JP2016030778A - CMP polishing liquid and polishing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide CMP (Chemical Mechanical Polishing) polishing liquid allowing for increase in polishing speed of a ruthenium-based metal compared to a case in which conventional CMP polishing liquid is used.SOLUTION: The CMP polishing liquid for polishing a ruthenium-based metal is provided that contains hydrogen peroxide, a metal oxidation agent (excluding hydrogen peroxide), an oxidized metal melting agent, an abrasive grain and water. The metal oxidation agent has an oxidation reduction potential with transfer of hydrogen ion, the oxidation reduction potential is 0.68 to 3.10 V with respect to a standard hydrogen electrode, pH of the CMP polishing liquid is 2.5 or more and less than 7.0, the content of the abrasive grain is 0.10 pts.mass or more based on the total 100 pts.mass of the content of the abrasive grain and the water.SELECTED DRAWING: Figure 6

Description

  The present invention relates to a CMP polishing liquid for polishing a ruthenium-based metal, and a polishing method using the same.

  In recent years, new microfabrication techniques have been developed along with higher integration and higher performance of semiconductor integrated circuits (LSIs). The chemical mechanical polishing (CMP: Chemical Mechanical Polishing; hereinafter referred to as “CMP”) method is one of them, such as planarization of an interlayer insulating material, formation of a metal plug, formation of a buried wiring, etc. in an LSI manufacturing process, particularly a multilayer wiring forming process. This technology is frequently used in

  In recent years, a damascene method for forming damascene wiring has been mainly employed in order to increase the integration density and performance of LSIs. An example of the damascene method will be described with reference to FIG. First, a groove (recess) 2 is formed on the surface of the insulating material 1 (FIGS. 1A and 1B). Next, the wiring metal 3 is deposited to fill the groove 2 (FIG. 1C). At this time, as shown in FIG. 1C, unevenness is formed on the surface of the wiring metal 3 due to the influence of the unevenness of the insulating material 1. Finally, the wiring metal 3 other than the portion buried in the groove 2 is removed by CMP (FIG. 1D).

  As the wiring metal (wiring part metal), a copper-based metal (copper, copper alloy, etc.) is often used. Copper-based metals can diffuse into the insulating material. In order to prevent this, a layered barrier metal is provided between the copper-based metal and the insulating material. As the barrier metal, a tantalum metal, a titanium metal, or the like is used. However, these barrier metals have low adhesion to copper-based metals. Therefore, instead of directly forming the wiring part on the barrier metal, in order to maintain the adhesion between the copper-based metal and the barrier metal, a copper-based metal thin film (copper seed layer) called a seed layer is provided after the copper-based metal is provided. It is common to deposit metal. That is, as shown in FIG. 2, the insulating material 1 having a recess on the surface, the barrier metal 4 provided on the insulating material 1 so as to follow the surface shape of the insulating material 1, and the shape of the barrier metal 4 A substrate (base body) having a seed layer 5 provided on the barrier metal 4 so as to follow, and a wiring metal 3 provided on the seed layer 5 so as to fill the recess and cover the entire surface. Used.

  In some cases, the barrier metal 4 and the seed layer 5 are formed by physical vapor deposition (hereinafter referred to as “PVD method”). However, in the PVD method, as shown in FIG. 3A, a metal (barrier metal or seed) formed on the inner wall surface of the groove portion by the PVD method in the vicinity of the opening portion of the groove portion (recess portion) formed in the insulating material 1. Layer) 6 tends to be partially thick. In this case, as the miniaturization of the wiring proceeds, as shown in FIG. 3B, the generation of voids 7 becomes conspicuous when the metals provided on the inner wall surface of the groove contact each other.

  As a means for solving this problem, a technique using a ruthenium-based metal having excellent adhesion with a copper-based metal has been studied. That is, a method using a ruthenium metal as a seed layer instead of a copper metal, or a method of providing a ruthenium metal between a seed layer using a copper metal and a barrier metal has been proposed. The ruthenium-based metal can be formed by a chemical vapor deposition method (Chemical Vapor Deposition, hereinafter referred to as “CVD method”) or an atomic layer deposition method (Atomic Layer Deposition, hereinafter referred to as “ALD method”). In the CVD method or the ALD method, generation of vacancies is easily suppressed, and it is possible to cope with the formation of fine wiring.

  When a ruthenium-based metal is used, a part of the ruthenium-based metal needs to be removed by CMP in the process of forming the damascene wiring. In contrast, several methods for polishing noble metals have been proposed. For example, platinum, iridium, ruthenium, rhenium, rhodium using a polishing liquid containing abrasive particles and at least one additive selected from the group consisting of diketones, heterocyclic compounds, urea compounds and amphoteric compounds A method of polishing noble metals such as palladium, silver, osmium and gold has been proposed (for example, see Patent Document 1 below). In addition, a method for polishing a noble metal using a chemical mechanical polishing system including an abrasive, a liquid carrier, and a sulfonic acid compound or a salt thereof has been proposed (for example, see Patent Document 2 below).

US Pat. No. 6,527,622 JP 2006-519490 A International Publication No. 2009/054370

  However, the conventional CMP polishing liquid for copper-based metals and the polishing polishing liquid for barrier metals do not specialize in removing ruthenium-based metals because the CMP polishing liquid is not specialized for removing ruthenium-based metals. A high polishing rate is not obtained. Patent Document 3 discloses a CMP polishing liquid for polishing a substrate having a layer containing ruthenium, which contains an oxidizing agent, abrasive particles, water, and a compound having a guanidine structure. Although described, it is desired to improve the polishing rate of ruthenium-based metals as compared with the conventional polishing liquid for CMP.

  The present invention provides a polishing slurry for CMP capable of improving the polishing rate of a ruthenium-based metal as compared with the case where a conventional polishing slurry for CMP is used, and a polishing method using the same.

  As a result of intensive studies, the present inventor has found that a first metal oxidizer that is hydrogen peroxide, a second metal oxidizer (except for hydrogen peroxide), a metal oxide solubilizer, abrasive grains, Water, and the second metal oxidant has a redox potential with the exchange of hydrogen ions, the redox potential is 0.68 to 3.10 V with respect to the standard hydrogen electrode, and is used for CMP. The pH of the polishing liquid is 2.5 or more and less than 7.0, and the content of abrasive grains is 0.1 parts by mass or more with respect to 100 parts by mass in total of the content of abrasive grains and the content of water. It has been found that the use of a CMP polishing liquid can improve the ruthenium-based metal polishing rate as compared with the conventional CMP polishing liquid.

  That is, the CMP polishing liquid according to the present invention is a CMP polishing liquid for polishing a ruthenium-based metal, and includes hydrogen peroxide, a metal oxidizing agent (excluding hydrogen peroxide), and metal oxide dissolution. Agent, abrasive grains, and water, and the metal oxidant has an oxidation-reduction potential accompanied by the exchange of hydrogen ions, and the oxidation-reduction potential is 0.68-3. 10V, the pH of the polishing slurry for CMP is 2.5 or more and less than 7.0, and the content of the abrasive is 100 parts by mass in total of the content of the abrasive and the content of the water And 0.10 parts by mass or more.

  According to the polishing slurry for CMP of the present invention, the ruthenium-based metal polishing rate can be improved as compared with the case where a conventional CMP polishing solution is used.

  The inventor presumes the reason why the ruthenium-based metal can be removed by CMP at a high polishing rate with the CMP polishing liquid according to the present invention as follows.

  That is, the present inventor paid attention to the polishing slurry for CMP in which the pH region is an acidic region, and the content of the abrasive grains was set to 0. 0 parts by mass with respect to a total of 100 parts by mass of the abrasive content and the water content. It has been found that when the amount is 10 parts by mass or more, it is effective for polishing and removing ruthenium-based metals at a high polishing rate.

  Next, as a result of searching for a metal oxidant capable of oxidizing a ruthenium-based metal in the acidic region, the present inventor has conceived that at least two kinds of metal oxidants are used, and then the first metal oxidant. And the second metal oxidizer can oxidize ruthenium-based metals in a pH range of 2.5 or more and less than 7.0, i.e., in such a pH range, It is effective that the metal oxidant has a redox potential that involves the exchange of hydrogen ions and a redox potential higher than the redox potential of the ruthenium-based metal (0.68 V with respect to the standard hydrogen electrode). I found it. When ruthenium is oxidized by coexistence of hydrogen peroxide as the first metal oxidant and a second metal oxidant having an oxidation-reduction potential accompanying the exchange of hydrogen ions in the polishing slurry for CMP. It is presumed that the oxidation catalytic action appears.

  Furthermore, the present inventor can remove the ruthenium metal at a high speed by containing a metal oxide solubilizer capable of forming a complex with the ruthenium metal oxidized with the metal oxidant in the CMP polishing liquid. I found out that I can do it.

  As described above, the CMP polishing liquid according to the present invention contains hydrogen peroxide, a metal oxidizer (except for hydrogen peroxide), a metal oxide solubilizer, abrasive grains, and water. In addition, the metal oxidant has a redox potential accompanying the exchange of hydrogen ions, the redox potential is 0.68 to 3.10 V with respect to the standard hydrogen electrode, and the pH of the polishing slurry for CMP is 2.5 or more It is less than 7.0, and the content of abrasive grains is 0.10 parts by mass or more with respect to 100 parts by mass in total of the content of abrasive grains and the content of water. Can be removed by polishing.

  The ruthenium-based metal may contain at least one selected from the group consisting of ruthenium, a ruthenium alloy, and a ruthenium compound.

  The metal oxidant includes at least one selected from the group consisting of nitric acid, bromic acid, sulfuric acid, peroxodisulfuric acid, hypochlorous acid, permanganic acid, iodic acid, periodic acid, perchloric acid, and salts thereof. You may go out. Thereby, the polishing rate of the ruthenium-based metal can be further improved.

  The metal oxidant may include at least one selected from the group consisting of ammonium nitrate, potassium bromate, ammonium peroxodisulfate, potassium peroxodisulfate, sodium hypochlorite, potassium permanganate, and potassium periodate. . Thereby, the polishing rate of the ruthenium-based metal can be further improved.

  The total of the content of the hydrogen peroxide and the content of the metal oxidant is 0.01 to 25.00 parts by mass with respect to 100 parts by mass as the total of the content of abrasive grains and the content of water. preferable. Thereby, the polishing rate of the ruthenium-based metal can be further improved, and the occurrence of roughness on the surface to be polished can be suppressed.

  The metal oxide solubilizer preferably contains an organic acid. Thereby, metal etching can be easily suppressed.

  The present inventor has the effect that the metal anticorrosive can form a complex with the ruthenium metal oxidized by the metal oxidant, and the ruthenium metal is polished and removed at a higher speed by using the metal anticorrosive. I found out that I can do it. The CMP polishing liquid according to the present invention may further contain a metal anticorrosive. Thereby, the polishing rate of the ruthenium-based metal can be further improved. Moreover, when the polishing liquid for CMP contains a metal anticorrosive agent, when the substrate to be polished is a semiconductor substrate, it is possible to prevent the conductive material that is polished and removed simultaneously with the barrier metal from being corroded.

  The metal anticorrosive agent preferably contains at least one selected from the group consisting of a compound having an imidazole skeleton, a compound having a triazole skeleton, a compound having a tetrazole skeleton, a compound having a pyrazole skeleton, and a compound having a pyrimidine skeleton. . Thereby, the polishing rate of the ruthenium-based metal can be further improved.

  The CMP polishing liquid according to the present invention may further contain an organic solvent. Thereby, the polishing rate of the ruthenium-based metal can be further improved.

  The polishing method according to the present invention includes an interlayer insulating film having a ridge and a groove on the surface, a barrier layer provided following the surface of the interlayer insulating film, and a conductive layer provided to cover the barrier layer. A first polishing step for polishing the conductive material layer in the substrate having the active material layer to expose the barrier layer located on the raised portion of the interlayer insulating film, and the barrier layer exposed by the first polishing step. And a second polishing step for exposing the raised portions of the interlayer insulating film by polishing using the above-described CMP polishing liquid.

  The interlayer insulating film may contain at least one selected from the group consisting of silicon compounds and organic polymers.

  The conductive material layer preferably contains at least one selected from the group consisting of copper, copper alloys, copper oxides, and copper alloy oxides.

  The barrier layer preferably contains at least one selected from the group consisting of ruthenium, ruthenium alloys and ruthenium compounds.

  According to the present invention, at least the ruthenium-based metal polishing rate can be improved as compared with the case where a conventional CMP polishing liquid is used. In addition, according to the present invention, the application (use) of the polishing slurry for CMP can be provided for polishing a substrate having a barrier layer containing a ruthenium-based metal.

FIG. 1 is a schematic cross-sectional view showing a damascene method for forming damascene wiring. FIG. 2 is a schematic cross-sectional view showing a substrate in which a seed layer is provided between a copper-based metal and a barrier metal. FIG. 3 is a schematic cross-sectional view showing a state of a metal formed by the PVD method. FIG. 4 is a schematic cross-sectional view showing a substrate on which a ruthenium-based metal is provided instead of the copper seed layer. FIG. 5 is a schematic cross-sectional view showing a substrate in which a ruthenium-based metal is provided between a copper seed layer and a barrier metal. FIG. 6 is a schematic cross-sectional view showing a process of polishing expectations using a CMP polishing liquid.

  Hereinafter, embodiments of the present invention will be described in detail. In this specification, the amount of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.

<CMP polishing liquid>
The CMP polishing liquid according to this embodiment is a CMP polishing liquid for polishing a ruthenium-based metal. The polishing slurry for CMP according to this embodiment contains at least hydrogen peroxide, a metal oxidizer (excluding hydrogen peroxide), a metal oxide solubilizer, abrasive grains, and water. The metal oxidizer (except hydrogen peroxide) of the CMP polishing liquid according to the present embodiment has a redox potential accompanying the transfer of hydrogen ions, and the redox potential is relative to a standard hydrogen electrode. 0.68 to 3.10V. The CMP polishing liquid according to this embodiment has a pH of 2.5 or more and less than 7.0. In the polishing slurry for CMP according to this embodiment, the content of abrasive grains is 0.10 parts by mass or more with respect to 100 parts by mass in total of the content of abrasive grains and the content of water.

[PH of polishing liquid for CMP]
The pH of the polishing slurry for CMP according to this embodiment is 2.5 or more and less than 7.0 from the viewpoint of increasing the polishing rate of the ruthenium-based metal. The pH of the CMP polishing liquid according to this embodiment is preferably 2.5 to 6.0 from the viewpoint of further increasing the ruthenium-based metal polishing rate. Further, the pH of the CMP polishing liquid according to the present embodiment is more preferably 2.5 to 4.5, and further preferably 2.5 to 4.0, considering the dispersibility of the abrasive grains. preferable. As an additional effect, in order to suppress the etching rate of conductive materials (for example, metals such as copper and copper alloys) as compared with the polishing rate of the barrier metal, in the range of pH 2.5 to less than 7.0, pH 2 Properties superior to those of less than 5 are obtained. Further, in the region where the pH is 7.0 or more, it is very effective for suppressing the etching action, but a practical ruthenium-based metal polishing rate cannot be obtained. When the pH is higher than 7.0, decomposition of the metal oxidant is promoted, and a secondary oxide layer that is harder to polish than the primary oxide layer is formed on the surface of the ruthenium-based metal, so that the polishing rate tends to decrease. The pH is defined as the pH at a liquid temperature of 25 ° C.

  The pH of the polishing slurry for CMP according to this embodiment can be adjusted by the content of the metal oxide solubilizer. Details will be described in the explanation of the metal oxide solubilizer described later.

  In this embodiment, the pH of the polishing slurry for CMP can be measured with a pH meter (for example, model number: PH81 manufactured by Yokogawa Electric Corporation). As the pH of the polishing liquid for CMP, standard buffer solutions (phthalate pH buffer solution pH: 4.01 (25 ° C.), neutral phosphate pH buffer solution pH 6.86 (25 ° C.), and borate pH buffer solution After calibrating three points using a liquid pH of 9.12 (25 ° C.), the electrode is put into a polishing liquid for CMP, and a value after 2 minutes or more has elapsed and can be adopted.

  Hereinafter, components of the CMP polishing liquid will be described.

[Metal oxide solubilizer]
The polishing slurry for CMP according to this embodiment contains a metal oxide dissolving agent. Examples of the metal oxide solubilizer include organic acids, organic acid esters, ammonium salts of organic acids, inorganic acids, ammonium salts of inorganic acids, etc. (compounds corresponding to metal anticorrosives and compounds corresponding to metal oxidants). There is no particular limitation as long as it is water-soluble. As the metal oxide solubilizer, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptane Acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid Organic acids such as phthalic acid, malic acid, tartaric acid, citric acid, p-toluenesulfonic acid, lactic acid and quinaldic acid; organic acid esters thereof; ammonium salts of the organic acids; inorganic acids such as hydrochloric acid and chromic acid; Examples thereof include ammonium salts of inorganic acids such as ammonium, ammonium dichromate, and ammonium dichromate. Among these, an organic acid is preferable from the viewpoint that metal etching is easily suppressed. Examples of the organic acid include glycolic acid, lactic acid, succinic acid, adipic acid, glutaric acid, malic acid, malonic acid, maleic acid, At least one selected from the group consisting of tartaric acid, benzoic acid, salicylic acid, quinaldic acid, butyric acid and valeric acid is preferred. These metal oxide solubilizers can be used alone or in combination of two or more.

  The polishing slurry for CMP according to this embodiment needs to have a pH of 2.5 or more and less than 7.0, and can be set to a desired pH by adjusting the content of the metal oxide solubilizer. Further, the pH of the CMP polishing liquid according to this embodiment can be adjusted by adding potassium hydroxide. Furthermore, the pH can be adjusted by adding an alkali component such as amino acid, ammonia, sodium hydroxide, tetramethylammonium hydroxide, or the like.

  The content of the metal oxide solubilizer is preferably 0.001 to 20 parts by mass, more preferably 0.002 to 10 parts by mass, more preferably 100 parts by mass of the total content of abrasive grains and water. Preferably it is 0.002-5 mass parts. When the content of the metal oxide solubilizer is 0.001 part by mass or more, a decrease in the polishing rate of the conductive material and the barrier metal tends to be suppressed, and when it is 20 parts by mass or less, etching is easily suppressed. And there is a tendency to suppress the occurrence of roughness on the surface to be polished.

[Abrasive grain]
The CMP polishing liquid according to this embodiment contains abrasive grains. The abrasive grain surface preferably has a positive zeta potential (positive charge) from the viewpoint of further increasing the polishing rate of the barrier metal, and has a zeta potential of +5 mV or more. Is more preferable, it is more preferable to have a zeta potential of +10 mV or higher, and it is particularly preferable to have a zeta potential of +20 mV or higher. The zeta potential of the abrasive can be easily adjusted by using a commercially available abrasive having a positive charge.

  When the pH is in the acidic region as in the CMP polishing liquid according to this embodiment, the colloidal silica particles in such a CMP polishing liquid tend to have a zeta potential of +20 mV or higher. As described above, when the abrasive grains have a zeta potential of +20 mV or higher, aggregation of the abrasive grains can be suppressed, and the abrasive grains can be well dispersed in the CMP polishing liquid.

  For the measurement of the zeta potential of the abrasive grains in the CMP polishing liquid, for example, trade name: Zetasizer 3000 HS manufactured by Spectris Co., Ltd. can be used. More specifically, the polishing slurry for CMP is diluted with water so as to have a recommended amount of scattered light of Zetasizer 3000 HS, and measured at room temperature (25 ° C.).

  The abrasive grains are not particularly limited, but preferably contain at least one selected from the group consisting of silica, alumina, ceria, titania, zirconia, germania, and modified products thereof.

  The modified product is obtained by modifying the surface of abrasive grains such as silica, alumina, ceria, titania, zirconia, and germania with an alkyl group.

  The method of modifying the surface of the abrasive grain with an alkyl group is not particularly limited, and examples thereof include a method of reacting a hydroxyl group present on the surface of the abrasive grain with an alkoxysilane having an alkyl group.

  The polishing slurry for CMP according to this embodiment preferably contains abrasive grains having an average particle diameter of 10 to 100 nm, and contains abrasive grains having an average particle diameter of 10 to 100 nm and containing colloidal silica. More preferred. Moreover, it is preferable that the polishing liquid for CMP which concerns on this embodiment contains the abrasive grain whose average particle diameter is 25-80 nm, and contains the abrasive grain which has an average particle diameter of 25-80 nm and contains colloidal silica. It is more preferable. If the average particle size is 10 nm or more, it is possible to suppress the reduction of the polishing rate of the barrier metal, and if it is 100 nm or less, it is possible to suppress the dispersion stability of the abrasive grains in the CMP polishing liquid from decreasing. it can.

  Here, the average particle diameter can be measured, for example, by the following method. That is, an appropriate amount of the polishing slurry for CMP is weighed, and diluted with water as necessary to prepare a measurement sample so that it falls within the range of scattered light intensity required by the dynamic light scattering particle size distribution analyzer. Next, the measurement sample is put into a dynamic light scattering particle size distribution meter for measurement, and the value obtained as D50 is taken as the average particle diameter. Examples of the dynamic light scattering particle size distribution meter having such a function include a product name: N5 type manufactured by BECKMAN COULTER. Moreover, the value of D50 of the particle size distribution measurement result can be used as the average particle diameter of the abrasive grains in the CMP polishing liquid (hereinafter referred to as the average particle diameter).

  These abrasive grains can be used alone or in combination of two or more. The content of the abrasive grains is 0.10 parts by mass or more with respect to a total of 100 parts by mass of the abrasive grain content and the water content, from the viewpoint of suppressing a decrease in the polishing rate of the ruthenium-based metal. As for content of an abrasive grain, 0.20 mass part or more is more preferable with respect to a total of 100 mass parts of content of an abrasive grain and water content, and 0.50 mass part or more is still more preferable. The content of abrasive grains is preferably 50.00 parts by mass or less with respect to a total of 100 parts by mass of the content of abrasive grains and the content of water from the viewpoint that generation of polishing scratches tends to be suppressed. 0.000 parts by mass or less is more preferable, and 25.00 parts by mass or less is even more preferable.

[Metal anticorrosive]
The CMP polishing liquid according to this embodiment may contain a metal anticorrosive. The metal anticorrosive agent is not particularly limited as long as it has a function of forming a protective film on the metal surface, but is conventionally known as long as it has an effective amount of water solubility to exert its effect. These materials can be used without particular limitation. These may be used alone or in combination of two or more. Specifically, anthranilic acid, salicylaldoxime, a compound having an imidazole skeleton (hereinafter referred to as “imidazole compound”), a compound having a triazole skeleton (hereinafter referred to as “triazole compound”), a compound having a tetrazole skeleton ( Examples thereof include compounds having a pyrazole skeleton (hereinafter referred to as “pyrazole compounds”), compounds having a pyrimidine skeleton (hereinafter referred to as “pyrimidine compounds”), and the like, among others, imidazole compounds. , A triazole compound, a tetrazole compound, a pyrazole compound, and a pyrimidine compound are preferred, and at least one selected from the group consisting of a pyrazole compound and a triazole compound is more preferred.

  Examples of imidazole compounds include 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-propylimidazole, 2-butylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, and 2-ethyl-4-methylimidazole. , 2-undecylimidazole, 2-aminoimidazole and the like.

  Examples of the triazole compound include 1,2,3-triazole; 1,2,4-triazole; 3-amino-1H-1,2,4-triazole, 1-acetyl-1H-1,2,3-triazolo [4 , 5-b] pyridine, 1H-1,2,3-triazolo [4,5-b] pyridine, 1,2,4-triazolo [4,3-a] pyridin-3 (2H) -one, 3H- Triazole derivatives such as 1,2,3-triazolo [4,5-b] pyridin-3-ol; benzotriazole; 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazole methyl ester Ter, 4-carboxyl-1H-benzotriazole butyl ester, 4-carboxyl-1H-benzotriazole octyl ester, 5-hexylbenzotriazole, [1,2,3-benzotriazolyl-1-methyl] [1,2, , 4-triazolyl-1-methyl] [2-ethylhexyl] amine, tolyltriazole, naphthotriazole, bis [(1-benzotriazolyl) methyl] phosphonic acid, benzotriazole derivatives such as 3-aminotriazole, and the like. Of these, benzotriazole and benzotriazole derivatives are preferred.

  Examples of the tetrazole compound include 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 1- (2-diaminoethyl) -5-mercaptotetrazole and the like. .

  Examples of the pyrazole compound include 3,5-dimethylpyrazole, 3-amino-5-methylpyrazole, 4-methylpyrazole, 3-amino-5-hydroxypyrazole and the like.

  Examples of the pyrimidine compound include pyrimidine, 1,2,4-triazolo [1,5-a] pyrimidine, 1,3,4,6,7,8-hexahydro-2H-pyrimido [1,2-a] pyrimidine, 1,3-diphenyl-pyrimidine-2,4,6-trione, 1,4,5,6-tetrahydropyrimidine, 2,4,5,6-tetraaminopyrimidine sulfate, 2,4,5-trihydroxy Pyrimidine, 2,4,6-triaminopyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-trimethoxypyrimidine, 2,4,6-triphenylpyrimidine, 2,4-diamino-6-hydroxyl Pyrimidine, 2,4-diaminopyrimidine, 2-acetamidopyrimidine, 2-aminopyrimidine, 2-methyl-5,7-diphenyl- (1,2,4) to Azolo (1,5-a) pyrimidine, 2-methylsulfanyl-5,7-diphenyl- (1,2,4) triazolo (1,5-a) pyrimidine, 2-methylsulfanyl-5,7-diphenyl Examples include -4,7-dihydro- (1,2,4) triazolo (1,5-a) pyrimidine, 4-aminopyrazolo [3,4-d] pyrimidine and the like.

  The content of the metal anticorrosive is preferably 0.001 to 10.00 parts by mass, more preferably 0.005 to 5.00 parts by mass with respect to 100 parts by mass as the total of the content of abrasive grains and the content of water. Parts, more preferably 0.01 to 2.00 parts by mass. When the content of the metal anticorrosive is 0.001 part by mass or more, it is easy to suppress etching of a conductive substance (for example, a metal for a wiring part), and there is a tendency that roughness of a polished surface is suppressed. When the amount is 10.00 parts by mass or less, a decrease in the polishing rate of the conductive material (for example, the metal for the wiring part) and the barrier metal tends to be easily suppressed.

[Metal oxidizing agent]
The CMP polishing liquid according to the present embodiment contains a first metal oxidant and a second metal oxidant. The first metal oxidant is hydrogen peroxide, and the second metal oxidant is a metal oxidant different from hydrogen peroxide. The second metal oxidant has an oxidation-reduction potential that involves the exchange of hydrogen ions. The oxidation-reduction potential is 0.68 to 3.10 V with respect to a standard hydrogen electrode (NHE) from the viewpoint of improving the ruthenium-based metal polishing rate. From the viewpoint of further improving the ruthenium-based metal polishing rate, the oxidation-reduction potential is preferably 0.80 to 2.30 V, and more preferably 0.84 to 2.00 V.

  The second metal oxidant is not particularly limited, but nitric acid, bromic acid, sulfuric acid, peroxodisulfuric acid, hypochlorous acid, permanganic acid, iodic acid, periodic acid, perchloric acid and salts thereof; Examples include ozone water. Examples of the salt include ammonium salt, potassium salt, sodium salt and the like. Specific examples include ammonium nitrate, potassium bromate, ammonium peroxodisulfate, potassium peroxodisulfate, sodium hypochlorite, potassium permanganate, and potassium periodate. As a 2nd metal oxidizing agent, it can use individually by 1 type or in mixture of 2 or more types.

  As a material for preparing the polishing slurry for CMP, a material that is separated into hydrogen peroxide as the first metal oxidant and second metal oxidant by decomposition or the like in the polishing liquid can be used. An example of such a metal oxidizing agent is peroxodisulfuric acid. When peroxodisulfuric acid and water coexist, peroxodisulfuric acid is hydrolyzed into hydrogen peroxide as the first metal oxidant and sulfuric acid as the second metal oxidant. Accordingly, the CMP polishing liquid prepared and produced by using peroxodisulfuric acid as the material for the CMP polishing liquid contains hydrogen peroxide as the first metal oxidant and the second metal oxidant. It will be.

  The content of the first metal oxidant is preferably in the following range. The content of the first metal oxidizer is preferably 0.005 to 5.00 parts by mass, more preferably 0.01 to 4 parts per 100 parts by mass in total of the content of abrasive grains and the content of water. 0.000 part by mass, more preferably 0.015 to 2.00 parts by mass. When the content of the first metal oxidant is 0.005 parts by mass or more, the metal is sufficiently oxidized and the ruthenium-based metal polishing rate tends to be further improved, and is 5.00 parts by mass or less. The surface to be polished tends to be prevented from being rough. Moreover, it is preferable that the compounding quantity of the 1st metal oxidizing agent at the time of preparing polishing liquid for CMP is the said range.

  The content of the second metal oxidant is preferably in the following range. The content of the second metal oxidizer is preferably 0.01 to 25.00 parts by mass, more preferably 0.02 to 20 parts per 100 parts by mass in total of the content of abrasive grains and the content of water. 0.000 part by mass, more preferably 0.05 to 15.00 parts by mass. When the content of the second metal oxidant is 0.01 parts by mass or more, the metal is sufficiently oxidized and the ruthenium-based metal polishing rate tends to be further improved, and is 25.00 parts by mass or less. The surface to be polished tends to be prevented from being rough. Moreover, it is preferable that the compounding quantity of the 2nd metal oxidizing agent at the time of preparing the polishing liquid for CMP is the said range.

  The content of the metal oxidant (the total of the content of the first metal oxidant and the content of the second metal oxidant) is preferably in the following range. The content of the metal oxidizer is preferably 0.01 to 25.00 parts by mass, more preferably 0.02 to 20.00 parts by mass with respect to a total of 100 parts by mass of the content of abrasive grains and the content of water. Parts, more preferably 0.05 to 15.00 parts by mass. When the content of the metal oxidizer is 0.01 parts by mass or more, the metal is sufficiently oxidized and the polishing rate of the ruthenium-based metal tends to be further improved, and when it is 25.00 parts by mass or less It tends to be suppressed that the surface is rough. Moreover, it is preferable that the compounding quantity of the metal oxidizing agent at the time of preparing CMP polishing liquid is the said range.

[Water-soluble polymer]
The CMP polishing liquid according to this embodiment can further contain a water-soluble polymer. The weight average molecular weight (Mw) of the water-soluble polymer is preferably 500 or more, more preferably 1500 or more, and still more preferably 5000 or more. The upper limit of the weight average molecular weight of the water-soluble polymer is not particularly limited, but is preferably 5 million or less from the viewpoint of excellent solubility. When the weight average molecular weight of the water-soluble polymer is 500 or more, a higher polishing rate of the ruthenium-based metal tends to be obtained. The weight average molecular weight of the water-soluble polymer can be measured using a standard polystyrene calibration curve by gel permeation chromatography (GPC) under the following conditions.

(GPC conditions)
Sample: 10 μl
Standard polystyrene: Standard polystyrene manufactured by Tosoh Corporation (Molecular weight: 190000, 17900, 9100, 2980, 578, 474, 370, 266)
Detector: manufactured by Hitachi, Ltd., RI-monitor, trade name: L-3000
Integrator: Hitachi, Ltd., GPC integrator, product name: D-2200
Pump: manufactured by Hitachi, Ltd., trade name: L-6000
Degassing device: Showa Denko Co., Ltd., trade name: Shodex DEGAS
Column: Hitachi Chemical Co., Ltd., trade name: GL-R440, GL-R430, GL-R420 connected in this order and used as eluent: tetrahydrofuran (THF)
Measurement temperature: 23 ° C
Flow rate: 1.75 ml / min
Measurement time: 45 min

  The water-soluble polymer is not particularly limited, and examples thereof include at least one selected from the group consisting of polycarboxylic acids, polycarboxylic acid salts, polycarboxylic acid esters, polysaccharides, and vinyl polymers. Water-soluble polymers include polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, polymethacrylic acid, polyamic acid, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrenecarboxylic acid), polyacrylic acid, polyacrylamide, Polycarboxylic acids such as amino polyacrylamide and polyglyoxylic acid; polycarboxylic acids such as polymethacrylic acid ammonium salt, polymethacrylic acid sodium salt, polyacrylic acid ammonium salt, polyacrylic acid sodium salt, polyamic acid ammonium salt, polyamic acid sodium salt Acid salt: polyaspartic acid ester, polyglutamic acid ester, polymethacrylic acid ester, polyamic acid ester, polymaleic acid ester, polyfumaric acid ester, polyacrylic acid ester, etc. Polycarboxylic acid esters; alginic acid, pectic acid, carboxymethylcellulose - scan, agar, mosquitoes - polysaccharides such Doran and pullulan, polyvinyl alcohol - le, and vinyl-based polymers such as polyvinyl pyrrolidone and acrolein and the like. These water-soluble polymers can be used alone or in combination of two or more.

  The content of the water-soluble polymer is preferably 0.001 to 15.00 parts by mass, more preferably 0.002 to 10.00 parts by mass with respect to 100 parts by mass in total of the content of abrasive grains and the content of water. Parts, more preferably 0.005 to 5.00 parts by mass. If the content of the water-soluble polymer is 0.001 part by mass or more, roughening of the surface to be polished tends to be suppressed, and if it is 15.00 parts by mass or less, it is contained in the CMP polishing liquid. There is a tendency that the stability of the abrasive grains is improved.

[Organic solvent]
The CMP polishing liquid according to the present embodiment can further contain an organic solvent. Although there is no restriction | limiting in particular as an organic solvent, The thing which can be mixed arbitrarily with water is preferable.

  Specific examples of the organic solvent include carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; lactones such as butyrolactone and propyrolactone; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol , Glycols such as triethylene glycol and tripropylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether and ethylene glycol monoethyl ether ,Propylene glycol No ethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, diethylene glycol monopropyl ether, dipropylene glycol Monopropyl ether, triethylene glycol monopropyl ether, tripropylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monobutyl ether, tripropylene glycol Glycol monoethers such as ethyl monobutyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, diethylene glycol diethyl ether, Dipropylene glycol diethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether, diethylene glycol dipropyl ether, dipropylene glycol dipro Such as pill ether, triethylene glycol dipropyl ether, tripropylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether, triethylene glycol dibutyl ether, tripropylene glycol dibutyl ether Derivatives of glycols such as glycol diethers; ethers such as tetrahydrofuran, dioxane, dimethoxyethane, polyethylene oxide, ethylene glycol monomethyl acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; methanol, ethanol, propanol, n- Butanol, Alcohols such as pentanol, n-hexanol, isopropanol (isopropyl alcohol), 3-methyl-3-methoxybutanol; ketones such as acetone and methyl ethyl ketone; phenols such as phenol; amides such as dimethylformamide; sulfolane and the like Sulfolanes; n-methylpyrrolidone; ethyl lactate and the like. Among these, at least one selected from the group consisting of carbonates, lactones, glycols and derivatives thereof, ethers, alcohols, ketones, phenols, amides, and sulfolanes is preferable, and glycol monoethers Alcohols and carbonates are more preferred. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.

  The content of the organic solvent is preferably 0.10 to 50.00 parts by mass, more preferably 0.20 to 30.00 parts by mass with respect to a total of 100 parts by mass of the content of abrasive grains and the content of water. More preferably, it is 0.50 to 10.00 parts by mass. When the content of the organic solvent is 0.10 parts by mass or more, the wettability of the polishing liquid to the substrate tends to be suppressed, and when it is 50.00 parts by mass or less, the dispersibility decreases. There is a tendency to be suppressed.

  The polishing liquid according to this embodiment may be stored as a one-part polishing liquid containing at least abrasive grains, a first metal oxidizer, a second metal oxidizer, a metal oxide solubilizer, and water. Well, a multi-liquid type (for example, the constituents of the polishing liquid are divided into the slurry and the additive liquid so that the slurry (first liquid) and the additive liquid (second liquid) are mixed to become the polishing liquid (for example, It may be stored as a two-component polishing solution set. The slurry includes at least abrasive grains and water, for example. The additive solution includes, for example, at least a second metal oxidant and water. It is preferable that a 1st metal oxidizing agent, a 2nd metal oxidizing agent, and another additive are contained in an additive liquid among slurry and an additive liquid. The constituents of the polishing liquid may be stored as a polishing liquid set divided into three or more liquids. For example, a three-component polishing comprising a slurry containing at least abrasive grains and water, a first additive liquid containing the first metal oxidant, and a second additive liquid containing the second metal oxidant. It may be stored as a liquid set. The second metal oxidizer may be mixed as a solid without dissolving in water to form a polishing liquid. For example, in the case of a compound that separates into hydrogen peroxide and the second metal oxidant in water, such as ammonium peroxodisulfate, it is preferable to add it as a solid.

  In the polishing liquid set, slurry and additive liquid are mixed immediately before polishing or at the time of polishing to prepare a polishing liquid. The one-part polishing liquid may be stored as a polishing liquid storage liquid with a reduced water content, and may be diluted with water during polishing. The multi-liquid type polishing liquid set may be stored as a slurry storage liquid and an additive liquid storage liquid with a reduced water content, and may be diluted with water during polishing.

<Polishing method>
The CMP polishing liquid according to this embodiment can be applied to the formation of a wiring layer in a semiconductor device. The polishing slurry for CMP according to the present embodiment can be used for CMP of a substrate (for example, a substrate) having, for example, a conductive substance, a barrier metal, and an interlayer insulating material. The shape of the conductive substance, the barrier metal, and the interlayer insulating material is, for example, a layer or a film (for example, a conductive substance layer, a barrier layer, and an interlayer insulating film). In the CMP under the same conditions, the polishing rate ratio of the conductive substance / barrier metal / interlayer insulating material is preferably 0.1 / 1/1 / 0.1-1.

  Examples of the constituent material of the interlayer insulating material include at least one selected from the group consisting of silicon compounds and organic polymers. Examples of the silicon compound include silicon dioxide, fluorosilicate glass, organosilicate glass obtained using trimethylsilane and dimethoxydimethylsilane as starting materials, silicon oxynitride, silica compounds such as silsesquioxane hydride, silicon carbide, Examples thereof include silicon nitride. Examples of the organic polymer include wholly aromatic low dielectric constant interlayer insulating materials. Among these, silicon dioxide is particularly preferable. These materials (for example, a film) can be formed (for example, a film) by a CVD method, a spin coating method, a dip coating method, or a spray method. Specific examples of the interlayer insulating material include an interlayer insulating material in an LSI manufacturing process, particularly a multilayer wiring forming process.

  Examples of the constituent material of the conductive substance include copper, copper alloy, copper oxide or copper alloy oxide, tungsten, tungsten alloy, silver, gold and other metals as main components, copper, copper alloy, Substances mainly composed of copper, such as copper oxide and copper alloy oxide, are preferred. As the conductive substance, the substance (for example, a film) formed by a known sputtering method or plating method can be used.

  The barrier metal is formed to prevent the constituent material of the conductive material from diffusing into the interlayer insulating material and to improve the adhesion between the interlayer insulating material and the conductive material. Examples of the barrier metal include tungsten-based metals such as tungsten, tungsten alloys, and tungsten compounds (for example, tungsten nitride); titanium-based metals such as titanium, titanium alloys, and titanium compounds (for example, titanium nitride); tantalum, tantalum alloys, and tantalum compounds (for example, Tantalum metals such as tantalum nitride); ruthenium metals such as ruthenium, ruthenium alloys and ruthenium compounds (eg ruthenium nitride); cobalt metals such as cobalt, cobalt alloys and cobalt compounds (eg cobalt nitride); manganese, manganese alloys, Manganese metals such as manganese compounds (eg, manganese nitride) are preferred, tantalum metals, cobalt metals, and ruthenium metals are more preferred, and ruthenium metals are even more preferred. The barrier metal may have a single layer structure composed of one kind of these or a laminated structure composed of two or more kinds of layers. In addition, description with "alloy" means that whose metal content exceeds 50 mass%, for example.

  As a polishing apparatus, for example, when polishing with a polishing cloth, the polishing apparatus generally includes a holder that can hold a substrate to be polished, and a polishing surface plate that is connected to a motor that can change the number of rotations and that can be attached to the polishing cloth. A typical polishing apparatus can be used. There is no restriction | limiting in particular as polishing cloth, A general nonwoven fabric, a polyurethane foam, a porous fluororesin, etc. can be used.

The polishing conditions are not limited, but the rotation speed of the surface plate is preferably a low rotation of 200 min ⁻¹ or less so that the substrate does not jump out. The pressure applied to the polishing cloth of the semiconductor substrate having the surface to be polished is preferably 1 to 100 kPa, and in order to satisfy the uniformity of the surface to be polished and the flatness of the pattern at 2 to 50 kPa. More preferably. During polishing, it is preferable to continuously supply the polishing slurry for CMP according to the present embodiment to the polishing cloth with a pump or the like. Although there is no restriction | limiting in this supply amount, it is preferable that the surface of polishing cloth is always covered with polishing liquid.

  The substrate after polishing is preferably washed in running water and then dried after removing water droplets adhering to the substrate using spin drying or the like. In addition, it is more preferable to dry after using a known cleaning method in which a commercially available cleaning solution is flowed to the surface of the substrate and a brush made of polyurethane is rotated to remove deposits on the substrate by pressing at a constant pressure. .

  In order to perform chemical mechanical polishing with the surface state of the polishing cloth always the same, it is preferable to perform a conditioning process of the polishing cloth before polishing. For example, using a dresser with diamond particles, the polishing cloth is conditioned with a liquid containing at least water. Subsequently, it is preferable to perform the polishing method according to the present embodiment and further add a substrate cleaning step.

  The polishing method according to the present embodiment is provided, for example, following an interlayer insulating material (for example, an interlayer insulating film) having convex portions (protrusions) and concave portions (grooves) on the surface, and following the surface of the interlayer insulating material. A conductive material in a substrate having a barrier metal (for example, a barrier layer) and a conductive material (for example, a conductive material layer) provided so as to cover the barrier metal is polished on the convex portion of the interlayer insulating material. A first polishing step that exposes the barrier metal located; and a first polishing step that exposes the protrusion of the interlayer insulating material by polishing the barrier metal exposed by the first polishing step using the CMP polishing liquid according to the present embodiment. 2 polishing steps. The conductive substance may cover the barrier metal so as to fill the recesses of the interlayer insulating material.

  The polishing method according to this embodiment can be suitably used in the second polishing step of polishing the barrier metal, and can suppress the occurrence of seams in the metal wiring portion.

  Next, the case where the substrate is a semiconductor substrate will be described as an example, and the polishing method according to the present embodiment will be described in more detail with reference to the drawings. An example in which a ruthenium-based metal is used when the substrate is a semiconductor substrate includes a damascene wiring formation process.

  For example, as shown in FIG. 4, there is a method using a barrier layer containing a ruthenium-based metal as a seed layer instead of a copper seed layer. In FIG. 4, reference numeral 11 denotes an interlayer insulating film, reference numeral 12 denotes a first barrier layer, reference numeral 13 denotes a second barrier layer, and reference numeral 14 denotes a conductive material layer. The barrier layer 13 includes a ruthenium metal. In the semiconductor substrate shown in FIG. 4, for example, a groove (recess) is formed on the surface of the interlayer insulating film 11, and the barrier layer 12 is formed on the interlayer insulating film 11 so as to follow the shape of the surface of the interlayer insulating film 11. Then, the barrier layer 13 is formed on the barrier layer 12 so as to follow the shape of the barrier layer 12, and finally, the conductive material layer 14 is formed on the barrier layer 13 so as to fill the recess and cover the entire surface. It is obtained by forming into. As a method for forming the barrier layer, a method other than the PVD method is preferable, at least one method selected from the group consisting of the CVD method and the ALD method is more preferable, and the CVD method is more preferable. Thereby, when forming fine wiring (for example, wiring width 15 nm or less), it can suppress further that a void | hole is produced in a wiring part, and when polishing using the polishing liquid for CMP which concerns on this embodiment, it is favorable. It becomes easy to remove the barrier layer at the polishing rate.

  Further, as shown in FIG. 5, there is a method of providing a barrier layer 13 between a seed layer 15 using a wiring metal and a barrier layer 12. That is, after forming the barrier layer 13 in FIG. 4, a step of forming the seed layer 15 using a wiring metal is added to obtain the semiconductor substrate having the structure shown in FIG.

  A process of polishing the substrate using the CMP polishing liquid according to the present embodiment will be described with reference to FIG. In FIG. 6, reference numeral 11 denotes an interlayer insulating film, reference numeral 12 denotes a first barrier layer, reference numeral 13 denotes a second barrier layer, and reference numeral 14 denotes a conductive material layer. The barrier layer 13 includes a ruthenium metal. 6A is a cross-sectional view showing a state before polishing the substrate, FIG. 6B is a cross-sectional view showing a state of the substrate after the first polishing step, and FIG. FIG. 10 is a cross-sectional view showing a state of the substrate after the second polishing step.

  First, the conductive material layer 14 is polished using a CMP polishing liquid for the conductive material to expose the barrier layer 13 existing on the convex portion of the interlayer insulating film 11, and is shown in FIG. 6B. A substrate having a structure is obtained (first polishing step). Next, the barrier layer 13 and the barrier layer 12 existing on the convex portion of the interlayer insulating film 11 and a part of the conductive material layer 14 existing in the concave portion of the interlayer insulating film 11 are polished, and the interlayer insulating film 11 is polished. The protrusion is exposed to obtain the substrate shown in FIG. 6C (second polishing step). Of these two polishing processes, it is preferable that the CMP polishing liquid according to this embodiment is used in at least the second polishing process. In order to improve the flatness, in the second polishing step, after the interlayer insulating film 11 is exposed, polishing may be continued for a predetermined time (over polishing).

  Hereinafter, the polishing method according to this embodiment will be further described by taking the formation of a wiring layer in a semiconductor device as an example.

  First, an interlayer insulating film such as silicon dioxide is laminated on a silicon substrate. Next, a concave portion (substrate exposed portion) having a predetermined pattern is formed on the surface of the interlayer insulating film by a known means such as resist layer formation or etching to form an interlayer insulating film having a convex portion and a concave portion. A barrier layer containing tantalum or the like is formed on the interlayer insulating film by vapor deposition or CVD to obtain a barrier layer that covers the interlayer insulating film along the surface irregularities. Further, a conductive material layer containing copper or the like is formed by vapor deposition, plating, CVD, or the like so as to fill the recess and cover the barrier layer. In the substrate thus obtained, the thickness of the interlayer insulating film is preferably about 0.01 to 2.0 μm, the thickness of the barrier layer is preferably about 0.001 to 0.1 μm, and the conductive material layer The thickness is preferably about 0.01 to 3.0 μm.

  Next, for example, the conductive material layer on the surface of the substrate is polished by CMP using a polishing liquid for a conductive material having a sufficiently high polishing rate ratio of the conductive material layer / barrier layer (first polishing step). ). Thus, a desired conductor pattern is obtained in which the barrier layer located on the convex portion of the interlayer insulating film is exposed on the surface and the conductive material layer is left in the concave portion. As this polishing proceeds, a part of the barrier layer located on the convex portion of the interlayer insulating film may be polished simultaneously with the conductive material layer. The pattern surface obtained by the first polishing step can be polished using the CMP polishing liquid according to the present embodiment as the surface to be polished in the second polishing step.

  In the second polishing step, the polishing surface plate and the substrate are supplied while supplying the polishing liquid for CMP according to this embodiment between the polishing cloth and the surface to be polished in a state where the surface to be polished of the obtained substrate is pressed against the polishing cloth. Are moved relative to each other to polish the barrier layer exposed in the first polishing step. The CMP polishing liquid according to the present embodiment can polish the conductive material layer, the barrier layer, and the interlayer insulating film, but in the second polishing step, at least the exposed barrier layer is polished.

  All the convex portions of the interlayer insulating film covered with the barrier layer are exposed, the conductive material layer that becomes the wiring layer (metal wiring portion) is left in the concave portion, and the cross section of the barrier layer is formed at the boundary between the convex portion and the concave portion. The polishing is finished when the desired exposed pattern is obtained.

  In order to ensure even more flatness at the end of polishing, overpolishing may be further performed to a depth including a part of the convex portion of the interlayer insulating film. For example, when the time until a desired pattern is obtained in the second polishing step is 100 seconds, polishing for an additional 50 seconds in addition to the polishing for 100 seconds is referred to as over-polishing 50%.

  An interlayer insulating film and a second-layer metal wiring are further formed on the metal wiring thus formed, and an interlayer insulating film is formed again between and on the wiring, and then polished to obtain a semiconductor substrate. A smooth surface over the entire surface. By repeating this step a predetermined number of times, a semiconductor device having a desired number of wiring layers can be manufactured.

  The CMP polishing liquid according to this embodiment can be used not only for polishing a metal film formed on a semiconductor substrate as described above, but also for polishing a substrate such as a magnetic head.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not restrict | limited to these Examples, unless it deviates from the technical idea of this invention. For example, the material type and blending ratio of the polishing liquid may be other than the type and ratio described in this example, and the composition and structure of the polishing target may be other than the composition and structure described in this example.

[Preparation of polishing liquid for CMP]
Example 1
0.10 parts by mass of potassium bromate, 0.20 parts by mass of 30% by mass hydrogen peroxide (0.06 parts by mass as hydrogen peroxide), 0.40 parts by mass of glycolic acid, an average particle diameter of 60 nm and about 5.00 parts by mass of commercially available colloidal silica having a zeta potential of +20 mV, 0.20 parts by mass of benzotriazole, 0.80 parts by mass of 3-methyl-3-methoxybutanol, and 95.00 parts by mass of water were weighed and mixed. , Stirred to prepare a polishing liquid 1 for CMP.

(Examples 2 to 12)
Each component shown in Table 1 was weighed, mixed and stirred, and operated in the same manner as in Example 1 to prepare CMP polishing liquids 2 to 12.

(Examples 13 to 21)
Each component shown in Table 2 was weighed, mixed and stirred, and operated in the same manner as in Example 1 to prepare CMP polishing liquids 13 to 21.

(Comparative Example 1)
0.10 parts by mass of nitric acid, 0.20 parts by mass of 30% by weight hydrogen peroxide (0.06 parts by mass as hydrogen peroxide), 0.40 parts by mass of glycolic acid, an average particle size of 60 nm and about +20 mV 5.00 parts by mass of commercially available colloidal silica having zeta potential, 0.20 parts by mass of benzotriazole, 0.80 parts by mass of 3-methyl-3-methoxybutanol, and 95.00 parts by mass of water are weighed, mixed, and stirred. Then, a polishing liquid 22 for CMP was produced.

(Comparative Examples 2-7)
Each component shown in Table 3 was weighed, mixed and stirred, and operated in the same manner as in Comparative Example 1 to prepare CMP polishing liquids 23 to 28.

(Comparative Examples 8 and 9)
Each component shown in Table 4 was weighed, mixed and stirred, and operated in the same manner as in Comparative Example 1 to prepare CMP polishing liquids 29 and 30.

(Examples 22 to 30)
Each component shown in Table 5 was weighed, mixed and stirred, and operated in the same manner as in Example 1 to prepare CMP polishing liquids 31 to 39.

(Comparative Examples 10 and 11)
Each component shown in Table 6 was weighed, mixed and stirred, and operated in the same manner as Comparative Example 1 to prepare CMP polishing liquids 40 and 41.

(Examples 31-38)
Each component shown in Table 6 and Table 7 was weighed, mixed and stirred, and operated in the same manner as in Example 1 to prepare CMP polishing liquids 42 to 49.

(Comparative Example 12)
Each component shown in Table 7 was weighed, mixed and stirred, and operated in the same manner as in Comparative Example 1 to prepare a polishing slurry 50 for CMP.

[Evaluation of polishing liquid for CMP]
(Evaluation of pH)
The pH in CMP polishing liquids 1 to 50 was measured using a product name: PH81 manufactured by Yokogawa Electric Corporation. Standard buffers (phthalate pH buffer pH: 4.01 (25 ° C.), neutral phosphate pH buffer pH 6.86 (25 ° C.) and borate pH buffer pH 9.12 (25 ° C.)) After calibrating three points using the electrode, the electrode was placed in the CMP polishing liquid, and the value (25 ° C.) after 2 minutes or more of stabilization was taken as the pH of the CMP polishing liquid.

(Evaluation of zeta potential)
The zeta potential of the abrasive grains in the polishing liquids 1 to 50 for CMP was measured using Spectris Co., Ltd., trade name: Zetasizer 3000 HS. As a result, the zeta potential in the CMP polishing liquids 23, 24, 26 and 28 was less than +10 mV, whereas the zeta potential in the CMP polishing liquids 1 to 22, 25, 27 and 29 to 50 was +20 mV or more. Indicated.

(Evaluation of average particle size)
0.2 g of the CMP polishing liquid was weighed out and diluted with 99.8 g of water (500-fold dilution) to prepare a measurement sample. Next, this measurement sample was put into a dynamic light scattering particle size distribution analyzer (manufactured by BECKMAN COULTER, trade name: COULTER N5 type) for measurement, and a value obtained as D50 was obtained as an average particle size. As a result, the average particle diameter in CMP polishing liquids 23, 24, 26, and 28 exceeded 100 nm, whereas the average particle diameter in CMP polishing liquids 1-22, 25, 27, and 29-50 was 10 ˜100 nm.

[Evaluation of polishing characteristics]
(Production of blanket substrate)
The following substrate was cleaved into small pieces of 20 mm × 20 mm and used for the following polishing.
Ruthenium blanket substrate: A silicon substrate on which a ruthenium film (thickness: about 90 mm) is formed by CVD.

(Substrate polishing process)
Using the CMP polishing liquid, the blanket substrate was subjected to chemical mechanical polishing for 60 seconds under the following polishing conditions.

{Polishing conditions}
Polishing apparatus: manufactured by Nano Factor Co., Ltd., trade name: FACT-200
Polishing pad: Rohm and Haas Electronic Materials CMP, trade name: VP-3200
Surface plate rotation speed: 80 min ^-1
Polishing pressure: 10 kPa
Supply amount of polishing liquid: 8 ml / min

(Evaluation of ruthenium polishing rate)
The polishing rate of the ruthenium blanket substrate polished under the above conditions was determined from the difference in film thickness of the ruthenium film before and after polishing. The film thickness of the ruthenium film was obtained by converting from the value of the sheet resistance obtained using a 4-probe resistance measuring instrument. The results are shown in Tables 1-7.

  Tables 1 to 7 show the composition of the polishing liquid for CMP and the measurement results. In Tables 1, 2, 5, and 6, the CMP polishing liquids of Examples and Comparative Examples marked with “*” separately contain hydrogen peroxide and sulfuric acid generated by decomposition of peroxodisulfuric acid. .

  As shown in Tables 1, 2, and 5 to 7, the polishing slurry for CMP contains a first metal oxidant (hydrogen peroxide) and a second metal oxidant, and the second metal oxidant is a hydrogen ion. The oxidation-reduction potential with respect to the standard hydrogen electrode is 0.68 to 3.10 V, and the abrasive content is the content of the abrasive grains and the water. When the content is 0.1 parts by mass or more with respect to a total of 100 parts by mass and the pH is 2.50 or more and less than 7.00, the ruthenium polishing rate is 5 Å / min or more and becomes a high polishing rate. You can see that

  On the other hand, as shown in Tables 3, 4, 6, and 7, in the comparative example, the ruthenium polishing rate is less than 5 ｍｉｎ / min, and may not be suitable as a polishing slurry for CMP for polishing ruthenium-based metals. Recognize. Further, in Comparative Examples 2, 3, 5 and 7 in Table 3, since the CMP polishing solution had a pH of less than 2.0, the CMP polishing solution had a zeta potential of +10 mV or less. It has been confirmed that it easily aggregates and is not suitable for practical storage stability.

  ADVANTAGE OF THE INVENTION According to this invention, the high grinding | polishing speed | rate of the barrier metal used for a barrier layer is realizable in the wiring formation process of a semiconductor device.

  DESCRIPTION OF SYMBOLS 1 ... Insulating material, 2 ... Groove part (concave part), 3 ... Wiring metal, 4 ... Barrier metal, 5,15 ... Seed layer, 6 ... Metal (barrier metal or seed layer), 7 ... Void (void), 11 ... Interlayer insulating film, 12 ... first barrier layer, 13 ... second barrier layer, 14 ... conductive material layer.

Claims (13)

A polishing liquid for CMP for polishing a ruthenium-based metal,
Contains hydrogen peroxide, a metal oxidizer (except for hydrogen peroxide), a metal oxide solubilizer, abrasive grains, and water.
The metal oxidant has an oxidation-reduction potential with the exchange of hydrogen ions;
The oxidation-reduction potential is 0.68 to 3.10 V with respect to a standard hydrogen electrode;
PH of the polishing liquid for CMP is 2.5 or more and less than 7.0,
Polishing liquid for CMP whose content of the said abrasive grain is 0.10 mass part or more with respect to a total of 100 mass parts of content of the said abrasive grain, and content of the said water.   The polishing slurry for CMP according to claim 1, wherein the ruthenium-based metal includes at least one selected from the group consisting of ruthenium, a ruthenium alloy, and a ruthenium compound.   The metal oxidant is at least one selected from the group consisting of nitric acid, bromic acid, sulfuric acid, peroxodisulfuric acid, hypochlorous acid, permanganic acid, iodic acid, periodic acid, perchloric acid, and salts thereof. The polishing slurry for CMP according to claim 1, comprising:   The metal oxidant includes at least one selected from the group consisting of ammonium nitrate, potassium bromate, ammonium peroxodisulfate, potassium peroxodisulfate, sodium hypochlorite, potassium permanganate, and potassium periodate. The polishing liquid for CMP as described in any one of 1-3.   The total content of the hydrogen peroxide and the metal oxidant is 0.01 to 25.00 parts by mass with respect to a total of 100 parts by mass of the abrasive content and the water content. Polishing liquid for CMP as described in any one of Claims 1-4.   The polishing slurry for CMP according to any one of claims 1 to 5, wherein the metal oxide dissolving agent contains an organic acid.   The polishing slurry for CMP according to any one of claims 1 to 6, further comprising a metal anticorrosive.   The metal anticorrosive comprises at least one selected from the group consisting of a compound having an imidazole skeleton, a compound having a triazole skeleton, a compound having a tetrazole skeleton, a compound having a pyrazole skeleton, and a compound having a pyrimidine skeleton, Item 8. A polishing slurry for CMP according to Item 7.   The polishing slurry for CMP according to any one of claims 1 to 8, further comprising an organic solvent. An interlayer insulating film having a raised portion and a groove on the surface; a barrier layer provided following the surface of the interlayer insulating film; and a conductive material layer provided so as to cover the barrier layer. A first polishing step of polishing the conductive material layer on the substrate to expose the barrier layer located on the raised portion of the interlayer insulating film;
The second barrier layer exposed by the first polishing step is polished using the CMP polishing liquid according to claim 1 to expose the raised portion of the interlayer insulating film. A polishing method comprising: a polishing step.   The polishing method according to claim 10, wherein the interlayer insulating film includes at least one selected from the group consisting of a silicon-based compound and an organic polymer.   The polishing method according to claim 10 or 11, wherein the conductive material layer includes at least one selected from the group consisting of copper, a copper alloy, a copper oxide, and a copper alloy oxide.   The polishing method according to any one of claims 10 to 12, wherein the barrier layer contains at least one selected from the group consisting of ruthenium, a ruthenium alloy, and a ruthenium compound.

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