TW201237954A - Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method - Google Patents

Abstract

An aqueous dispersion for chemical mechanical polishing relating to the present invention is characterized in comprising: (A) abrasive grains; (B) a polyvalent carboxylic acid compound in which the total fat chain length present between carboxyl groups is 9 carbons or greater; and (C) an anionic surfactant.

Description

201237954 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a chemical mechanical honing water dispersion and a chemical mechanical honing method. [Prior Art] In recent years, with the increase in the semiconductor device or the multilayer wiring, the wiring formed in the semiconductor device has progressed to be fine. Along with this, a method of flattening the wiring layer by chemical mechanical honing (hereinafter also referred to as "CMP") is used. For example, Japanese Patent Publication No. 2002-518845 proposes to deposit a conductor metal such as aluminum, copper or tungsten on a fine groove or hole provided in an insulating film such as ruthenium oxide provided on a semiconductor substrate by sputtering or plating. The damascene process of removing the remaining laminated metal film by CMP, leaving only the metal of the fine trench or the hole portion. When manufacturing a semiconductor device by a damascene process, it is necessary to perform the steps of removing the wiring material on the general barrier metal film by CMP (the first honing step), and then removing the barrier metal film by CMP and further optionally A step of planarizing the wiring material and the interlayer insulating film (second honing step). The aforementioned first honing step requires selective honing of the wiring material at a high speed. However, at the end of the first honing step (at the time when the other material film such as the barrier metal film is exposed), it is difficult to simultaneously suppress the corrosion or dent of the wiring while maintaining the high honing speed for the wiring material. For this technical issue, various reviews have been made based on the composition of the chemical mechanical honing water dispersion 201237954. For example, International Publication No. 2008/01 3226 proposes a technique for using an additive for suppressing corrosion of wiring metals in a chemical mechanical honing water-based dispersion, and the proposal in Japanese Laid-Open Patent Publication No. 2006-2292-15 is used. A technique for suppressing the recessed long-chain dicarboxylic acid of the wiring material. [Disclosure of the Invention] However, even with such techniques, it is difficult to suppress the corrosion of the wiring metal in the fine wiring and at the same time achieve a high honing speed and a reduction in the dent of the wiring material. In particular, in the contact portion between the wiring material and the barrier metal film, since the different kinds of metals having different standard electrode potentials are in contact with each other to form a battery between the metals, there is a case where the standard electrode potential causes the base metal to corrode (dissolve). This corrosion is called galvanic corrosion, and as the wiring is miniaturized, the contact area between the wiring material and the barrier metal film is increased, which is a very large problem. Therefore, in order to solve the above problems, the present invention provides a chemical mechanical honing water dispersion which can suppress the corrosion of the fine wiring metal and simultaneously achieve high-speed honing of the wiring material and reduce the depression of the honed surface. Body. [Means for Solving the Problems] The present invention has been made in order to solve one of the above problems, and can be realized by the following aspects or application examples.

-6-S 201237954 [Application Example 1] The chemical mechanical honing aqueous dispersion of the present invention is characterized by containing (A) honing particles, and (B) the total length of the aliphatic chain existing between the carboxyl groups is carbon a polyvalent carboxylic acid compound of 9 or more and (C) an anionic surfactant. [Application Example 2] The chemical mechanical honing aqueous dispersion according to Application Example 1, wherein the component (B) is a compound represented by the following formula (1), HOOC-CCR^^n-COOH (1) (In the above formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group, and η represents an integer of 9 or more). [Application Example 3] The chemical mechanical honing aqueous dispersion according to Application Example 1 or Application Example 2, wherein the aforementioned (Β) component is dodecanedioic acid or tridecanedioic acid. . [Application Example 4] The chemical mechanical honing water-based dispersion according to any one of Application Examples 1 to 3, wherein the content of the aforementioned (Β) component is 〇 relative to the total mass of the chemical mechanical honing water-based dispersion. 〇1% by mass or more and 〇·5% by mass to 201237954. [Application Example 5] The chemical mechanical honing water-based dispersion according to any one of Application Examples 1 to 4, wherein the component (C) is an alkylbenzenesulfonic acid, an alkenyl succinic acid, or the like Select at least one of them. [Application Example 6] The chemical mechanical honing aqueous dispersion according to any one of Application Examples 1 to 5, wherein the content of the component (C) is 0.005 by mass based on the total mass of the chemical mechanical honing aqueous dispersion. % or more and 0.2% by mass or less. [Application Example 7] The chemical mechanical honing water dispersion according to any one of Application Examples 1 to 6, which further contains (D) an amino acid. [Application Example 8] The chemical mechanical honing aqueous dispersion according to any one of Application Examples 1 to 7 has a pH of 8 or more and 1 Torr or less. [Application Example 9] As in Application Examples 1 to 8 The chemical mechanical honing aqueous dispersion of any of the examples further contains (E) an organic acid having a nitrogen-containing hetero ring.

-8 - S 201237954 [Application Example 10] The chemical mechanical honing water according to any one of Application Examples 1 to 9 is a dispersion which further contains (F) an oxidizing agent. [Application Example 1] The aqueous dispersion for chemical mechanical honing according to any one of Application Examples 1 to 10, further comprising (G) a water-soluble polymer. [Application Example 12] The chemical mechanical honing method according to the present invention is characterized in that it includes a barrier metal film formed to cover the bottom surface to the side surface of the concave portion, and an insulating film having a concave portion formed thereon The barrier metal film is embedded in the substrate of the metal film made of copper or a copper alloy in the concave portion, and the chemical mechanical honing water-based dispersion according to any one of Application Examples 1 to 1 is used. The step of planarizing the metal film. [Effect of the Invention] According to the chemical mechanical honing water-based dispersion of the present invention, it is possible to achieve high honing speed of the wiring material and reduce the depression in the honed surface while suppressing corrosion of the wiring material in the fine wiring. Good chemical mechanical honing. And 'the chemical mechanical honing method according to the present invention can suppress the occurrence of corrosion and reduce the depression while honing the wiring material -9-201237954 at a high honing speed by using the aforementioned chemical mechanical honing water-based dispersion. And get a good honing surface. [Embodiment] Hereinafter, preferred embodiments of the present invention will be described in detail. 1. Chemical mechanical honing water-based dispersion A chemical mechanical honing aqueous dispersion according to an embodiment of the present invention, characterized in that it contains (A) honing particles and (B) a total of fat chain lengths existing between carboxyl groups. It is a polycarboxylic acid compound having a carbon number of 9 or more and (C) an anionic surfactant. Hereinafter, each component constituting the chemical mechanical honing water-based dispersion of the present embodiment will be described in detail. 1·1· (A) Honing granules The chemical mechanical honing water-based dispersion of the present embodiment contains (A) 磨 abrasive grains (hereinafter simply referred to as "(A) component"). The component (A) is not particularly limited as long as it has a function of mechanically honing a wiring material such as aluminum, copper or tungsten, and examples thereof include cerium oxide particles, cerium oxide particles, alumina particles, and chromium oxide. Particles, titanium oxide particles, and the like. The (A) honing particles are preferably cerium oxide particles. These (A) honing particles may be used singly or in combination of two or more. The cerium oxide particles are exemplified by (a) a fumed cerium dioxide synthesized by a smoking method in which a ruthenium chloride or the like is reacted with oxygen and hydrogen in the gas phase.

-10- S 201237954 Separation of cerium oxide synthesized by lyophilization of a metal alkoxide by hydrolysis and condensation. (C) Colloidal cerium oxide synthesized by an inorganic colloid method or the like which purifies impurities by purification. Among these, from the viewpoint of stability at pH 8 to 11 and excellent compatibility with an anionic surfactant, it is more preferable that (b) is synthesized by hydrolysis and condensation of a metal alkoxide. Colloidal cerium oxide synthesized by gel method and (c) colloidal cerium oxide synthesized by an inorganic colloid method or the like which purifies impurities. (A) The shape of the honing particles is preferably spherical. Among them, the "spherical shape" includes a slightly spherical shape without an acute angle portion, and is not necessarily a close to a true ball, and may be an elliptical ball. By using the spherical (A) honing particles, occurrence of honing defects such as scratches in the honed surface can be suppressed. The average particle diameter of the (A) honing particles is preferably from 1 Torr to 3 Å, more preferably from 10 to 200 nm', more preferably from 15 to 100 nm. In the case of having an average particle diameter in the above range, it is possible to provide a chemical mechanical honing aqueous dispersion which is excellent in stability and which has sufficient honing speed for the wiring material and which is less likely to cause sedimentation and separation of the abrasive grains. Further, (A) the average particle diameter of the honing particles was obtained by observing each particle by a transmission electron microscope, and calculating from the cumulative particle diameter and the number. (A) The content of the honing granules is preferably 〇·〇1% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less, based on the total mass of the chemical mechanical honing water-based dispersion. It is good for 〇. 〇 5 mass% or more and 1 mass% or less. (A) When the content of the honing particles is within the above range, it can be a chemical mechanical honing water-based dispersion which has sufficient honing speed for the wiring material and which is less likely to cause sedimentation/separation of the honing particles and is excellent in stability. . -11 - 201237954 1.2 (B) A polycarboxylic acid compound having a total of aliphatic chain lengths between carboxyl groups and having a carbon number of 9 or more. The chemical mechanical honing water-based dispersion of the present embodiment contains (B) a carboxyl group. The total length of the aliphatic chain is a polycarboxylic acid compound having a carbon number of 9 or more (hereinafter also referred to as "(B) component"). The component (B) is not particularly limited as long as it is a polyvalent carboxylic acid having a carbon number of 9 or more in total, and is, for example, a compound HOOC-(CR' represented by the following formula (1). R2) „-COOH (1) (In the above formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group, and η represents an integer of 9 or more.) Specific examples of the (Β) component are listed as straight. Chain or branched undecanedioic acid, linear or branched dodecanedioic acid, linear or branched tridecanedioic acid, linear or branched tetradecanedioic acid , linear or branched pentadecanedioic acid, linear or branched hexadecanedioic acid, linear or branched heptadecanedioic acid, linear or branched octadecane a diacid, a linear or branched hexadecandioic acid, a linear or branched eicosane diacid, etc. The compound which can be used as the (Β) component is not particularly specific as long as it is a dicarboxylic acid as described above. The restriction is that if the carbon number of the aliphatic chain length between the carboxyl groups is 9 or more, the tricarboxylic acid or the tetracarboxylic acid compound may be used, and the middle or the end of the aliphatic chain may have An aromatic ring. Furthermore, in the aliphatic chain length is present between the carboxyl

The total of -12-S 201237954 may be appropriately determined by considering the solubility of the component (B) in water. For example, when the component (B) is a carboxylic acid, the total length of the aliphatic chain between the carboxyl groups is preferably 18 or less', more preferably 丨4 or less. In the chemical mechanical honing water-based dispersion of the present embodiment, by containing the component (B), it is possible to effectively suppress corrosion of the wiring material in the fine wiring and to reduce the depression in the honed surface to achieve good chemical mechanical honing. . Among the above-exemplified components (B), from the viewpoint of improving the honing speed of the wiring metal, it is preferably dodecanedioic acid. These components (B) may be used alone or in combination of two or more. The effect of the component (B) is presumed as follows. In general, oxalic acid (ethane diacid), malonic acid (propane diacid), tartaric acid (2,3-dihydroxybutanedioic acid), malic acid (2-hydroxybutanedioic acid), glutaric acid (pentyl) a compound having two or more carboxyl groups, such as alkanoic acid), citric acid (2-hydroxypropane-1,2,3-tricarboxylic acid), maleic acid (cis-butenedioic acid), etc., can form a countermetal Ion coordination and stability of five to seven members of the ring. According to this, metal ions can be easily sequestered. Therefore, it is considered that these compounds exhibit a function of promoting honing by forming a metal complex film by being adsorbed on the surface of the wiring material. For example, as shown in the following formula (2), oxalic acid is a structure which is easy to sequester a metal because its two carboxyl groups and metal ions form a stable five-membered ring chelate compound. 【化1】

-13- 201237954 On the other hand, it is considered that the (B) component has a long interval between the two carboxyl groups, so it is difficult to form a five- to seven-membered ring chelate compound with metal ions, and it is difficult to promote chelation by metal. Dissolved. That is, the effect of the component (B) cannot be explained by the same mechanism of action of the additive such as oxalic acid to form a five- to seven-membered cyclic chelate. The mechanism by which the component (B) is effective for the wiring metal is considered to be derived from a portion having a hydrophobic long-chain hydrocarbon. For example, since oxalic acid is composed only of a hydrophilic carboxyl group, the hydrophilicity of the complex film formed on the surface of the wiring metal is also high, and it is considered that the wiring metal is easily dissolved. On the other hand, since the component (B) such as dodecanedioic acid has a hydrophobic portion formed of ten carbon chains, the hydrophobicity of the complex film is also high, and it is difficult to dissolve the wiring metal. Effectively suppress depression or corrosion. The content of the component (B) is preferably 0.01% by mass or more and 0.5% by mass or less, more preferably 0.05% by mass or more and 0.3% by mass or less based on the total mass of the chemical mechanical honing water-based dispersion. When the content of the component (B) is within the above range, a sufficient honing speed for the wiring material can be obtained, and corrosion of the wiring material in the fine wiring can be effectively suppressed, and the depression in the honed surface can be reduced to achieve a good chemical mechanical operation. Honing. (C) Anionic surfactant The chemical mechanical honing aqueous dispersion of the present embodiment contains (C) an anionic surfactant (hereinafter also referred to simply as "(C) component"). (C) The ingredients are listed, for example, as a fatty acid salt, an alkyl sulfate, an alkyl ether -14-

S 201237954 Sulfate salt, alkyl ester carboxylate, α-sulfofatty acid ester salt, alkyl polyoxyalkylene sulfate, alkyl phosphate, monoalkyl phosphate salt, alkyl naphthalene sulfonate And α-olefin sulfonate, alkanesulfonate, alkylbenzenesulfonic acid and salts thereof, alkenyl succinic acid and salts thereof, polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, betaines-based compounds and the like. These (C) components may be used alone or in combination of two or more. As for the component (C), it is easy to adsorb to the surface of the wiring material, and it is preferable to have an anionic surfactant having a structure represented by the following general formula (3) in terms of reducing the effect of depression or corrosion. . [Chemical 2]

In the above formula (3), R3 and R4 each independently represent a hydrogen atom, a metal atom, or a substituted or unsubstituted alkyl group. When R3 and R4 are an alkyl group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms is preferred. Further, when R3 and R4 are a metal atom, it is preferably an alkali metal, more preferably sodium or potassium. R5 represents a substituted or unsubstituted alkenyl group or a sulfonic acid group (-SOsX) wherein R5 is an alkenyl group, preferably a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms. When R5 is a sulfonic acid group (-S〇3X), X is a hydrogen ion, an ammonium ion or a metal ion. When X is a metal ion, X is preferably a sodium ion or a potassium ion. The specific trade name of the compound represented by the above formula (3) is exemplified by the trade name "Newcol 291-M" having a sulfonic acid group (-S03Na) in R5 (Can be -15-201237954 from Japan Emulsifier Co., Ltd. ), the trade name "Newcol 292..PG" (available from Japan Emulsifier Co., Ltd.), the trade name "PELEX ΤΑ j (available from Kao Co., Ltd.), and the product name "LATEMULASK" (Can be purchased from Kao Co., Ltd.) and so on. Further, the alkylbenzenesulfonate is exemplified by, for example, mercaptobenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, and the like. Sodium salt, potassium salt, ammonium salt. Among these, the dodecylbenzenesulfonate is preferred because it is adsorbed on the surface of the wiring material, thereby reducing the effect of depression or corrosion. By combining the above (Β) component and the component (C), it is possible to achieve high corrosion resistance and high flatness which are unpredictable when used alone. The reason for this is considered to be a mechanism for protecting the wiring metal by both the dissolution suppressing effect of the wiring metal by the complex film formed of the (Β) component and the interfacial activity of the (C) component on the wiring metal surface. And the implementer. As described above, the component (C) is preferably at least one selected from the group consisting of an alkylbenzenesulfonate and an alkenyl succinate, but it is apparent from the inventors of the present invention that ammonium dodecylbenzenesulfonate is used in combination. With di-potassium alkenyl succinate, it is most effective in reducing the occurrence of dents or corrosion. The content of the component (C) is preferably 0.005% by mass or more and 0.2% by mass or less based on the total mass of the chemical mechanical honing water-based dispersion, and more preferably 0.01% by mass or more and 0.1% by mass or less. When the content of the component (C) is within the above range, a sufficient honing speed for the wiring material can be obtained, and corrosion of the wiring material in the fine wiring can be effectively suppressed, and the depression in the honed surface can be reduced, and good can be achieved. Chemical mechanical honing. -16-

S 201237954 Further, the ratio (MB/MC) of the content (Mb) of the component (B) to the content (Me) of the component (C) is preferably 〇·1 or more and 15 or less, more preferably 0.5 or more. 14 or less. When the ratio of the MB/MC is within the above range, the balance between the content of the component (B) and the component (C) is good, so that sufficient honing speed for the wiring material can be obtained, and corrosion of the wiring material in the fine wiring can be effectively suppressed. It is easier to achieve good chemical mechanical honing by reducing the depression in the honed surface. 1.4. (D) Amino acid The chemical mechanical honing water-based dispersion of the present embodiment may optionally contain (D) an amino acid (hereinafter also referred to simply as "(D) component"). (D) The amino acid easily forms a coordinate bond with a metal ion (especially a copper ion) and has a high chelate-coordinating ability on the surface of the wiring material. According to this, on the one hand, it is adsorbed on the surface of the wiring material and suppresses surface roughness and maintains high flatness, and on the other hand, the honing speed can be promoted by improving the affinity with metal ions. Further, since the (D) amino acid can be easily coordinated to the metal ions dissolved in the chemical mechanical honing water-based dispersion by the honing of the wiring material, the precipitation of the metal can be prevented. As a result, the honing defect such as scratches can be reduced. The (D) amino acid is exemplified by glycine, alanine, phenylalanine, arginine, histidine, leucine, isoleucine, lysine, cysteine, methionine. , valine, serine, threonine, valine, tyrosine, glutamic acid, aspartic acid, glycine glycine, tryptophan and the like. Among these, glycine acid is preferred from the viewpoint of promoting the honing speed of the wiring material. These (D) amino acids may be used singly or in combination of two or more kinds -17 to 201237954. The content of the component (D) is preferably 0.1% by mass or more and 2.0% by mass or less, more preferably 0.3% by mass or more and 1.8% by mass or less based on the total mass of the chemical mechanical honing aqueous dispersion. When the content of the component (D) is in the above range, chemical mechanical polishing can be performed on the honing speed of the wiring material. (E) Organic acid having a nitrogen-containing heterocyclic ring. The chemical mechanical honing water-based dispersion of the present embodiment can be visualized. It is necessary to add (E) an organic acid having a nitrogen-containing hetero ring (hereinafter also referred to simply as "(E) component)". The component (E) protects the surface of the surface to be honed by forming a water-insoluble complex with the metal constituting the wiring material, thereby reducing the depression of the surface to be honed. The nitrogen-containing heterocyclic ring contained in the component (E) is a heterocyclic ring such as a pyrrole structure, an imidazole structure or a triazole structure, and a heterocyclic ring such as a pyridine structure, a pyrimidine structure, a pyrazine structure or a piperidine structure. The heterocyclic ring can also form a condensed ring. More specifically, for example, an anthracene structure, an isoindole structure, a benzimidazole structure, a benzotriazole structure, a quinoline structure, an isoquinoline structure, a quinazoline structure, a porphyrin structure, a pyridazine structure, and a quinine are exemplified. An oxazoline structure, an acridine structure, and the like. The (E) component is exemplified by, for example, quinolinic acid, quina D acid, 8-perylquinoline, 8-aminosarin, quinoline-8-carboxylic acid, 2-pyridinecarboxylic acid, xanthuric acid (xanthurenic). Acid), 4-pyreline_2_carboxylic acid (kynurenic acid), 7-hydroxy-5-methyl-1,3,4-triazaporphyrin, allopurinol, hypoxanthine (hypoxanthine), nicotinic acid, picolinic acid, methyl picidate and bicolin acid, etc., preferably quinolinic acid. These (E) into -18-

S 201237954 can be used alone or in combination of two or more. The content of the component (E) is preferably 〇·1 1% by mass or more and 5% by mass or less, more preferably 〇·1% by mass or more and 2% by mass or less, based on the total mass of the chemical mechanical honing water-based dispersion. . When the content of the component (E) is within the above range, the depression of the surface to be honed can be reduced, and chemical mechanical honing can be achieved with sufficient honing speed of the wiring material. 1.6. (F) Oxidizing agent The chemical mechanical honing water-based dispersion of the present embodiment may optionally contain (F) an oxidizing agent (hereinafter also referred to as "(F) component"). (F) The oxidizing agent has a honed surface which oxidizes the surface of the metal constituting the wiring material to cause chemical mechanical honing activity, and can improve the honing speed of the wiring material. The (F) oxidizing agent is exemplified by, for example, hydrogen peroxide, persulfuric acid, persulfate, hypochlorous acid, hypochlorite, iron nitrate, diammonium nitrate planing, hydrazine molybdate, thirteenth tungstic acid, potassium periodate. , peracetic acid, ozone, etc. Among these oxidizing agents, ammonium persulfate, potassium persulfate, and hydrogen peroxide are preferred in view of oxidizing power, compatibility with a protective film, and ease of handling. These (F) oxidizing agents may be used alone or in combination of two or more. The content of the component (F) is preferably 0.05% by mass or more and 4% by mass or less based on the total mass of the aqueous dispersion. The amount is more preferably 0.1% by mass or more and 3% by mass or less. When the content of the component (F) is within the above range, chemical mechanical honing can be achieved for a sufficient honing speed of the copper film. 1.7. (G) Water-soluble polymer -19-201237954 The chemical mechanical honing water-based dispersion of the present embodiment may optionally contain (G) a water-soluble polymer (hereinafter also referred to as "(G) component"). (G) component It has a function of adsorbing on the surface of the surface to be honed to reduce honing friction. Therefore, when the component (G) is added to the chemical mechanical honing water dispersion, the depression of the honed surface can be reduced. The component (G) is exemplified by, for example, polyvinyl alcohol, hydroxyethyl cellulose, polyvinylpyrrolidine copper, polypropylene decylamine or the like. These (G) components may be used alone or in combination of two or more. The weight average molecular weight (Mw) of the component (G) is preferably 10,000 or more and 1.5 million or less, more preferably 40,000 or more and 1.2,000,000 or less. In the present specification, "weight average molecular weight" means a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography). The content of the component (G) should be adjusted so that the viscosity of the chemical mechanical honing water-based dispersion at room temperature becomes less than 2 mPa_s. Chemical mechanical honing water When the viscosity of the dispersion at a normal temperature is 2 mPa·s or more, the viscosity is too high and it is not stably supplied to the honing cloth. As a result, there is a problem that the temperature of the honing cloth rises or the honing unevenness occurs. Chemical mechanical honing water The viscosity of the dispersion can be determined substantially by the weight average molecular weight or content of the component (G), but it should be adjusted on the one hand in consideration of the balance.

1.8. pH The pH of the chemical mechanical honing aqueous dispersion of the present embodiment is preferably 8.0 or more and 10.0 or less, more preferably 8.5 or more and 9.5 or less. When the pH of the chemical mechanical honing water-based dispersion is in the above range,

-20- S 201237954 The honing speed of the wiring material can effectively suppress the corrosion of the wiring material in the fine wiring and reduce the depression in the honed surface to achieve good chemical mechanical honing. The means for adjusting the pH of the chemical mechanical honing water-based dispersion is, for example, a method of adding a base to a chemical mechanical honing water-based dispersion. The base which can be added is exemplified by, for example, ammonia, potassium hydroxide, sodium hydroxide, TMAH (tetramethylammonium hydroxide) or the like. Among these, ammonia or potassium hydroxide is preferred. These bases may be used singly or in combination of two or more. 1.9. Manufacturing Method The chemical mechanical honing water-based dispersion of the present embodiment can be directly added to pure water by mixing (A) component, (B) component, (C) component, and other components as needed. Prepared by stirring. The chemical mechanical honing water-based dispersion thus obtained can be used as it is, but a chemical mechanical honing water-based dispersion containing (i.e., concentrating) each component at a high concentration can be prepared and diluted to a desired concentration at the time of use. . Further, a plurality of liquids (for example, 'two or three kinds of liquids) containing any one of the above-mentioned components may be prepared and used in combination at the time of use. In this case, the mixture can be supplied to the chemical mechanical honing device after mixing a plurality of liquids into a chemical mechanical honing water dispersion, and a plurality of liquids can be individually supplied to the chemical mechanical honing device and pressed. A chemical mechanical honing water dispersion is formed on the disk. As a specific example, a liquid (I) containing an aqueous dispersion containing water and the component (A) is mixed with a liquid (π) composition-21 - 201237954 containing water and (B) component and (C) component. These liquids are used to prepare a kit for the above-described chemical mechanical honing water-based dispersion. The concentration of each component in the liquid (I) and the liquid (Π) is not particularly limited as long as the concentration of each component in the chemical mechanical honing aqueous dispersion which is mixed in the final preparation is within the above range. For example, it is prepared to contain liquids (I) and (II) of each component at a higher concentration than the concentration of the chemical mechanical honing water-based dispersion, and to dilute the liquids (I) and (II) as needed, and to mix them. A chemical mechanical honing aqueous dispersion having a concentration of each component in the above range is prepared. Specifically, when the liquid (I) and the liquid (Π) are mixed in a weight ratio of 1:1, it is preferred to prepare a liquid (I) and a liquid (II) at twice the concentration of the chemical mechanical honing water dispersion. ). Further, it is also possible to prepare a liquid (I) and a liquid (Π) at a concentration of more than twice the concentration of the chemical mechanical honing water dispersion, and to mix the components in a weight ratio of 1:1 so that the components fall within The manner of the foregoing range is diluted with water. As described above, by separately preparing the liquid (I) and the liquid (Π), the storage stability of the aqueous dispersion can be improved. When the above-mentioned kit is used, the mixing method of the liquid (I) and the liquid (II) is not particularly limited as long as the above-mentioned chemical mechanical honing water-based dispersion can be formed at the time of honing. For example, the chemical mechanical honing water-based dispersion may be prepared by mixing the liquid (I) and the liquid (II), and then supplied to the chemical mechanical honing device, or the liquid (I) and the liquid (II) may be independently used. ) supplied to a chemical mechanical honing device and mixed on a platen. Alternatively, the liquid (I) and the liquid (Π) may be independently supplied to the chemical mechanical honing device and mixed on the inside of the device, or a mixing tank may be provided in the chemical mechanical honing device to be mixed in the mixing tank. In addition, when mixing on the line, in order to obtain a more even water system

-22- S 201237954 For bulk, you can also use an in-line mixer. 1.10. Use of the chemical mechanical honing water-based dispersion according to the present embodiment, the sufficient honing speed of the wiring material can be obtained, and the corrosion of the wiring material in the fine wiring can be effectively suppressed, and the honed surface can be reduced. Deformation can achieve good chemical mechanical honing. Therefore, the chemical mechanical honing water-based dispersion of the present embodiment can be preferably used in the step of removing the wiring material on the barrier metal film by CMP (first honing step). The wiring material to be subjected to chemical mechanical honing is not particularly limited, but it is most suitable when it is copper or a copper alloy because the effect of the present invention is easily obtained. Here, the copper content in the copper alloy is preferably 95% by mass or more. 2. Chemical mechanical honing method The chemical mechanical honing method of the present embodiment is characterized in that it includes a barrier metal film formed to cover the bottom surface to the side surface of the concave portion, and an insulating film having a concave portion formed thereon, to cover the barrier rib The metal film is embedded in a substrate of a metal film made of copper or a copper alloy in the concave portion, and the metal film is planarized by the chemical mechanical honing aqueous dispersion. Hereinafter, a specific example of the chemical mechanical honing method of the present embodiment will be described in detail with reference to the drawings. 2·1·Processed body Fig. 1 is a cross-sectional view schematically showing a target object to be used in the chemical mechanical honing method of the present embodiment -23-201237954. Hereinafter, a method of manufacturing the object to be processed 100 shown in Fig. 1 will be described. (1) First, the low dielectric constant insulating film 10 is formed by a coating method or a plasma CVD method. The low dielectric constant insulating film 10 is exemplified by an inorganic insulating film and an organic insulating film. The inorganic insulating film is exemplified by, for example, a SiOF film (k = 3.5 to 3.7), a SiO film containing Si-H (k = 2.8 to 3_0), and the like. The organic insulating film is exemplified by a SiO 2 film containing carbon (k = 2.7 to 2.9), a si02 film containing a methyl group (1 { = 2.7 to 2.9), a polyimide film (1^3.0 to 3.5), and a poly pair. a parylene film (k = 2.7 to 3.0), a Teflon (registered trademark) film (k = 2.0 to '2.4), an amorphous carbon (k = < 2.5), etc. (k in the brackets above) Indicates the dielectric ratio). (2) The insulating film 12 is formed on the dielectric constant insulating film 10 by a CVD method or a thermal oxidation method. The insulating film 12 is exemplified by, for example, a TEOS film. The insulating film 12 is used to protect a low dielectric constant insulating film having a low mechanical strength. The film is formed by a film which is affected by the honing pressure, and is also called a so-called cap layer. (3) The wiring recessed portion 1 1 is formed by etching so that the low dielectric constant insulating film 10 and the insulating film 12 are in communication. The barrier metal film 14 is formed by covering the surface of the insulating film 12 and the bottom surface of the wiring recess 11 to the side surface by a CVD method. The barrier metal film 14 is preferably Ta or TaN from the viewpoint of adhesion to a copper (or copper alloy) film and excellent barrier properties to a copper (or copper alloy) film. (5) Further, copper (or a copper alloy) is deposited on the barrier metal film 14 by an electroplating method to form a copper (or copper alloy) film 16, whereby the object to be processed 100 is obtained. • twenty four-

S 201237954 2.2. Chemical Mechanical Honing Method Figure 2 is a cross-sectional view showing the first honing step after the end of the first honing step. Fig. 3 is a cross-sectional view schematically showing the body after the second honing step. First, the copper (or copper alloy) film 16 deposited on the barrier metal film 14 is removed by CMP (first honing step). In the first honing, the chemical mechanical honing water-based dispersion of the present embodiment is used to expose the straight metal film 14 by CMP honing copper (or copper alloy) film 16 as shown in FIG. 2, and then the barrier metal film 14 is exposed. Stop the CMP. Further, the chemical mechanical honing water of the present embodiment is characterized in that the honing speed to the copper (or copper alloy) film 16 is extremely high, and the honing speed to the barrier metal film 14 is low. Therefore, as shown in Fig. 2, it becomes difficult to stop the CMP when the barrier metal film 14 is exposed. Next, the unnecessary barrier metal film p-copper alloy film 16 is removed by CMP (second honing step). This second honing step is performed by a chemical mechanical honing aqueous dispersion using the honing step. As shown in Fig. 3, the unnecessary film is continuously honed by CMP until the low-edge film 10 is exposed. Thus, the flat semiconductor device 200 of the honed surface is obtained. A commercially available mechanical honing device can be used as the chemical mechanical honing method of the present embodiment. Commercially available chemical mechanical honing devices are exemplified by the models "EPO-112" and "EPO-222" manufactured by the company: the processing of the processing body is not required. For example, when the barrier is discharged, the dispersion is temporarily, but the opposite is shown, so CMP [or copper (or the use of the CMP. For example, a chemical machine with excellent dielectric constant such as Lapmaster -25-201237954 SFT) Made by the company, model "LGP-5 10", "LGP-5 52"; manufactured by Applied Materials, model "Mirra", etc. The preferred honing conditions should be appropriately set according to the chemical mechanical honing device used, but for example When "EPO-112" is used as the chemical mechanical honing device, the following conditions may be met: • Platen rotation number; preferably 30 to 120 rpm, more preferably 40 to 100 rpm. Bearing head rotation number; preferably 30 to 120 rpm More preferably 40 to 100 rpm • platen revolutions/carrier head rotation ratio; preferably 0.5 to 2, more preferably 0.7 to 1.5. honing pressure; preferably 60 to 200 gf/cm 2 , more preferably 100 ~150gf/cm2 • Chemical mechanical honing water-based dispersion supply rate; preferably 50 to 400 mL/min, more preferably 100 to 300 mL/min. 3. Examples Hereinafter, the present invention will be described by way of examples, but the present invention It is not subject to any limitations of these examples. 3.1. Chemical mechanical honing water system Preparation of the dispersion 3.1.1. Preparation of the colloidal cerium oxide aqueous dispersion The water glass No. 3 (ceria concentration: 24% by mass) was diluted with water to obtain a diluted sodium citrate aqueous solution having a cerium oxide concentration of 3.0% by mass. The diluted aqueous solution of sodium citrate is passed through a hydrogen-type cation exchange resin to remove most of the sodium ions to obtain an active aqueous solution of citric acid having a pH of 3. Then, a 10% by mass aqueous potassium hydroxide solution is immediately added under stirring to adjust the pH to 7.2, then continue to heat to boiling, hot for 3 hours. In the resulting aqueous solution

-26- S 201237954 Add a 10-fold amount of the active solution previously adjusted to pH 7.2 to grow colloidal cerium oxide. Next, the above-mentioned colloidal ceria-containing liquid was concentrated under reduced pressure to obtain a cerium oxide concentration: 32.0% by mass, pH: 7 cerium oxide aqueous dispersion. The colloidal cerium oxide aqueous dispersion type cation exchange resin layer was removed, and most of the sodium was removed, and then a potassium hydroxide aqueous solution was added to obtain a colloidal cerium oxide aqueous dispersion having a cerium oxide particle concentration of 8.0 and a pH of 8.0. The obtained colloidal cerium oxide was observed through a lens to obtain an average particle diameter of 3.1.2. Preparation of a chemical mechanical honing water-based dispersion, 50 parts by mass of ion-exchanged water, and converted into a mass fraction of the silica. Aqueous yttrium oxide dispersion, dodecane difer fraction, 0.5 parts by mass of glycine, 0.5 parts by mass of quinolinic acid, 5 parts by mass of rosilone oxime, ammonium pentanobenzenesulfonate 0.04 succinic acid After 0.0005 parts by mass of potassium was fed into 1.8 parts by mass of ammonium persulfate added with polyethylene, the pH was adjusted with ammonia water and ΐ. Finally, the total amount of all the components was added to 100 parts of ion-exchanged water and added to a bottle made of polyethylene, and then filtered through a pore size filter to obtain the chemical mechanical honing of Example 1 to remove the type and content of each component. In the same manner as in the chemical mechanical honing of the first embodiment, the same procedure as in the chemical mechanical honing of the first embodiment was carried out, and the water-soluble dispersion of the aqueous solution of the other examples and the comparative examples was prepared. Hydrogen plus 1 〇 mass% 2 8.0% by mass Electron microscopy 2 6 nm ° Equivalent to 0.5 ! 0.02 mass of polyvinylpyrazine mass, olefin bottle, add simmer for 15 minutes, 1 μιη The water-based dispersion chemical system described in the film aqueous dispersion 硏-27- 201237954 Water-based dispersion. The components described in Tables 1 to 5 are each used as described below. • Dodecanedioic acid (manufactured by Wako Pure Chemical Industries, Ltd., trade name "dodecanedioic acid") • Tridecanedioic acid (manufactured by Wako Pure Chemical Industries, Ltd., trade name "tridecanedioic acid" ” • Azelaic acid (trade name “Azelaic Acid” manufactured by Wako Pure Chemical Industries Co., Ltd.) • DBS-A (ammonium dodecylbenzenesulfonate) • Dipotassium alkenyl succinate (Kao Co., Ltd.) Manufactured 'product name' LATEMUL ASK', alkenyl succinate dipotassium) • Glycine (manufactured by Wako Pure Chemical Industries, Ltd., the trade name “Glycine”) • Alanine (made by Wako Pure Chemical Industries Co., Ltd.) 'Product name "DL_α-alanine") • Quinolinic acid (trade name "2,3_pyridine dicarboxylic acid" manufactured by Wako Pure Chemical Industries Co., Ltd.) ft ^ • Quinidine acid (Wako Pure Chemical Industries Co., Ltd.) Co., Ltd. manufactures 'commodity $ 'quinolinecarboxylic acid") • Ammonium persulfate (manufactured by Wako Pure Chemical Industries, Ltd. ' ® ^ ammonium peroxodisulfate)) • Hydrogen peroxide (manufactured by Wako Pure Chemical Industries Co., Ltd.) ® Hydrogen peroxide ") • PVP (Wako Pure Chemical Industries, Ltd., under the trade name" Poly #

-28- S 201237954 Pyrrolidinone K90", polyvinylpyrrolidone) 3.2. Chemical mechanical honing test 3.2.1 Evaluation of honing of non-patterned substrate honing pad made of porous polyurethane (NITT A The HASS company's 'Model 1C 1000' is installed in a chemical mechanical honing device (manufactured by Ebara Seisakusho Co., Ltd., model "EP01 12"), and is supplied with "3.1.2. Chemical mechanical honing water dispersion. The honing speed measurement substrate was subjected to honing treatment for one minute under the following honing conditions for one minute of the chemical mechanical honing water-based dispersion prepared in the following manner, and the honing speed was evaluated by the following method. The results are shown together in Tables 1 to 5. 3.2.2. Determination of honing speed (1) Substrate for honing speed measurement • Layer 8 of copper film with a film thickness of 1 5,000 angstroms and enamel with thermal oxide film (2) Honing conditions • Bearing head Number of revolutions: 30 rpm • Load capacity of the load head: 200 gf/cm2 • Number of revolutions of the turret: 70 rpm • Supply rate of chemical mechanical honing water dispersion: 15 〇 mL/min. Supply of chemical mechanical honing water dispersion in this case The speed is the total amount of supply of all the feed liquid divided by the time per unit time. -29- 201237954 (3) Evaluation method of honing speed Using a conductive film thickness measuring device (manufactured by KLA-Tencor Co., Ltd., "OMUNIMAP RS75"), the film thickness of the ketone film before and after honing treatment was measured and chemical mechanical The honing speed is calculated by honing the reduced film thickness and honing time. The honing speed is preferably 70 Å nm/min or more, more preferably 750 nm/min or more. 3.2.3. Evaluation of the honing of the wafer of the drawing type The ramming pad made of porous polyurethane (manufactured by NITTA HASS, model "IC1000") was attached to the chemical mechanical honing device (荏原株式会社公司) In the production model, "EP0112", the chemical mechanical honing water dispersion prepared in "3.1.2. Preparation of chemical mechanical honing water dispersion" is supplied to the following drawings. The wafer is subjected to honing treatment in the same manner as the honing condition in the above-mentioned "3.2.2. Measurement of honing speed" except that the molybdenum film is detected as the honing end point on the honed surface. The method was evaluated for flatness and corrosion. (1) The wafer of the drawing type is used to deposit a nitride film of 1,000 angstroms on a ruthenium substrate, and the PETE0S film is sequentially laminated thereon, and then processed by "SEMATECH 8 54" mask pattern. A test substrate made of a 250 angstrom molybdenum film, a 1,000 angstrom copper seed film, and a 10 angstrom copper plating film was sequentially laminated. -30-

S 201237954 (2) Evaluation method of flatness Using a high-resolution profiler (HRP240ETCH manufactured by KLA-Tencor Co., Ltd.), the copper wiring width (line, L) was measured for the honing surface of the pattern after the honing process. Insulation film width (pitch, 凹陷μηι/ΙΟΟμϊη in the copper wiring portion of the amount of recess (nm). It is listed in Table 1 to Table 5. The amount of depression is preferably 100 nm or less, more or less. (3) Evaluation method of corrosion 2cmx2cm immersed from the honed surface of the wafer of the drawing type, immersed in any of the chemical mechanical honing water dispersion prepared in 3.1.2. Chemical mechanical honing water dispersion, washed and dried After that, the copper distribution width (line, L) / insulating film width (the pitch of the copper fine wiring portion of 0.18 μm / 0.18 μm) was observed using a scanning electron microscope (manufactured by Hitachi S4800). The results are shown in Table 1 to Table 5. Table 1 In Table 5, "X" indicates that the copper is dissolved in a poor state, and "△" indicates that the copper wiring near the crucible dissolves slightly in a gap, and is "not as good as before the copper wiring is immersed." No obvious dissolution is seen The model "wafer is S" is the result of a region where f is 80nm, and the system is "medium minute, and the model ", S) is listed at the junction of the film and the film." 201237954

[II

Example 7 Colloidal ceria dodecanedioic acid § 〇 DBS-A 0.005 alkenyl succinate dipotassium 0.0005 glycine \ n quinolinic acid ammonium persulfate ΟΟ 00 < 3 Example 6 Colloid Ceria dodecanedioic acid g 〇 DBS-A s ο alkenyl succinate dipotassium 0.0005 glycine bismuth persulfate S yan cu S 〇ON οό 〇 Example 5 colloidal cerium oxide σν dodecane Diacid DBS-A g ο In 0.0025 bismuth glycinate) Quinolinic acid persulfate money CN CS S 〇8 〇 Example 4 Colloidal oxidation is more than οο m 11 11 -f CO DBS-A g ο it; In 0.002 Glycine οο quinolinic acid cn persulfate Ο S Ο S 〇 〇 Example 3 colloidal cerium oxide r- ο dodecanedioic acid g ο DBS-A g ο alkenyl succinate dipotassium 0.0005 glycine acid ο Quinolinic acid CSJ O Persulfate table o csi will Q. S 〇σ> οο 〇 〇 Example 2 Colloidal Oxidation CO ο Dodecanedioic acid s DBS-A g ο Alkenyl succinate dipotassium 0.001 Glycine (Οο quinolinic acid to o' ammonium persulfate σ> T- £ S 〇00 00 〇〇0 〇g Example 1 Glue Ceria to ο dodecanedioic acid s ο DBS-A 0.04 alkenyl succinate diacetate 0.0005 glycine LO ο quinolinic acid in o ammonium persulfate oo Q- 〇 od § <3 § type addition (% by mass) Type of addition (% by mass) Type of addition (% by mass) Type of addition (% by mass) Type of addition (% by mass) Type of addition (% by mass) m «1wi1 郷 Addition amount (% by mass) Type Adding amount (% by mass) X α Honing speed (m/min) Corrosion amount (nm) (A) 硏 abrasive grains (B) Polycarboxylic acid compound (C) Anionic surfactant (8) Amino acid carbonyl 趦 mm ΨΡ-Ν km ω Vw/ (F ) oxidant (G) water-soluble polymer evaluation item S s -32 201237954 [8] Example 14 Colloidal ceria CJ) Dodecanedioate DBS-A s ο alkenyl Dipotassium citrate 0.002 bismuth glycinate quinolate acid ammonium persulfate CN CL, s c> 〇 < ο 〇 〇 Example 13 Colloidal dioxide oxidation compared to oo 趑11 跶11 + Μ c5 DBS-A g ο code sea Min 猢 11 0.0015 Glycine quinolate acid persulfate money SP: so § Diphth Example 12 Colloidal cerium oxide 11 尨 11 + ο DBS-A s ο «11 0.001 Glycine un »—4 Quinoline cn 〇Persulfate Ο) | so 〇\ 00 2 ON 〇§ Example 11 Colloidal cerium oxide vq 饀11 跶11 + ο DBS-A s ο Dipotassium succinate 0.0005 yttrium quinolinate 〇α Persulfate saddle CU so 〇〇〇〇沄ON <3 Example 10 Colloidal cerium oxide oo Zhao 11 蜞1 1 + g ο DBS- A alkenyl succinate dipotassium 0.0005 glycine quinolinic acid (Ν Ν persulfate money Q, so ^ Η ON ο 〇〇 Example 9 colloidal dioxide oxidation compared to Zhao 11 back 11 + TO ο DBS-A g ο olefin Potassium pericarbonate 0.0005 Glycine r·': Quinoline CO Persulfate S 1 Cu so § Example 8 Colloidal silica sand vq Dodecanedioic acid TO ο DBS-A ρ alkenyl succinic acid Dipotassium 0.0005 Glycine quinolinic acid persulfate saddle ON IX. so ON οό 〇〇〇Μ λ ^ tlmtl m Adding amount (% by mass) Type addition amount (% by mass) Type addition amount (% by mass) Type addition amount ( Mass%) Type addition amount (% by mass) Type _ g M a Ϊ m ilmtl Ρ Add amount (% by mass) Type amount valence %) ffi a 硏Speed (m/min) Corrosion amount (nm) (A) honing grain (B) polycarboxylic acid compound (c) anionic surfactant (D) amino acid feeding 氍 mm W (F) oxidizing agent 〆 〆 ί编/- -τ ? Ή , Evaluation item -33- 201237954 Example 21 Colloidal cerium ceria dodecanedioate! DBS-A terpene bisphenol potassium acetate 0.0005 glycine quinolinic acid vrj ammonium persulfate ΟΟ Η Dh s c5 p H 〇〇 <1 Example 20 Colloidal cerium oxide dodecanedioic acid ο DBS-A decyl succinic acid dipotassium 0.001 glycine Γ ^; quinolinic acid persulfate彦0-. sov〇σ; g < 〇 Example 19 Colloidal cerium oxide οο dodecanedioic acid g ο DBS-A S CD alkenyl succinate dipotassium 0.0015 glycine acid CO quinolinic acid CO per sulphate money S so 〇〇沄r- 〇Example 18 Colloidal cerium oxide ON Dodecanedioic acid Luο DBS-A S 二 Alkenyl succinate dipotassium 0.002 Glycolate quinolinate cs Persulfate money cu so § o 〇 Example 17 Colloidal cerium oxide dodecanedioic acid s ο DBS-A s ο Alkenyl succinate dipotassium 0.0005 Glycine 1 1 Persulfate money cu s ci 〇\ Od o P 〇 Example 16 Colloidal cerium oxide dodecanedioic acid g ο DBS-A s ο alkenyl succinate dipotassium 0.0005 quinamic acid quinalic acid CN persulfate s S P-. S o Os 〇 〇o 〇 〇 Example 15 Colloidal cerium oxide dodecanedioic acid g ο DBS-A s ο 饀 m mw 饀 0.0005 alanine r- (quinoline persulfate money ί SS o ON oo (% by mass) Surface addition amount (% by mass) m ws tirnil Addition amount (% by mass) Μ 〇mi< w Adding amount (% by mass) Μ W1S tlrnil m Adding amount (% by mass) I Adding amount (% by mass) Leg m Adding amount (% by mass) u Adding amount (% by mass) X a Honing speed (m/min) Corrosion amount (nm) (A) Honing grain (Β) polycarboxylic acid compound (c) Anionic Surfactant (D) Amino acid relatives shouting 筚 酹 / < - ν ω ___» (F) oxidizing agent 〆 ii - L , t § D ✓ Evaluation item - 34- s 201237954 [s] Example 27 Colloidal cerium oxide dodecanedioic acid c> DBS-A sc? Baohai 跋«11 0.0005 Glycine quinolinic acid persulfate money PS 〇〇〇od 〇〇<3 § Implementation Example 26 Colloidal cerium dioxide dodecanedioic acid t-Η Ο DBS-A so alkenyl succinate dipotassium 0.001 glycine quinolinic acid persulfate consuming CL, S ci ON 00 s 〇 〇 S Example 25 colloid Ceria; dodecanedioic acid g ο DBS-A go 知海截«11 趑 趑 0.0015 甘 甘 〇〇 quinoline CO per sulphate money P IX. S < 5 〇 〇 Example 24 colloid Ceria: dodecanedioic acid s ο DBS-A s C5 enedilic acid dipotassium 0.002 glutamic acid quinolinic acid CN persulfate money S C3 (X. S 〇 < as ο 〇 〇 Example 23 Colloidal cerium oxide-; dodecanedioic acid g ο DBS-A alkenyl succinate dipotassium 0.0005 glycine quinolinic acid CN hydrogen peroxide —— Η CU ο ON od ο <3 § Example 22 Colloidal cerium oxide dodecanedioic acid g ο DBS-A so alkenyl succinate dipotassium 0.0005 glycine porphyrin acid 03 ammonium persulfate s 1 1 ON od Γ- 0 〇 species addition amount (mass%) The amount of addition (% by mass) The amount of addition (% by mass) The amount of addition (% by mass) The amount of addition (% by mass) Amount %) Kind of addition amount (% by mass) K a Honing speed (m/min) Corrosion] Depression amount (nm) (A) 硏 abrasive grain (Β) polycarboxylic acid compound (c) Anionic surfactant (D) Amino acid 趦蜮筚 ω (F) oxidant (G) water-soluble polymer evaluation item - 35 - 201237954 [5 撇] Comparative Example 4 colloidal cerium oxide r-; dodecanedioic acid 1 1 1 1 Amino acid quinolinic acid CNj Persulfate 〇〇 〇〇 X X Comparative Example 3 ... 1 Colloidal cerium dioxide diacid TO S DBS-A « « «11 跋 0.000 0.0005 glycine quinolate acid cs ammonium persulfate 〇ON οό i X 〇Comparative Example 2 _1 Colloidal cerium oxide 1 1 DBS-A S 〇13⁄4 ftil 涯趣0.0005 1 Glycinic acid quinoline acid cs thiazepine OU C? σ\ 〇d 〇00 X Comparative Example 1 1 1 Dodecanedioic acid w c > DBS-A S 海 海 海 海 0.000 0.000 0.000 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 (% by mass) m 郷 Addition amount: (% by mass) Type addition amount (% by mass) mm _ 舾 _ PI Μ Owij 卿 _ 翘. ΐ« η ii type addition amount reimbursement %) Legging Addition amount (% by mass) Type 丨 Addition amount (% by mass) X a Honing speed (m/min)! Corrosion I Depression amount (nm) (A) Honing grain j (B) Polycarboxylic acid compound (c) Anion Sexual surfactant (D) Amino acid relatives <0#: #·Ν 酹 酹 ω (F) oxidant (6) Water-soluble high liver evaluation item 3.3. Evaluation results Chemical mechanical 依据 according to Examples 1 to 27 The water-based dispersion was used, and the honing speed of the copper film was sufficiently high as 700 nm/min or more. No corrosion of the copper wiring was observed in the corrosion evaluation, and the amount of the depression was sufficiently low as 90 nm or less.

S-36-201237954 In contrast, Comparative Example 1 is a composition obtained by removing the (A) colloidal cerium oxide from the composition of Example 3. According to the chemical mechanical honing water-based dispersion of Comparative Example 1, since the honing speed of the copper film was remarkably lowered, practical problems occurred. Comparative Example 2 is a composition in which the composition of Example 3 was removed from the dodecanedioic acid of the component (B). According to the chemical mechanical honing water-based dispersion of Comparative Example 2, the copper wiring was peeled off in the corrosion evaluation, and the suppression of corrosion was judged to be insufficient. Further, it was judged that the flatness of the copper film was also poor. In Comparative Example 3, the dodecanedioic acid of Example 3 was changed to the composition of the azelaic acid of n = 8 in the compound represented by the formula (1). According to the chemical mechanical honing water-based dispersion of Comparative Example 3, the copper wiring was found to be detached in the corrosion evaluation, and the suppression of corrosion was judged to be insufficient. Further, it was also judged that the flatness of the copper film was poor. 〇 Comparative Example 4 is a composition of the interface active agent which removed the component (C) from the composition of Example 3. According to the chemical mechanical honing water-based dispersion of Comparative Example 4, the copper wiring was peeled off in the corrosion evaluation, and the suppression of corrosion was judged to be insufficient. Further, it was also judged that the flatness of the copper film was poor. From the above results, by using the chemical mechanical honing water-based dispersions of Examples 1 to 27, it is possible to suppress the corrosion of the wiring material in the fine wiring, and at the same time, the high honing speed of the wiring material and the reduced honed surface. The depression is judged to achieve good chemical mechanical honing. Further, the chemical mechanical honing water-based dispersion of the present invention contains Cu, Al, W, Ti, TiN, Ta, TaN, V, Mo, Ru, Zr, Μη, Ni, Fe, Ag, Mg, Μη, Si. The laminated structure of these elements, or the structure in which -37-201237954 does not substantially exist as a barrier metal, is also expected to be effective. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing a target object to be used in the chemical mechanical honing method of the present embodiment. Fig. 2 is a cross-sectional view schematically showing the object to be processed after the end of the first honing step. Fig. 3 is a cross-sectional view schematically showing the object to be processed after the end of the second honing step. [Description of main component symbols] 1 0 : Low dielectric constant insulating film 1 1 : Wiring recess 12 for wiring: Insulating film (protective film) 14 : Barrier metal film 16 : Copper (or copper alloy) film 1 : Object to be processed 200 : semiconductor device

Claims (1)

201237954 VII. Patent application scope: 1. A chemical mechanical honing water dispersion, characterized in that it contains (A) honing particles, and (B) the total length of the aliphatic chain existing between the carboxyl groups is a carbon number of 9 or more. a carboxylic acid compound and (C) an anionic surfactant. 2. The chemical mechanical honing water dispersion according to claim 1, wherein the component (B) is a compound represented by the following formula (!), HOOC-(CR'R2)n-COOH ... (1) (In the above formula (1), 'R1 and R2 each independently represent a hydrogen atom or an alkyl group, and n represents an integer of 9 or more). 3. The chemical mechanical honing water-based dispersion according to item 2 of the patent application, wherein the aforementioned (Β) component is dodecanedioic acid or tridecanedioic acid. 4. The chemical mechanical honing water-based dispersion according to the first aspect of the patent application, wherein the content of the (Β) component is 〇·〇1 mass% or more with respect to the total mass of the chemical mechanical honing water-based dispersion. · 5 mass% or less. 5. The chemical mechanical honing water-based dispersion according to the first aspect of the invention, wherein the component (C) is at least one selected from the group consisting of alkylbenzenesulfonic acid, alkenyl succinic acid, and the like. 6. The chemical mechanical honing water-based dispersion according to claim 1, wherein the content of the component (C) is 0.005% by mass or more and the mass of the chemical mechanical honing water-based dispersion is 0.005% by mass or more. %the following. 7. The chemical mechanical honing water dispersion according to the first aspect of the patent application, which further comprises (D) an amino acid. -39- 201237954 8. The chemical mechanical honing water-based dispersion according to the first aspect of the patent application, wherein the pH is 8 or more and 10 or less. 9. The chemical mechanical honing water dispersion according to the first aspect of the patent application, which further comprises (E) an organic acid having a nitrogen-containing heterocyclic ring. 1 〇 · The chemical mechanical honing water of the first application of the patent scope is a dispersion, which in turn contains (F) an oxidizing agent. 1 1 The chemical mechanical honing water-based dispersion according to the first aspect of the patent application, which further contains (G) a water-soluble polymer. 12. A chemical mechanical honing method comprising: a barrier metal film formed so as to cover a bottom surface to a side surface of the concave portion, and an insulating film formed with a concave portion, and burying the concave portion so as to cover the barrier metal film In the substrate of the metal film made of copper or a copper alloy, the step of planarizing the metal film is carried out by using a chemical mechanical honing aqueous dispersion according to any one of claims 1 to 11. . -40- S