することを含む半導体集積回路装置の製造方法が提供される。
以下において、本発明において使用される材料について説明する。研磨前のパターン付きウェハの概略断面を図4(a)に示す。図4(a)においてSi基板1上に、絶縁層2、バリア層3および配線金属層(銅層)4が形成されている。
絶縁層としては、以下記載の、テトラエトキシシラン、シラン等を用いたプラズマCVDによるSiO2膜、低誘電率材料膜(SiOF膜、有機SOG膜等)、さらにこれらとキャップ層と組み合わせた構成、の全てがあり得る。
本発明に係る研磨用組成物は、図4には図示されていないが、絶縁層上にキャップ層が形成された場合についても好適に使用できる。たとえば、低誘電率絶縁層上にキャップ層、バリア層および金属配線層を順次積層してなる多層構造において、キャップ層を完全に除去した後、絶縁層を削り込んで平坦化する場合にも適用できる。
バリア層とは、絶縁層上に、たとえばスパッタ法により製膜されたTa、TaN、Ti、TiN、Ru等からなる群から選ばれる少なくとも1種を含む層で、銅層から絶縁層への銅の拡散を妨げる目的で配置されるが、本発明においては銅層の研磨において、その配線部が現れる時点を見出すためのストッパーとしての役目も果たしている。
銅層は絶縁層上にバリア層を介して製膜される。その製膜方法としては、バリア層製膜後にスパッタ法によりCuシード層を100nm厚程製膜し、更にそのCuシード層上に電解メッキ法によりCu層を形成する方法を例示できる。
以下、本発明に係る研磨用組成物に使用し得る各種材料について述べる。
本研磨用組成物は、錯体形成剤を含んでいてもよい。錯体形成剤とは、銅と錯体を形成する物質を意味する。錯体形成剤を含有させることにより、その機構は明らかでないが銅の研磨速度が増大する。具体的には、以下のとおりである。
本研磨用組成物は、脂環族樹脂酸を含む。樹脂酸とは天然樹脂中に遊離またはエステルとして存在する有機酸(カルボン酸)であり、脂環族樹脂酸とはその樹脂酸のうち脂環構造を有する化合物をいう(共立出版(株)発行「化学大辞典4」の「樹脂酸」の項参照)。本発明における脂環族樹脂酸としては、脂環族樹脂酸を含有する天然樹脂、天然樹脂から精製(同時に異性化等が起こることもある)された脂環族樹脂酸を主成分とする精製樹脂酸、天然樹脂から抽出された単一化合物である脂環族樹脂酸やその2種以上の混合物、などがある。
酸化剤は、その機構は定かではないが、銅などの金属を酸化し金属イオン又は酸化物を生成する役割を演じる。酸化剤による反応で生成した銅イオンと錯体形成剤とが錯体を形成することで、研磨が進行すると考えられる。
本発明の研磨用組成物における主たる液状媒体は水であり、水のみまたは水と水溶性溶媒との混合物からなることが好ましい。水としては、イオン交換し、異物が除去された純水を用いることが好ましい。水溶性溶媒としては、水溶性アルコール、水溶性ポリオール、水溶性エステル、水溶性エーテルなどを使用できる。本発明の研磨用組成物における液状媒体は水のみまたは水を80質量%以上含む水と水溶性有機溶媒との混合溶媒が好ましく、実質的に水のみからなることが最も好ましい。また、本発明の研磨用組成物における液状媒体の割合は90質量%以上、特に95質量%以上からなることが好ましい。この液状媒体の実質的全量は水からなることが好ましく、その場合本発明の研磨用組成物における水の含有量は、90質量%以上、特に95質量%以上であることが好ましい。
研磨に先立ち研磨用濃縮組成物を希釈し、その希釈物を研磨に使用する場合、上記および後述の各成分の割合はこの希釈物における割合である。研磨用濃縮組成物は通常液状媒体(特に水)で希釈され、したがって、その場合液状媒体を除く各成分の相対的割合は希釈の前後で通常は変化しない。
本研磨組成物が、脂環族樹脂酸と、研磨用組成物中における含有量が0.1~1.5質量%で、かつ平均一次粒子径が10~40nmで、平均二次粒子径が30~80nmであり、かつ平均二次粒子径×含有量が10~40(単位:nm×質量%)の範囲にあるコロイダルシリカと、テトラメチルアンモニウムイオンとを含むと、第1研磨工程における銅配線の研磨速度を良好としつつバリア層の研磨速度を抑えられることが判明した。これは恐らく、テトラメチルアンモニウムイオンが嵩高の立体構造を有しているため、陽イオン性のテトラメチルアンモニウムイオンがアルカリ性下でマイナスに帯電しているコロイダルシリカ表面に電荷的に吸着することで、銅研磨に必要最低限な研削力は維持しつつも、バリア層に対しては、十分な研削力の低減をしていると考えられる。なお、銅層の研磨速度/バリア層の研磨速度(比)は150以上が好ましい。
また、1.4質量%超であると研磨組成物のpH上昇による銅膜の腐食の発生や研削力の大幅な低下により銅研磨速度の低下や銅残りが発生し易くなる。
本発明の研磨用組成物のpH値は、7.5~12、特に8~11、さらには8.5~10.5であることが好ましい。より好ましくは9~10である。pH値が7.5より低いと、本発明の研磨用組成物中に含有させた脂環族樹脂酸が、研磨用組成物中で分離して不均一になるおそれがある。銅を高速に研磨するためには、pH値を8.0以上とすることが好ましい。pH値が12より高いと銅膜の腐蝕が顕著なため好ましくない。銅膜の研磨残りや腐蝕を充分に抑制するためには、pH値を11以下とすることが好ましい。
本研磨組成物においては、上記テトラメチルアンモニウムイオンに加えて、カリウムイオンが共存すると研磨剤の濃縮度を上げるのに有効である。この研磨剤組成物の分野においては、研磨剤を濃縮して使用するというニーズが非常に高いため、この効果は大である。
本発明の研磨用組成物に配合される砥粒はコロイダルシリカである。コロイダルシリカは、シリカの中でも分散性、安定性、研磨力などの点からより優れている。
砥粒の含有量は、0.1~0.75質量%であることがより好ましい。平均二次粒子径×含有量は、特に10~25の範囲にあることがより好ましい。
本研磨用組成物は、防錆剤を含むことが好ましい。防錆剤としては、具体的には、イミダゾール誘導体であることが、特にピットを防止できる点で好ましい。イミダゾール誘導体とは、具体的には、イミダゾールおよび、イミダゾールについて、下式に示す1~5位がメチル基で置換されていてもよく、4,5位は、置換基が付いていてもよいベンゼン環の一部となっていてもよい、誘導体である。
本発明の研磨方法に用いられる研磨用組成物には、本発明の趣旨に反しない限り、上記の成分の他に還元剤、粘度調整剤、分散剤、防腐剤等を適宜配合することもできる。ただし、これらの含有量は、通常合計で10質量%以下、特に5質量%以下、さらには3質量%以下であることが好ましい。
本発明に係る研磨用組成物は、絶縁層上にバリア層を介して設けられた銅層を研磨して、銅埋込み配線と絶縁層とを交互に形成するパターン形成のための研磨方法であって、上記の研磨用組成物である第1の研磨用組成物で研磨する第1研磨工程と、その後、絶縁層上にバリア層を介して設けられた銅層を研磨して、銅埋込み配線と絶縁層とを交互に形成するパターン形成において、第2の研磨用組成物で研磨する第2研磨工程と、を備えた研磨方法に好ましく使用することができる。
被研磨物として、ブランケットウエハとパターン付きウェハとを使用した。
このパターン付きウェハは、Si基板1上に形成された埋め込み配線が埋め込まれる凹部と凸部とが形成されたSiO2よりなる絶縁層2上に、スパッタリングにより成膜された厚さ25nmのタンタル膜からなるバリア層3と、さらにその上に、スパッタリング法により製膜された銅シード層100nmと湿式メッキで成膜された所定の膜厚の銅膜からなる配線金属層4とが積層され、配線幅が100μmから180nmの様々な幅の配線パターンが形成されている。
研磨機としては、APPLIED MATERIALS社製全自動CMP装置 MIRRAを使用した。研磨パッドとしては、2層パッドIC1400のXYK-groove(ニッタハース社製)を使用し、MEC100-PH3.5L(三菱マテリアル社製)を用いてコンディショニングをおこなった。
ブランケットウエハを用いた銅研磨速度およびタンタル研磨速度の測定は、膜厚計RS-75(KLA-Tencor社製)を使用しておこなった。すなわち、銅のブランケットウエハおよびタンタルのブランケットウエハについて、研磨前の膜厚と1分間研磨した後の膜厚とを測定し、その差からそれぞれ銅研磨速度(nm/分)およびタンタル研磨速度(nm/分)を求めた。
パターン付きウェハの研磨は、光学式研磨終点検出法により研磨終点をモニターしながらおこなった。すなわち、研磨の進行に伴ってタンタルからなるバリア層が露出し始めて生じる反射率の低下がほぼ止まって一定となる研磨終点から、更に研磨終点時間の20%に相当するOver研磨を行った。
本出願は、2008年11月10日出願の日本特許出願2008-287404および2009年4月21日出願の日本特許出願2009-102942に基づくものであり、その内容はここに参照として取り込まれる。
2 絶縁層
3 バリア層
4 配線金属層
6 銅埋込み配線
7 ディッシング量
8 銅膜の初期膜厚
9 銅膜の初期段差
17 ディッシング部分
18 エロージョン部分
19 最大段差
20 Global部
21 銅残り
22 銅残りのない部分
23 配線密度の高い箇所
Claims (12)
- 絶縁層上にバリア層を介して設けられた銅層を研磨して、銅埋め込み配線と絶縁層とを交互に形成するパターン形成において、前記銅層に隣接した前記バリア層が露出するまで研磨する工程に用いられる研磨用組成物であって、
脂環族樹脂酸と、
研磨用組成物中における含有量が0.1~1.5質量%で、かつ平均一次粒子径が10~40nmで、平均二次粒子径が30~80nmであり、かつ平均二次粒子径×含有量が10~40の範囲にあるコロイダルシリカと、
テトラメチルアンモニウムイオンと
を含む、研磨用組成物。 - さらにカリウムイオンを含む、請求項1に記載の研磨用組成物。
- テトラメチルアンモニウムイオンの研磨用組成物中における含有量が、水酸化テトラメチルアンモニウム換算で0.1~1.4質量%である請求項1または2に記載の研磨用組成物。
- カリウムイオンの研磨用組成物中における含有量が水酸化カリウム換算で0.6質量%以下である請求項2又は3に記載の研磨用組成物。
- テトラメチルアンモニウムイオン/カリウムイオンの比が、水酸化テトラメチルアンモニウム/水酸化カリウム換算の質量比で0.3以上である請求項2~4のいずれかに記載の研磨用組成物。
- 前記脂環族樹脂酸がロジンである、請求項1~5のいずれかに記載の研磨用組成物。
- 更に酸化剤を含む、請求項1~6のいずれかに記載の研磨用組成物。
- 更に錯体形成剤を含む、請求項1~7のいずれかに記載の研磨用組成物。
- 半導体集積回路装置の製造方法であって、
当該半導体集積回路装置が、溝を有する絶縁層と、当該溝に形成された銅埋め込み配線とを備えており、
当該絶縁層上にバリア層と銅層とがこの順に形成された当該半導体集積回路装置用の多層構造体を、請求項1~8のいずれかに記載の研磨用組成物を用いて、前記銅層に隣接した前記バリア層が露出するまで研磨することを含む半導体集積回路装置の製造方法。 - 前記バリア層が、Ta、TaN、Ti、TiNおよびRuからなる群から選ばれる少なくとも1種を含む、請求項9に記載の半導体集積回路装置の製造方法。
- 前記多層構造体が、前記絶縁層と前記バリア層との間にキャップ層を備えている、請求項9または10に記載の半導体集積回路装置の製造方法。
- 前記溝を有する絶縁層が二酸化ケイ素膜又は3以下の比誘電率を有する、請求項9~11のいずれかに記載の半導体集積回路装置の製造方法。
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US8304346B2 (en) | 2012-11-06 |
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US20110212621A1 (en) | 2011-09-01 |
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