Semiconductor wiring polishing composition

Abstract

The present invention provides a composition for polishing semiconductor wiring, the composition having exceptional polishing speed and being such that the occurrence of dishing is suppressed.　This composition for polishing semiconductor wiring includes a compound represented by formula (1).　Formula (1): R1O-(C3H6O2)n-H (In the formula, R1 represents a hydrogen atom, a C1-24 hydrocarbon group that optionally has a hydroxyl group, or R2CO, and R2 represents a C1-24 hydrocarbon group. n represents the average degree of polymerization of glycerol units indicated in parentheses, and is 2-60.)

Description

[Technical field]

[0001] The present invention relates to a composition for polishing semiconductor wiring. This application claims priority from Japanese Patent Application No. 2019-054531, filed in Japan on March 22, 2019, the contents of which are incorporated herein by reference. [Background technology]

[0002] In recent years, copper-containing metals (e.g., copper, copper alloys, etc.) have been used as wiring materials in semiconductor wiring processes. Usually, when copper-containing metals are used as wiring materials, a copper wiring structure is formed by a method using chemical mechanical polishing (hereinafter sometimes referred to as "CMP") or the like.

[0003] Specifically, first, a barrier layer made of a tantalum-containing compound such as Ta or TaN is formed on the surface of an insulator layer of a semiconductor wafer having a trench (wiring groove), and then a conductor layer made of a copper-containing metal is formed on the barrier layer so as to completely fill at least the trench.

[0004] Then, a polishing step is performed. In the first polishing step, a portion of the conductor layer is polished. In the next polishing step, the conductor layer is polished until the barrier layer in the areas other than the trenches is exposed. The barrier layer in the areas other than the trenches is then also removed by polishing to expose the insulator layer. This forms a copper wiring portion on the semiconductor wafer.

[0005] The polishing composition used for forming the above-mentioned semiconductor wiring is required to have two contradictory functions. The first is to be able to quickly remove the conductor layer, i.e., to have an excellent polishing speed. The second is to suppress the occurrence of dishing (dish-shaped depressions) on the wiring metal surface.

[0006] Such polishing compositions disclosed include those containing two types of polyether-type nonionic surfactants with different HLB values ​​and abrasive particles (e.g., Patent Document 1), and those containing a tetraazole compound and an oxidizing agent (e.g., Patent Document 2). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2006-49709 A [Patent Document 2] JP 2006-49790 A Summary of the Invention [Problem to be solved by the invention]

[0008] However, even when the polishing compositions disclosed in Patent Documents 1 and 2 are used, the above-mentioned two conflicting functions are not fully satisfied, and there is still room for improvement. In particular, since copper is a soft metal, the center of the trench surface is polished more deeply during polishing, and dishing is likely to occur.

[0009] SUMMARY OF THE PRESENT EMBODIMENT An object of the present invention is to provide a composition for polishing semiconductor wiring which has an excellent polishing rate and suppresses the occurrence of dishing. Another object of the present invention is to provide a polishing method including a step of polishing a semiconductor wafer having an insulator layer with a trench on its surface and a conductor layer formed on the surface of the insulator layer using a semiconductor wiring polishing composition that has an excellent polishing rate and suppresses the occurrence of dishing. Another object of the present invention is to provide a method for manufacturing a semiconductor device, which includes a step of polishing a semiconductor wafer having an insulator layer with a trench on its surface and a conductor layer formed on the surface of the insulator layer, using a semiconductor wiring polishing composition that has an excellent polishing rate and suppresses the occurrence of dishing. [Means for solving the problem]

[0010] As a result of intensive research to solve the above problems, the present inventors have found that a semiconductor wiring polishing composition containing a compound represented by the following formula (1) has an excellent polishing rate and suppresses the occurrence of dishing. The present invention has been completed based on these findings.

[0011] That is, the present invention provides a semiconductor wiring polishing composition (hereinafter, sometimes referred to as "the polishing composition of the present invention") containing a compound represented by the following formula (1). R 1 O-(C3H6O2) n -H (1) (In the formula, R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms which may have a hydroxyl group, or R 2 CO, wherein R 2 represents a hydrocarbon group having 1 to 24 carbon atoms. n represents the average degree of polymerization of the glycerin unit shown in parentheses, which is 2 to 60.

[0012] The semiconductor wiring polishing composition is preferably such that the water contact angle of the copper plate surface after polishing the copper plate under the polishing conditions described below is 20° or less. [Polishing conditions] Using a polishing apparatus, the polishing composition was supplied to a polyurethane laminated polishing pad at a supply rate of 200 mL / min, and the copper plate was polished for 60 seconds while applying a polishing pressure of 13.8 kPa to the copper plate by rotating both the polishing platen and the carrier at 100 rpm.

[0013] It is preferable that the semiconductor wiring polishing composition has a ratio of the polishing rate (nm / min) determined under the test condition 1 below to the dishing amount (nm) determined under the test condition 2 below [polishing rate (nm / min) / dishing amount (nm)] of 10 or more. [Test condition 1] Using a polishing machine, the polishing composition is supplied to a polyurethane laminated polishing pad at a supply rate of 200 mL / min, and the copper plate is polished for 60 seconds while applying a polishing pressure of 13.8 kPa to the copper plate by rotating both the polishing plate and the carrier at 100 rpm. After the polishing is completed, the polishing rate (nm / min) is calculated from the difference in thickness of the copper plate before and after polishing. [Test condition 2] Using a polishing machine, the polishing composition is supplied to a polyurethane laminated polishing pad at a supply rate of 200 mL / min, and a copper pattern wafer having a conductor layer made of copper provided on an insulator layer having a trench on its surface via a barrier layer is polished by rotating both the polishing platen and the carrier at 100 rpm while applying a polishing pressure of 13.8 kPa to the copper pattern wafer having a conductor layer made of copper provided on an insulator layer having a trench on its surface via a barrier layer, until the upper surface of the barrier layer is exposed. After polishing, the dishing amount (nm) is calculated from the step between the trench on the copper pattern wafer surface and the upper surface of the barrier layer.

[0014] The semiconductor wiring polishing composition preferably further contains an anionic surfactant.

[0015] The semiconductor interconnect polishing composition preferably contains the compound represented by formula (1) in an amount of 0.01 to 20 g / L.

[0016] In the semiconductor wiring polishing composition, the compound represented by formula (1) preferably has a weight average molecular weight of 100 to 3,000.

[0017] In the semiconductor wiring polishing composition, the compound represented by formula (1) preferably has an HLB value of 14 or more.

[0018] The semiconductor wiring polishing composition further contains an oxidizing agent, and the content of the oxidizing agent is preferably 1 to 50 parts by weight per 1 part by weight of the compound represented by formula (1).

[0019] The semiconductor wiring polishing composition preferably further contains abrasive grains, and the content of the abrasive grains is preferably 1 to 50 parts by weight per 1 part by weight of the compound represented by formula (1).

[0020] It is preferable that the semiconductor wiring polishing composition further contains an oxidizing agent and abrasive grains, the ratio of the content of the oxidizing agent to the abrasive grains (oxidizing agent / abrasive grains; weight ratio) is 20 / 80 to 80 / 20, and the total content of the oxidizing agent and the abrasive grains is 5 to 100 parts by weight per 1 part by weight of the compound represented by formula (1).

[0021] The present invention also provides a polishing method (hereinafter sometimes referred to as the "polishing method of the present invention") comprising a step of polishing a semiconductor wafer having an insulator layer with a trench on its surface and a conductor layer formed on the surface of the insulator layer using the semiconductor wiring polishing composition.

[0022] The present invention also provides a method for manufacturing a semiconductor device (hereinafter sometimes referred to as the "method for manufacturing a semiconductor device of the present invention"), which includes a step of polishing a semiconductor wafer having an insulator layer with a trench on its surface and a conductor layer formed on the surface of the insulator layer using the semiconductor wiring polishing composition.

[0023] In this specification, the term "semiconductor wiring" refers to a semiconductor wafer having a trench (wiring groove) formed by laminating a conductor layer containing a copper-containing metal on the surface of an insulator layer of the semiconductor wafer having a trench (wiring groove), and then removing the conductor layer outside the trench to fill the trench with the conductor layer. Effect of the Invention

[0024] According to the present invention, a semiconductor wiring polishing composition having excellent polishing speed and suppressed dishing can be obtained. In addition, the composition has excellent wettability and good compatibility with the copper plate surface, so that a high polishing speed can be maintained. Therefore, the composition can be suitably used in the semiconductor wiring process.

[0025] In addition, by using the polishing composition of the present invention, a polishing process can be carried out with an excellent polishing rate and with the occurrence of dishing suppressed, thereby realizing efficient production of high-quality semiconductor wafers and semiconductor devices. [Brief description of the drawings]

[0026] [Figure 1] FIG. 11 is a schematic cross-sectional view of a semiconductor wafer for explaining the amount of dishing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] Specific embodiments of the present invention will now be described. 1. Polishing composition for semiconductor wiring The polishing composition of the present invention is a polishing composition that can be suitably used in a semiconductor wiring process. The polishing composition of the present invention contains a compound represented by the following formula (1) (hereinafter, sometimes referred to as a "polyglycerin derivative") as an essential component.

[0028] (Compound represented by formula (1)) R 1 O-(C3H6O2) n -H (1) (In the formula, R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms which may have a hydroxyl group, or R 2 CO, wherein R 2 represents a hydrocarbon group having 1 to 24 carbon atoms. n represents the average degree of polymerization of the glycerin unit shown in parentheses, which is 2 to 60.

[0029] The C3H6O2 in the parentheses of formula (1) may have only the structure shown in formula (2) below, may have only the structure shown in formula (3) below, or may have both the structures shown in formulas (2) and (3) below. -CH2-CHOH-CH2O- (2) -CH(CHOH)CHO- (3)

[0030] R 1 In one molecule, 5 to 75% of the atoms are hydrogen.

[0031] R 1 , R 2The hydrocarbon group in the formula (I) includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining two or more of these groups.

[0032] Examples of the aliphatic hydrocarbon group include linear or branched alkyl groups having 1 to 24 carbon atoms (preferably 5 to 20, more preferably 10 to 20, and even more preferably 12 to 18), such as a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, an isooctyl group, a decyl group, an isodecyl group, a dodecyl group, a tetradecyl group, an isododecyl group, a myristyl group, an isomyristyl group, a cetyl group, an isocetyl group, a stearyl group, and an isostearyl group; and a vinyl group. linear or branched alkenyl groups having 2 to 24 carbon atoms (preferably 10 to 20, and more preferably 8 to 18), such as a propenyl group, an allyl group, a hexenyl group, a 2-ethylhexenyl group, or an oleyl group; linear or branched alkapolyenyl groups having 2 to 24 carbon atoms (preferably 2 to 18), such as an alkadienyl group, an alkatrienyl group, an alkatetranyl group, a linoleyl group, or a linolenyl group; linear or branched alkynyl groups having 2 to 24 carbon atoms, such as an ethynyl group, or a propynyl group.

[0033] As the alkyl group, a linear or branched alkyl group having 8 to 18 carbon atoms (particularly preferably having 8 to 15 carbon atoms, and particularly preferably having 10 to 15 carbon atoms), such as a dodecyl group or an isostearyl group, is preferred. Furthermore, as the alkenyl group, a linear or branched alkenyl group having 8 to 18 carbon atoms, such as a hexenyl group or an oleyl group, is preferred.

[0034] Examples of the alicyclic hydrocarbon group include 3- to 24-membered (preferably 3- to 15-membered, particularly preferably 5- to 8-membered) cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclooctyl group; 3- to 24-membered (preferably 3- to 15-membered, particularly preferably 5- to 8-membered) cycloalkenyl groups such as a cyclopentenyl group and a cyclohexenyl group; perhydronaphthalene-1-yl group, a norbornyl group, an adamantyl group, a tricyclo[5.2.1.0 2,6]decan-8-yl group, tetracyclo[4.4.0.1 2,5 .1 7,10 ]Dodecan-3-yl group and other bridged cyclic hydrocarbon groups.

[0035] Examples of the aromatic hydrocarbon group include aryl groups having 6 to 24 carbon atoms (preferably 6 to 15 carbon atoms), such as a phenyl group and a naphthyl group.

[0036] The hydrocarbon group formed by combining an aliphatic hydrocarbon group and an alicyclic hydrocarbon group includes a cycloalkyl-substituted alkyl group such as a cyclopentylmethyl group, a cyclohexylmethyl group, or a 2-cyclohexylethyl group (for example, C 3-20 Cycloalkyl-substituted C 1-4 In addition, the hydrocarbon group formed by combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group includes an aralkyl group (e.g., C 7-18 Aralkyl groups, etc.), alkyl-substituted aryl groups (e.g., 1 to 4 C 1-4 A phenyl group or a naphthyl group substituted with an alkyl group, etc.

[0037] R 2 Examples of the group represented by CO include aliphatic acyl groups such as acetyl, propionyl, butyryl, isobutyryl, stearoyl, and oleoyl groups; and aromatic acyl groups such as benzoyl, toluoyl, and naphthoyl groups.

[0038] R 1 Among them, R is preferably at least one selected from the group consisting of an alkyl group, an acyl group, and a hydrogen atom. 1 It is particularly preferable that the alkyl group is at least one selected from the group consisting of a linear alkyl group (particularly, a methyl group, an ethyl group, a propyl group, a decyl group, or a stearyl group, and particularly, a methyl group), an aliphatic acyl group (particularly, an acetyl group, a butyl group, a stearoyl group, or an oleoyl group, and particularly, an acetyl group or an oleoyl group), and a hydrogen atom.

[0039] R1 Among them, a linear or branched alkyl group is preferable because it can improve the polishing rate while suppressing the occurrence of dishing, and a linear or branched alkyl group having 8 to 18 carbon atoms is particularly preferable, and a linear or branched alkyl group having 8 to 15 carbon atoms is particularly preferable.

[0040] In formula (1), n ​​represents the average degree of polymerization of glycerin. As shown in the method for producing the compound represented by formula (1) described later, for example, when producing a polyglycerol ether from an alcohol and glycidol, the value of n can be easily changed by adjusting the molar ratio of the reacting alcohol and 2,3-epoxy-1-propanol (trade name "Glycidol", manufactured by Daicel Corporation).

[0041] The average degree of polymerization n is, for example, 2 to 60, preferably 2 to 40, more preferably 4 to 20, and even more preferably 4 to 10. When n is 2 or more, water solubility is further improved, and cleaning properties are also excellent. In addition, the adsorption to the polished metal surface is good, and the formation of a hydrophilic coating is also excellent. When n is 60 or less, good hydrophilicity is exhibited, and water dispersibility is further improved. Unnecessary foaming is suppressed, and workability is further improved. In this specification, the method for calculating the average degree of polymerization of glycerin constituting polyglycerin is not particularly limited, and examples thereof include a method of calculating from a hydroxyl value, a method of determining the composition of polyglycerin by gas chromatography, liquid chromatography, thin layer chromatography, gas chromatography mass spectrometry, liquid chromatography mass spectrometry, or the like, and a method of calculating the average degree of polymerization.

[0042] Examples of the metal to be polished include copper, silver, gold, zinc, tin, palladium, nickel, cobalt, chromium, manganese, titanium, aluminum, and alloys of two or more metals selected from these metals. Among these, copper or a copper alloy is preferable.

[0043] The average degree of polymerization n in formula (1) is preferably 5 to 9, more preferably 5 to 8, and particularly preferably 5 to 7, in that the polishing rate can be improved while the occurrence of dishing is suppressed.

[0044] The weight average molecular weight of the compound represented by formula (1) is, for example, 100 to 3000. In particular, from the viewpoint of good adsorption to the polished metal surface and excellent formation of a hydrophilic coating, it is preferably 200 to 3000, more preferably 200 to 2000, even more preferably 300 to 2000, and most preferably 400 to 1500. In addition to the above viewpoint, from the viewpoint of excellent workability, it is more preferably 400 to 1000, and most preferably 400 to 800. In this specification, the weight average molecular weight is measured by gel permeation chromatography (GPC).

[0045] From the viewpoint of excellent dispersion stability, the compound represented by formula (1) has an HLB (hydrophile-lipophile balance) value of, for example, 14 or more, preferably 14 to 20, and more preferably 14 to 18. The HLB value can be calculated by the Griffin method.

[0046] As the compound represented by formula (1) in the present invention, at least one selected from the compounds represented by the following formulae (1-1) to (1-7) is preferable, and at least one selected from the compounds represented by the following formulae (1-1) to (1-4), (1-6), and (1-7) is particularly preferable. C 12 H 25 O-(C3H6O2)4-H (1-1) C 12 H 25 O-(C3H6O2) 10 -H (1-2) C 18 H 37 -O-(C3H6O2)4-H (1-3) C 18 H 37 -O-(C3H6O2) 10 -H (1-4) CH2=CH-CH2-O-(C3H6O2)6-H (1-5) HO-(C3H6O2) 10 -H (1-6) HO-(C3H6O2) 20 -H (1-7)

[0047] As a method for producing the compound represented by formula (1) in the present invention, for example, 1 Compounds represented by the formula (R 1 (The same as above) and 2,3-epoxy-1-propanol are added to the polyglycerin. 1 A compound represented by X (wherein X represents a halogen atom). 1 is the same as above. For example, a method of reacting a polyglycerin with an alkyl halide, an acid halide, etc., [3] a method of reacting a polyglycerin with a reactive derivative of a carboxylic acid such as an acid anhydride, etc., and [4] a method of reacting a polyglycerin with the following formula (4) [ka] (In the formula, R 1 is the same as above) and a method of reacting the compound with a polyol such as a glycidyl ether compound represented by the following formula:

[0048] Examples of the alkali catalyst used in the above method [1] include sodium hydroxide, potassium hydroxide, lithium hydroxide, metallic sodium, sodium hydride, etc. These may be used alone or in combination of two or more.

[0049] Examples of the alkyl halide used in the above method [2] include alkyl chloride, alkyl bromide, and alkyl iodide.

[0050] As the polyglycerin used in the above methods [2] to [4], for example, commercially available products such as "PGL 03P (polyglycerin trimer)", "PGL 06 (polyglycerin hexamer)", "PGL 10PSW (polyglycerin decamer)", and "PGL XPW (polyglycerin 40mer)" (manufactured by Daicel Corporation) can be suitably used.

[0051] Examples of the polyol used in the above method [4] include 2,3-epoxy-1-propanol, ethylene glycol, propylene glycol, 1,3-propanediol (trimethylene glycol), glycerin, xylitol, and sorbitol.

[0052] The polishing composition of the present invention contains at least one compound represented by the above formula (1). As described above, the compound represented by the above formula (1) includes polyglycerin, polyglycerin monoether, and polyglycerin monoester. Therefore, the polishing composition of the present invention contains at least one polyglycerin derivative selected from polyglycerin, polyglycerin monoether, and polyglycerin monoester.

[0053] The polishing composition of the present invention may contain, as the polyglycerin derivative, polyglycerin, polyglycerin monoether, and polyglycerin monoester, for example, polyglycerin diether or polyglycerin diester corresponding to the above-mentioned compound. In the polishing composition of the present invention, the total content of polyglycerin, polyglycerin monoether, and polyglycerin monoester is preferably 75% by weight or more, more preferably 90% by weight or more, of the total amount of polyglycerin derivatives contained in the polishing composition of the present invention, from the viewpoint of imparting good hydrophilicity. In addition, the total content of polyglycerin diether and polyglycerin diester is preferably 5% by weight or less, particularly preferably 1% by weight or less, of the total amount of polyglycerin derivatives contained in the polishing composition of the present invention. The content of each component contained in the polyglycerin derivative is obtained by separating each component by high performance liquid chromatography, calculating the peak area with a differential refractive index detector, and calculating the area ratio.

[0054] The content (g / L) of the compound represented by the above formula (1) in the polishing composition of the present invention is not particularly limited, but is preferably 0.01 g / L or more, more preferably 0.05 g / L or more, even more preferably 0.1 g / L or more, and most preferably 0.3 g / L or more. When the content of the compound represented by the above formula (1) is in the above range, a hydrophilic film is formed on the metal to be polished, and excessive decrease in the polishing rate is further suppressed. In addition, the content of the compound represented by the above formula (1) is preferably 20 g / L or less, more preferably 10 g / L or less, even more preferably 5 g / L or less, and most preferably 3 g / L or less. When the content of the compound represented by the above formula (1) is in the above range, the occurrence of dishing is further suppressed while maintaining the polishing power. The content of the compound represented by the above formula (1) is the total content of all the compounds represented by the above formula (1) in the polishing composition of the present invention.

[0055] (Other ingredients) Anionic surfactants: The polishing composition of the present invention preferably further contains an anionic surfactant from the viewpoint of maintaining a high polishing rate and further suppressing the occurrence of dishing. Only one type of anionic surfactant may be used, or two or more types may be used.

[0056] The anionic surfactant preferably contains a compound represented by the following formula (5) and / or the following formula (6). R 3 -Y 1 (5) R 3 -X 1 -Y 1 (6) (Wherein, R 3 represents an alkyl group, an alkenyl group, or an aryl group; X 1 represents a polyoxyalkylene group; Y 1 indicates an anionic functional group)

[0057] R 3 Examples of the alkyl group in the formula (I) include linear or branched alkyl groups having 1 to 20 carbon atoms (preferably 5 to 15, and particularly preferably 8 to 12), such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a decyl group, and a dodecyl group.

[0058] R 3 Examples of the alkenyl group in the formula include alkenyl groups having about 2 to 20 carbon atoms, such as a vinyl group, an allyl group, a 1-butenyl group, and an oleyl group.

[0059] R 3 In the above, examples of the aryl group include aryl groups having 6 to 10 carbon atoms, such as a phenyl group and a naphthyl group. The aryl group may have a substituent bonded thereto. Examples of the substituent include C 1-5 Alkyl group, C 1-5 An example of an aryl group having a substituent is a tolyl group.

[0060] Y 1 The anionic functional group is preferably a residue of carboxylic acid, phosphoric acid, phosphorous acid, sulfuric acid, sulfurous acid, sulfonic acid, or a salt thereof, and among these, a sulfate residue, a sulfurous acid residue, a sulfonic acid residue, or a salt thereof is preferable, in terms of being able to improve the polishing rate while suppressing the occurrence of dishing. In addition, the compound represented by the above formula (5) or the above formula (6) may contain a counter ion such as an ammonium cation, an amine cation, or an alkali metal cation (e.g., a lithium cation, a sodium cation, a potassium cation, etc.). Among these, from the viewpoint of improving the polishing rate, it is preferable to be at least one selected from the group consisting of potassium cation, ammonium cation, and amine cation, more preferably ammonium cation or triethanolamine cation, and most preferably ammonium cation.

[0061] X in the above formula (6) 1 The polyoxyalkylene group in is, for example, [(OR 4 ) t The R 4 represents an alkylene group having 1 to 4 carbon atoms (preferably, an alkylene group having 2 to 4 carbon atoms). 4 ) is the average number of repetitions of t R 4 may be the same or different.

[0062] Specific examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, and a poly(oxyethylene-oxypropylene) group.

[0063] The average number of repetitions t is not particularly limited, but is, for example, a number not greater than 6. The upper limit of the average number of repetitions t is preferably 4, more preferably 3, particularly preferably 2.5, and most preferably 2. The lower limit of the average number of repetitions t is, for example, 0.5, preferably 1. By having the average number of repetitions t within the above range, the occurrence of metal corrosion (called "slits") at the wiring edge portions in the conductor layer is further suppressed.

[0064] When the polishing composition of the present invention contains an anionic surfactant, the mechanism by which a hydrophilic coating is formed on the surface of a metal to be polished is presumed to be as follows. However, the mechanism of the present invention is not limited to the following presumption.

[0065] The polyglycerin derivative contained in the polishing composition of the present invention has the effect of adsorbing to the hydrophobic surface of the protective film formed on the polished metal surface by the anionic surfactant to form a protective film. The hydrophobic portion of the polyglycerin derivative is bonded to the hydrophobic surface of the protective film formed by the anionic surfactant, and the hydrophilic portion of the polyglycerin derivative is located on the opposite side to the hydrophobic surface of the protective film formed by the anionic surfactant. Therefore, the surface of the protective film formed by the polyglycerin derivative on the hydrophobic surface of the protective film formed by the anionic surfactant has hydrophilicity. When a protective film (hydrophilic film) made of polyglycerin is formed on the hydrophobic surface of the protective film formed by the anionic surfactant, the affinity with the polished surface is improved, and the polishing rate of the polished surface by the polishing composition of the present invention is improved. As a result, the polishing rate of the polished metal surface by the polishing composition of the present invention is suppressed from excessively decreasing even by the use of the anionic surfactant.

[0066] When the polishing composition of the present invention contains an anionic surfactant, the content (g / L) of the anionic surfactant in the polishing composition of the present invention is not particularly limited, but is preferably 0.01 g / L or more, more preferably 0.03 g / L or more, even more preferably 0.05 g / L or more, even more preferably 0.08 g / L or more, and most preferably 0.1 g / L or more. When the content of the anionic surfactant is within the above range, a protective film sufficient to suppress excessive polishing is formed on the polished metal surface, and dishing occurrence is further suppressed. In addition, the content of the anionic surfactant is preferably 10 g / L or less, more preferably 5 g / L or less, even more preferably 1 g / L or less, even more preferably 0.5 g / L or less, and most preferably 0.3 g / L or less. When the content of the anionic surfactant is within the above range, the protective film formed on the polished metal surface becomes moderately thick, and the polishing rate is further maintained. The content of the anionic surfactant is the total content of all anionic surfactants in the polishing composition of the present invention.

[0067] The content of the anionic surfactant is, for example, 0.05 to 1.00 parts by weight, preferably 0.1 to 0.8 parts by weight, and particularly preferably 0.2 to 0.5 parts by weight, relative to 1 part by weight of the compound represented by formula (1).

[0068] Protective Film Forming Agent: From the viewpoint of further suppressing the occurrence of dishing, the polishing composition of the present invention preferably further contains a protective film forming agent. The protective film forming agent has the effect of adsorbing to the surface of the polished surface to form a protective film. The surface of the protective film formed by this protective film forming agent is hydrophobic. When the protective film is formed, the affinity with the polished metal surface decreases, and the polishing speed decreases. As a result, even when polishing at a high speed, excessive removal of the polished metal surface is suppressed, and the occurrence of dishing is further suppressed. Note that the protective film forming agent does not include the above-mentioned polyglycerin derivative or anionic surfactant. The protective film forming agent may be used alone or in combination with two or more types.

[0069] The protective film forming agent may be, for example, benzotriazole or a benzotriazole derivative. The benzotriazole derivative is a compound in which the hydrogen atom bonded to the five-membered ring of benzotriazole is replaced with another atomic group. Among them, in the polishing composition of the present invention, from the viewpoint of more effectively suppressing the occurrence of dishing, benzotriazole is preferred.

[0070] The protective film made of benzotriazole has a hydrophobic surface because the five-membered ring portion of the benzotriazole is bonded to the surface of the metal to be polished and the benzene ring portion of the benzotriazole is located on the opposite side of the surface of the metal to be polished (copper or copper alloy). The protective film made of a benzotriazole derivative has a hydrophobic surface because the five-membered ring portion of the benzotriazole derivative is bonded to the surface of the metal to be polished and the benzene ring portion of the benzotriazole derivative is located on the opposite side of the surface of the metal to be polished.

[0071] When the polishing composition of the present invention contains a protective film forming agent, the content (g / L) of the protective film forming agent in the polishing composition of the present invention is not particularly limited, but is preferably 0.001 g / L or more, more preferably 0.01 g / L or more. By the content of the protective film forming agent being within the above range, a protective film sufficient to strongly suppress excessive polishing of the polished metal surface is formed on the polished metal surface, and the occurrence of dishing is more effectively suppressed. In addition, the content of the protective film forming agent is preferably 1 g / L or less, more preferably 0.2 g / L or less, for example. By the content of the protective film forming agent being within the above range, the protective film formed on the polished metal surface becomes moderately thick, and the polishing rate is more effectively maintained. The content of the protective film forming agent is the total content of all protective film forming agents in the polishing composition of the present invention.

[0072] Oxidizer: The polishing composition of the present invention preferably further contains an oxidizing agent from the viewpoint of further improving the polishing rate. The oxidizing agent has the function of oxidizing the metal to be polished and has the function of further improving the polishing rate by the polishing composition of the present invention. The oxidizing agent may be used alone or in combination of two or more kinds.

[0073] Examples of the oxidizing agent include peroxides such as hydrogen peroxide and ammonium persulfate. Among them, hydrogen peroxide is preferred from the viewpoint of reducing metal contamination of the metal surface to be polished that is caused by the oxidizing agent.

[0074] When the polishing composition of the present invention contains an oxidizing agent, the content (g / L) of the oxidizing agent in the polishing composition of the present invention is not particularly limited, but is preferably 1 g / L or more, more preferably 3 g / L or more, and most preferably 5 g / L or more. By the content of the oxidizing agent being within the above range, the polishing speed for the metal to be polished can be further improved. In addition, the content of the oxidizing agent is preferably 30 g / L or less, more preferably 20 g / L or less, and most preferably 15 g / L or less. By the content of the oxidizing agent being within the above range, the occurrence of dishing can be further suppressed. The content of the oxidizing agent is the total content of all oxidizing agents in the polishing composition of the present invention.

[0075] When the polishing composition of the present invention contains an oxidizing agent, the content of the oxidizing agent is, for example, 1 to 50 parts by weight, preferably 2 to 40 parts by weight, particularly preferably 5 to 30 parts by weight, and most preferably 10 to 30 parts by weight, relative to 1 part by weight of the compound represented by Formula (1).

[0076] When the compound represented by formula (1) and the oxidizing agent are contained within the above ranges, the compound represented by formula (1) coats and protects the surface of the metal to be polished, thereby mitigating the chemical polishing action of the oxidizing agent and preventing the occurrence of dishing (dish-shaped depressions) on the surface of the metal to be polished.

[0077] Etching agent: The polishing composition of the present invention preferably further contains an etching agent from the viewpoint of further improving the polishing rate. The etching agent has an effect of etching the metal to be polished, and has a function of further improving the polishing rate by the polishing composition of the present invention. The etching agent may be used alone or in combination of two or more.

[0078] Examples of the etching agent include α-amino acids such as glycine, alanine, valine, etc. Among them, glycine is preferred from the viewpoint of further increasing the polishing rate for the metal to be polished.

[0079] When the polishing composition of the present invention contains an etching agent, the content (g / L) of the etching agent in the polishing composition of the present invention is not particularly limited, but is preferably 0.5 g / L or more, more preferably 1 g / L or more, even more preferably 3 g / L or more, and most preferably 5 g / L or more. By the content of the etching agent being within the above range, the polishing speed for the metal to be polished can be further improved. In addition, the content of the etching agent is preferably 50 g / L or less, more preferably 30 g / L or less, even more preferably 20 g / L or less, and most preferably 15 g / L or less. By the content of the etching agent being within the above range, the occurrence of dishing can be further suppressed. The content of the etching agent is the total content of all etching agents in the polishing composition of the present invention.

[0080] Abrasive: The polishing composition of the present invention preferably further contains abrasive grains from the viewpoint of further improving the polishing rate. The abrasive grains play a role of mechanically polishing the metal to be polished, and have the function of further improving the polishing rate by the polishing composition of the present invention. The abrasive grains may be used alone or in combination of two or more kinds.

[0081] Examples of the abrasive grains include silica (precipitated silica, fumed silica, colloidal silica, synthetic silica), ceria, alumina, titania, zirconia, germania, manganese oxide, diamond, etc. Among these, colloidal silica is preferred from the viewpoint of reducing surface defects of the metal to be polished after polishing.

[0082] The average primary particle size of the abrasive grains is, for example, preferably 3 nm or more, more preferably 5 nm or more, and most preferably 8 nm or more. When the average primary particle size of the abrasive grains is equal to or more than the lower limit, the polishing rate can be effectively improved. The average primary particle size of the abrasive grains is, for example, preferably 200 nm or less, more preferably 100 nm or less, and most preferably 50 nm or less. When the average primary particle size of the abrasive grains is equal to or less than the upper limit, the abrasive grains can be prevented from settling in the polishing composition of the present invention. The average primary particle size of the abrasive grains is calculated from the specific surface area of ​​the abrasive grains measured by the BET method.

[0083] When the polishing composition of the present invention contains abrasive grains, the content (g / L) of the abrasive grains in the polishing composition of the present invention is not particularly limited, but is preferably 0.5 g / L or more, more preferably 1 g / L or more, and most preferably 5 g / L or more. By the content of the abrasive grains being within the above range, the polishing speed for the metal to be polished can be further improved. In addition, the content of the abrasive grains is preferably 100 g / L or less, more preferably 50 g / L or less, and most preferably 20 g / L or less. By the content of the abrasive grains being within the above range, the occurrence of dishing can be further suppressed. The content of the abrasive grains is the total content of all the abrasive grains in the polishing composition of the present invention.

[0084] When the polishing composition of the present invention contains abrasive grains, the content of the abrasive grains is, for example, 1 to 50 parts by weight, preferably 2 to 40 parts by weight, particularly preferably 5 to 30 parts by weight, and most preferably 10 to 30 parts by weight, per part by weight of the compound represented by Formula (1).

[0085] When the compound represented by formula (1) and abrasive grains are contained within the above range, the compound represented by formula (1) coats the surface of the abrasive grains, suppressing the aggregation of the abrasive grains and enhancing the dispersibility of the abrasive grains, thereby preventing the agglomerates of the abrasive grains from contacting the surface of the metal being polished and causing dishing (dish-shaped depressions).

[0086] The polishing composition of the present invention further preferably contains an abrasive together with the above-mentioned oxidizing agent, since the compound represented by formula (1) exhibits the effect of suppressing aggregation of the abrasive and enhancing the dispersibility of the abrasive, and the oxidizing agent has the effect of improving the polishing rate, thereby making it possible to improve the polishing rate while suppressing the occurrence of dishing.

[0087] The total content (g / L) of the abrasive grains and the oxidizing agent in the polishing composition of the present invention is, for example, 1 g / L or more, preferably 5 g / L or more, particularly preferably 10 g / L or more, and most preferably 15 g / L or more. The upper limit of the total content of the abrasive grains and the oxidizing agent is, for example, 50 g / L, preferably 40 g / L, and most preferably 30 g / L.

[0088] The total content of the abrasive grains and the oxidizing agent is, for example, 5 to 100 parts by weight, preferably 10 to 80 parts by weight, particularly preferably 20 to 60 parts by weight, and most preferably 30 to 50 parts by weight, per part by weight of the compound represented by formula (1).

[0089] The content of the abrasive grains is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, particularly preferably 0.5 to 3 parts by weight, and most preferably 0.5 to 2 parts by weight, per part by weight of the oxidizing agent.

[0090] The ratio of the contents of the abrasive grains and the oxidizing agent (oxidizing agent / abrasive grains; weight ratio) is, for example, 20 / 80 to 80 / 20, preferably 30 / 70 to 70 / 30, and particularly preferably 40 / 60 to 60 / 40.

[0091] Other Ingredients: The polishing composition of the present invention may further contain other components within the range in which the effects of the present invention are not hindered. Examples of the other components include water, pH adjusters, alcohols, chelates, etc. In the polishing composition of the present invention, pure water is usually used as the water, and ultrapure water is particularly preferred. Ultrapure water refers to water with an impurity content of 0.01 μg / L or less. In the present specification, "pure water" also includes ultrapure water.

[0092] Water contact angle of the polishing composition of the present invention: After polishing a copper plate using the polishing composition of the present invention under the polishing conditions described below, the water contact angle of the copper plate surface at 25° C. is preferably 20° or less, more preferably 18° or less, and even more preferably 16° or less. By having the above-mentioned properties, the polishing composition of the present invention is even more excellent in the effect of combining two contradictory performances, namely, controlling the wettability of the metal surface to be polished, providing an excellent polishing rate, and suppressing the occurrence of dishing. [Polishing conditions] Using a polishing apparatus, the polishing composition was supplied to a polyurethane laminated polishing pad at a supply rate of 200 mL / min, and the copper plate was polished for 60 seconds while applying a polishing pressure of 13.8 kPa to the copper plate by rotating both the polishing platen and the carrier at 100 rpm.

[0093] The purity of the copper plate is preferably 99.9% or more, more preferably 99.99% or more, and even more preferably 99.999% or more. As such a copper plate, for example, a commercially available copper blanket wafer can be used.

[0094] The contact angle between the copper plate surface and water after the polishing can be measured using a contact angle meter. Methods for measuring the water contact angle include, but are not limited to, the liquid drop method and the sliding method. Examples of commercially available contact angle meters include the CA-X contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.).

[0095] Ratio of polishing rate (nm / min) / dishing amount (nm) of the polishing composition of the present invention; In the polishing composition of the present invention, the ratio of the polishing rate (nm / min) determined under the following test condition 1 to the amount of dishing (nm) determined under the following test condition 2 [polishing rate (nm / min) / amount of dishing (nm)] is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more. When the ratio of the polishing rate to the amount of dishing is 10 or more, the effect of suppressing the occurrence of dishing is more excellent while maintaining a high polishing rate. [Test condition 1] Using a polishing machine, the polishing composition is supplied to a polyurethane laminated polishing pad at a supply rate of 200 mL / min, and the copper plate is polished for 60 seconds while applying a polishing pressure of 13.8 kPa to the copper plate by rotating both the polishing plate and the carrier at 100 rpm. After the polishing is completed, the polishing rate (nm / min) is calculated from the difference in thickness of the copper plate before and after polishing. [Test condition 2] Using a polishing machine, the polishing composition is supplied to a polyurethane laminated polishing pad at a supply rate of 200 mL / min, and a copper pattern wafer having a conductor layer made of copper provided on an insulator layer having a trench on its surface via a barrier layer is polished by rotating both the polishing platen and the carrier at 100 rpm while applying a polishing pressure of 13.8 kPa to the copper pattern wafer having a conductor layer made of copper provided on an insulator layer having a trench on its surface via a barrier layer, until the upper surface of the barrier layer is exposed. After polishing, the dishing amount (nm) is calculated from the step between the trench on the copper pattern wafer surface and the upper surface of the barrier layer.

[0096] From the viewpoint of rapid polishing, the polishing rate measured under the above test condition 1 is preferably 500 nm / min or more, more preferably 600 nm / min or more, and even more preferably 700 nm / min or more. Generally, since the initial thickness of the conductor layer is about 1000 nm, a polishing rate of 500 nm / min or more is practical because the processing time per semiconductor wafer is within 2 minutes.

[0097] From the viewpoint of producing high-quality semiconductor wafers with suppressed dishing, the amount of dishing measured under the above test condition 2 is preferably 50 nm or less, more preferably 40 nm or less, and further preferably 30 nm or less.

[0098] pH of the polishing composition of the present invention: The pH of the polishing composition of the present invention at 25°C is not particularly limited, but from the viewpoint of more excellent adsorption to the surface of the polished metal, it is preferable that it is near neutral to acidic. Specifically, from the viewpoint of more excellent adsorption to the surface of the polished metal and forming a good protective film, the pH is preferably 2 or more, more preferably 4 or more, and most preferably 6 or more. In addition, from the viewpoint of further improving the storage stability of the polishing composition of the present invention and stably forming a protective film, the pH is preferably 10 or less, more preferably 9 or less, and most preferably 8.5 or less. Here, the pH at 25°C can be measured using a commercially available pH meter, and refers to the value measured 1 minute after immersing an electrode in the polishing composition of the present invention.

[0099] Next, an example of a method for producing the polishing composition of the present invention will be described.

[0100] An example of a method for producing the polishing composition of the present invention is not limited in any way, and can be prepared, for example, by appropriately mixing a compound represented by formula (1) with water together with other components (e.g., anionic surfactants, protective film forming agents, oxidizing agents, etching agents, abrasive grains, pH adjusters, etc.).

[0101] The contents of the components of the polishing composition of the present invention described above are the contents at the time of use. Therefore, the polishing composition of the present invention may be supplied in a form that can be prepared at the time of use (hereinafter, may be referred to as "material for preparing the polishing composition of the present invention").

[0102] The material for preparing a polishing composition of the present invention is a material that can be used to prepare the polishing composition of the present invention by diluting it with water, for example. The material for preparing a polishing composition of the present invention can be in various liquid forms such as a solution, an emulsion, a suspension, etc., and can also be in various forms such as a solidified or semi-solidified or encapsulated gel, capsule, powder, particle, granule, etc.

[0103] When the material for preparing the polishing composition of the present invention is in the form of a solution (concentrate), the dilution ratio is not particularly limited, but from the viewpoint of reducing distribution costs and storage space, a dilution ratio of 2 times or more is preferable, 10 times or more is more preferable, and 50 times or more is even more preferable.

[0104] When the polishing composition preparation material of the present invention is in the form of a solution (concentrate), the content of the compound represented by the above formula (1) is, for example, preferably 3% by weight or more, more preferably 15% by weight or more, based on 100% by weight of the polishing composition preparation material of the present invention. The lower limit of the content is preferably 75% by weight or less, more preferably 50% by weight or less. If it is equal to or more than the lower limit, it is more excellent in reducing distribution costs and storage space. If it is equal to or less than the upper limit, it is more excellent in handleability (ease of preparation).

[0105] The material for preparing the polishing composition of the present invention can be produced according to known production methods for liquids, solids, semi-solids, gels, capsules, powders, granules, etc., except for the step of adding the compound represented by formula (1) to the water.

[0106] The polishing composition of the present invention described above can be suitably used in the manufacturing method and polishing method for semiconductor devices described in detail below.

[0107] Method for manufacturing a semiconductor device and method for polishing a semiconductor wafer of the present invention: The polishing composition of the present invention can be suitably used in a polishing method (polishing method of the present invention) including a step of polishing a semiconductor wafer having an insulator layer with a trench on its surface and a conductor layer formed on the surface of the insulator layer, and in a semiconductor device manufacturing method (semiconductor device manufacturing method of the present invention) including the above step.

[0108] The semiconductor wafer, which is the object to be polished in the polishing method of the present invention, has an insulator layer having a trench on its surface and a conductor layer formed on the surface of the insulator layer. The conductor layer is made of a copper-containing metal (e.g., copper, copper alloy, etc.). In addition, a barrier layer for preventing the diffusion of the copper-containing metal is present between the conductor layer and the insulator layer. The width of the trench (representing the thickness of the wiring) is not particularly limited. Examples of barrier metal materials constituting the barrier layer include low-resistance metal materials such as TiN, TiW, Ta, TaN, W, and WN. Among them, Ta and TaN are preferable from the viewpoint of excellent barrier performance.

[0109] Usually, in the semiconductor wiring process, a part of the conductor layer is polished in the first polishing step. In the subsequent polishing step (so-called finish polishing), the conductor layer is polished until the barrier layer in the area other than the trench is exposed. Then, finally, the barrier layer in the area other than the trench is also removed by polishing to expose the insulator layer. This forms a copper-containing metal wiring part (i.e., the trench is filled with the conductor layer) on the semiconductor wafer. In particular, the polishing composition of the present invention has an excellent polishing rate and suppresses the occurrence of dishing, so that it can be suitably used for the above-mentioned finish polishing application. EXAMPLES

[0110] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0111] The compound represented by formula (1) (polyglycerol derivative) was produced as follows.

[0112] (Production Example 1) 1 mol of lauryl alcohol was mixed with 4 mol of 2,3-epoxy-1-propanol (trade name "Glycidol", manufactured by Daicel Corporation) to give polyglycerin derivative (A1) (C 12 H 25 O-(C3H6O2)4-H, molecular weight: 482) was obtained.

[0113] (Production Example 2) A polyglycerol derivative (A2) (C 12 H 25 O-(C3H6O2) 10 -H, molecular weight: 926) was obtained.

[0114] (Production Example 3) A polyglycerol derivative (A3) (C 12 H 25 O-(C3H6O2)6-H, molecular weight: 630) was obtained.

[0115] (Production Example 4) Polyglycerin derivative (A4) (C 18 H 37 O-(C3H6O2) 10 -H, molecular weight: 1010) was obtained.

[0116] (Production Example 5) 1 mol of glycerin was mixed with 9 mol of 2,3-epoxy-1-propanol (trade name "Glycidol", manufactured by Daicel Corporation) to obtain polyglycerin derivative (A5) (HO-(C3H6O2) 10 -H, molecular weight: 758) was obtained.

[0117] As a comparative example, a compound not having the structure represented by formula (1) was prepared as follows.

[0118] (Comparative Manufacturing Example 1) To 1 mol of ethylene glycol, 48 mol of ethylene oxide was added, and then 38 mol of propylene oxide was added to obtain a polyoxyalkylene derivative (A6) (molecular weight: 4378).

[0119] (Comparative Manufacturing Example 2) To 1 mol of ethylene glycol, 32 mol of ethylene oxide was added, and then 20 mol of propylene oxide was added to obtain a polyoxyalkylene derivative (A7) (molecular weight: 2630).

[0120] (Comparative Manufacturing Example 3) Polyoxyalkylene derivative (A8) (molecular weight: 626) was obtained by adding 10 mol of ethylene oxide to 1 mol of lauryl alcohol.

[0121] (Comparative Manufacturing Example 4) A polyoxyalkylene derivative (A9) (molecular weight: 1066) was obtained by adding 20 mol of ethylene oxide to 1 mol of lauryl alcohol.

[0122] The compounds obtained in the above Production Examples and Comparative Production Examples were mixed with water in an appropriate amount with the components shown in Table 1 to prepare the following Examples. (Examples 1 and 5 are reference examples) and a comparative polishing composition were prepared.

[0123] The polishing compositions obtained in the Examples and Comparative Examples were evaluated as follows. The pH of each polishing composition is shown in Table 1.

[0124] (Polishing test) Polishing was performed under the following conditions, and (1) water contact angle, (2) polishing rate, and (3) dishing amount were evaluated. Polishing equipment: Mirra single-sided CMP polishing machine (manufactured by Applied Materials) Polished object: (1) For water contact angle evaluation: 200 mm diameter copper blanket wafer (2) For evaluation of polishing speed: 200 mm diameter copper blanket wafer (3) For dishing evaluation: copper pattern wafer (854 mask pattern) (Manufactured by SEMATECH) Polishing pad: Polyurethane laminated pad IC-1000 / SubaIV (Rohm and Haas) Polishing pressure: 13.8kPa Polishing platen rotation speed: 100 rpm Polishing composition supply rate: 200mL / min Carrier rotation speed: 100 rpm

[0125] (Evaluation method) (1) Water contact angle The water contact angle was measured by measuring the water contact angle of the wafer surface after polishing the copper blanket wafer of the polished object (1) for 60 seconds using a wafer cleaning evaluation device "CA-X200" (manufactured by Kyowa Interface Science Co., Ltd.) The water contact angle was measured after rinsing the surface of each wafer after polishing with pure water. (2) Polishing speed The polishing rate was determined by polishing the copper blanket wafer of the polished object (2) for 60 seconds, and dividing the difference in thickness of each wafer before and after polishing by the polishing time. A sheet resistance measuring instrument "VR-120" (manufactured by Kokusai Electric System Services Co., Ltd.) was used to measure the thickness of each wafer. (3) Amount of dishing The dishing amount was evaluated by the polishing amount of the copper pattern wafer of the polished object (3). Specifically, the copper pattern wafer of the polished object (3) is formed by sequentially providing a barrier layer made of tantalum and a conductor layer made of copper having a thickness of 1000 nm on an insulator layer made of silicon dioxide having a trench on the surface, and has an initial recess of 500 nm deep on the upper surface. Before polishing the copper pattern wafer of the above (3) using the polishing composition of the examples and comparative examples, it was pre-polished under the above polishing conditions using a commercially available polishing material (trade name "PLANERLITE-7105", manufactured by Fujimi Inc.) until the thickness of the conductor layer became 300 nm. Then, using the polishing composition of the examples and comparative examples, the copper pattern wafer of the polished object (3) after pre-polishing was polished under the above polishing conditions until the upper surface of the barrier layer was exposed. After polishing, the dishing (D) amount (nm) was measured from the step between the conductor layer 14 in the trench 11 on the surface of the copper pattern wafer and the upper surface of the barrier layer 13 using a contact surface measuring device "Profiler HRP340" (manufactured by KLA-Tencor Corporation) as shown in Figure 1. The evaluation results of (1) to (3) above are shown in Table 1.

[0126] (Pot Life) The copper blanket wafer of the polished object (2) was polished under the above-mentioned polishing test conditions using each polishing composition of the Examples and Comparative Examples immediately after preparation and each polishing composition of the Examples and Comparative Examples that had been prepared and then left to stand in a thermostatic chamber at 25°C for 14 days. Thereafter, the polishing rate was calculated by dividing the difference in thickness of each wafer before and after polishing by the polishing time, and the polishing rate of the polishing composition immediately after preparation was compared with the polishing rate of the polishing composition after storage at 25°C for 14 days to evaluate the pot life of each polishing composition based on the following criteria. The pot life can be used to evaluate whether the performance of the polishing composition of the present invention is stably maintained even after storage for a specified period of time. The results are shown in Table 1.

[0127] Evaluation criteria: ○ (Good): Polishing speed decrease rate is 10% or less △ (slightly poor): The decrease in polishing speed is more than 10%.

[0128] [Table 1]

[0129] (Evaluation of Results) As shown in Table 1, the polishing compositions of the Examples had excellent polishing rates and significantly suppressed the occurrence of dishing. In other words, it was clear that the compositions had two contradictory functions. On the other hand, the polishing compositions of the Comparative Examples did not provide practically satisfactory results in either the polishing rate or the dishing. In particular, in the Comparative Examples, the ratios of [polishing rate (nm / min) / amount of dishing (nm)] were all less than 10, and it was clear that the amount of dishing increased in proportion to the polishing rate.

[0130] Details of each component listed in the table are as follows.

[0131] <Anionic surfactant> (B1): Ammonium polyoxyethylene lauryl ether sulfate having an average repeat number of oxyethylene units of 2 (B2): Polyoxyethylene lauryl ether sulfate triethanolamine having an average repeat number of oxyethylene units of 1.5 (B3): Ammonium polyoxyethylene lauryl ether sulfonate having an average repeat number of oxyethylene units of 2 (B4): Ammonium lauryl sulfonate (B5): Ammonium laurylbenzenesulfonate (B6): Ammonium lauryl sulfate (B7): Polyoxyethylene alkyl phenyl ether phosphate having an average repeat number of oxyethylene units of 4 (B8): Potassium oleate (B9): Potassium polyoxyethylene alkyl ether acetate having an average repeat number of oxyethylene units of 2 (B10): Ammonium polyoxyethylene lauryl ether acetate having an average repeat number of oxyethylene units of 2 <Protective film forming agent> (C1): Benzotriazole <Oxidizing agent> (D1): Hydrogen peroxide <Etching agent> (E1): Glycine <Abrasive grains> (F1): Colloidal silica, average primary particle diameter 30 nm <pH adjuster> (G1): Potassium hydroxide

[0132] As a summary above, the configuration of the present invention and its variations are appended below. [1] A composition containing a compound represented by the following formula (1). R 1 O-(C3H6O2) n -H (1) (In the formula, R 1 represents a hydrogen atom, a hydrocarbon group having 1 to 24 carbon atoms which may have a hydroxyl group, or a group represented by R 2 CO, and the said R 2 represents a hydrocarbon group having 1 to 24 carbon atoms. n represents the average degree of polymerization of the glycerin units shown in the parentheses and is 2 to 60) [2] The composition according to [1], wherein the content of the compound represented by the formula (1) is 0.01 to 20 g / L. [3] The composition according to [1] or [2], wherein the weight average molecular weight of the compound represented by the formula (1) is 100 to 3000. [4] The composition according to any one of [1] to [3], wherein the HLB value of the compound represented by the formula (1) is 14 or more. [5] The composition according to any one of [1] to [4], wherein the compound represented by the formula (1) is a compound represented by the following formula (1’). R 1 O-(C3H6O2) n -H (1’) (In the formula, R 1 represents a linear or branched alkyl group having 8 to 18 carbon atoms which may have a hydroxyl group. n represents the average degree of polymerization of the glycerin units shown in the parentheses and is 5 to 8) [6] The composition according to any one of [1] to [5], further comprising an anionic surfactant. [7] The composition according to [6], wherein the anionic surfactant is a compound represented by the following formula (6'): R 3 -X 1 -Y 1 (6') (Wherein, R 3 represents a linear or branched alkyl group having 1 to 20 carbon atoms; X 1 represents a polyoxyethylene group and / or a polyoxypropylene group; Y 1 indicates the residue of sulfuric acid, sulfurous acid, sulfonic acid, or their salts. [8] The composition according to any one of [1] to [5], containing 0.05 to 1.00 parts by weight of a compound represented by the following formula (6') per 1 part by weight of the compound represented by formula (1): R 3 -X 1 -Y 1 (6') (Wherein, R 3 represents a linear or branched alkyl group having 1 to 20 carbon atoms; X 1 represents a polyoxyethylene group and / or a polyoxypropylene group; Y 1 indicates the residue of sulfuric acid, sulfurous acid, sulfonic acid, or their salts. [9] The composition according to any one of [1] to [8], further comprising an oxidizing agent, the content of the oxidizing agent being 1 to 50 parts by weight per part by weight of the compound represented by formula (1).

[10] The composition according to any one of [1] to [8], further comprising a peroxide, wherein the content of the peroxide is 1 to 50 parts by weight per part by weight of the compound represented by formula (1).

[11] The composition according to any one of [1] to

[10] , further comprising an abrasive grain, the content of the abrasive grain being 1 to 50 parts by weight per part by weight of the compound represented by formula (1).

[12] The composition according to any one of [1] to

[10] , further comprising silica, wherein the content of the silica is 1 to 50 parts by weight per part by weight of the compound represented by formula (1).

[13] The composition according to any one of [1] to

[10] , further comprising an oxidizing agent and an abrasive grain, wherein the ratio of the content of the oxidizing agent to the abrasive grain (oxidizing agent / abrasive grain; weight ratio) is 20 / 80 to 80 / 20, and the total content of the oxidizing agent and the abrasive grain is 5 to 100 parts by weight per part by weight of the compound represented by formula (1).

[14] The composition according to any one of [1] to

[10] , further comprising a peroxide and / or silica, wherein the total content of the oxidizing agent and the abrasive grains is 5 to 100 parts by weight per part by weight of the compound represented by formula (1).

[15] The composition according to any one of [1] to

[10] , further comprising a peroxide and silica, wherein the ratio of the content of the peroxide to the content of the silica (peroxide / silica; weight ratio) is 20 / 80 to 80 / 20, and the total content of the oxidizing agent and the abrasive grains is 5 to 100 parts by weight per part by weight of the compound represented by formula (1).

[16] The composition according to any one of [1] to

[15] , wherein the water contact angle at 25°C of a copper plate surface after polishing the copper plate under the following polishing conditions is 20° or less. [Polishing conditions] Using a polishing apparatus, the polishing composition was supplied to a polyurethane laminated polishing pad at a supply rate of 200 mL / min, and the copper plate was polished for 60 seconds while applying a polishing pressure of 13.8 kPa to the copper plate by rotating both the polishing platen and the carrier at 100 rpm.

[17] The composition according to any one of [1] to

[16] , wherein the ratio of the polishing rate (nm / min) determined under the following test condition 1 to the amount of dishing (nm) determined under the following test condition 2 [polishing rate (nm / min) / amount of dishing (nm)] is 10 or more. [Test condition 1] Using a polishing machine, the polishing composition is supplied to a polyurethane laminated polishing pad at a supply rate of 200 mL / min, and the copper plate is polished for 60 seconds while applying a polishing pressure of 13.8 kPa to the copper plate by rotating both the polishing plate and the carrier at 100 rpm. After the polishing is completed, the polishing rate (nm / min) is calculated from the difference in thickness of the copper plate before and after polishing. [Test condition 2] Using a polishing machine, the polishing composition is supplied to a polyurethane laminated polishing pad at a supply rate of 200 mL / min, and a copper pattern wafer having a conductor layer made of copper provided on an insulator layer having a trench on its surface via a barrier layer is polished by rotating both the polishing platen and the carrier at 100 rpm while applying a polishing pressure of 13.8 kPa to the copper pattern wafer having a conductor layer made of copper provided on an insulator layer having a trench on its surface via a barrier layer, until the upper surface of the barrier layer is exposed. After polishing, the dishing amount (nm) is calculated from the step between the trench on the copper pattern wafer surface and the upper surface of the barrier layer.

[18] The composition according to any one of [1] to

[17] , which is a composition for polishing a semiconductor wiring.

[19] Use of the composition according to any one of [1] to

[18] as a composition for polishing semiconductor wiring.

[20] A method for producing a composition for polishing semiconductor wiring, using the composition according to any one of [1] to

[18] .

[21] A polishing method comprising a step of polishing a semiconductor wafer having an insulator layer having a trench on its surface and a conductor layer formed on the surface of the insulator layer, with the composition according to any one of [1] to

[18] .

[22] A method for manufacturing a semiconductor device, comprising a step of polishing a semiconductor wafer having an insulator layer having a trench on its surface and a conductor layer formed on the surface of the insulator layer, with the composition according to any one of [1] to

[18] . [Explanation of symbols]

[0133] 1. Semiconductor wafer 11. Trench 12 Insulator layer 13 Barrier layer 14 Conductor layer D dishing amount

Claims

1. The composition comprises a compound represented by the following formula (1), an oxidizing agent, and an abrasive grain, the content of the oxidizing agent is 10 to 30 parts by weight relative to 1 part by weight of the compound represented by formula (1); The content of the abrasive grains in the composition for polishing semiconductor wiring is 10 to 30 parts by weight per part by weight of the compound represented by formula (1). R １ O-(C ３ H ６ O ２ ) ｎ -H (1) (In the formula, R １ represents a hydrocarbon group having 1 to 24 carbon atoms. n represents the average degree of polymerization of the glycerin unit shown in parentheses, which is 6 to 10.

2. 2. The semiconductor wiring polishing composition according to claim 1, wherein the copper plate surface has a water contact angle of 20° or less at 25° C. after polishing the copper plate under the following polishing conditions: [Polishing conditions] Using a polishing apparatus, the polishing composition was supplied to a polyurethane laminated polishing pad at a supply rate of 200 mL / min, and the copper plate was polished for 60 seconds while applying a polishing pressure of 13.8 kPa to the copper plate by rotating both the polishing platen and the carrier at 100 rpm.

3. A semiconductor wiring polishing composition as described in claim 1 or 2, in which the ratio of the polishing rate (nm / min) determined under the following test condition 1 to the dishing amount (nm) determined under the following test condition 2 [polishing rate (nm / min) / dishing amount (nm)] is 10 or more. [Test condition 1] Using a polishing apparatus, the polishing composition was supplied to a polyurethane laminated polishing pad at a supply rate of 200 mL / min, and the copper plate was polished for 60 seconds while applying a polishing pressure of 13.8 kPa to the copper plate by rotating both the polishing platen and the carrier at 100 rpm. After polishing, the polishing rate (nm / min) is calculated from the difference in thickness of the copper plate before and after polishing. [Test condition 2] Using a polishing machine, the polishing composition is supplied to a polyurethane laminated polishing pad at a supply rate of 200 mL / min, and a copper pattern wafer having a conductor layer made of copper provided on an insulator layer having a trench on its surface via a barrier layer is polished by rotating both the polishing platen and the carrier at 100 rpm while applying a polishing pressure of 13.8 kPa to the copper pattern wafer having a conductor layer made of copper provided on an insulator layer having a trench on its surface via a barrier layer, until the upper surface of the barrier layer is exposed. After polishing, the dishing amount (nm) is calculated from the step between the trench on the copper pattern wafer surface and the upper surface of the barrier layer.

4. 4. The semiconductor wiring polishing composition according to claim 1, further comprising an anionic surfactant.

5. 5. The semiconductor wiring polishing composition according to claim 1, wherein the content of the compound represented by formula (1) is 0.01 to 20 g / L.

6. 6. The semiconductor wiring polishing composition according to claim 1, wherein the compound represented by formula (1) has a weight average molecular weight of 100 to 3,000.

7. 7. The semiconductor wiring polishing composition according to claim 1, wherein the compound represented by formula (1) has an HLB value of 14 or more.

8. The semiconductor wiring polishing composition according to any one of claims 1 to 7, wherein the ratio of the content of the oxidizing agent to the abrasive grains (oxidizing agent / abrasive grains; weight ratio) is 20 / 80 to 80 / 20, and the total content of the oxidizing agent and the abrasive grains is 20 to 60 parts by weight per 1 part by weight of the compound represented by formula (1).

9. A polishing method comprising a step of polishing a semiconductor wafer having an insulator layer having a trench on its surface and a conductor layer formed on the surface of the insulator layer, using the semiconductor wiring polishing composition according to any one of claims 1 to 8.

10. A method for manufacturing a semiconductor device, comprising a step of polishing a semiconductor wafer having an insulator layer having a trench on its surface and a conductor layer formed on the surface of the insulator layer, using the semiconductor wiring polishing composition according to any one of claims 1 to 8.

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