TW202313925A - Polishing liquid, polishing method, component manufacturing method, and semiconductor component manufacturing method - Google Patents

Abstract

This polishing liquid contains cerium oxide abrasive grains and ammonium salt, and has a pH of at least 9.00. This polishing method uses the polishing liquid to polish a member to be polished that contains copper. This component manufacturing method enables a component to be obtained by using the member to be polished which has been polished using the polishing method. This semiconductor component manufacturing method enables a semiconductor component to be obtained by using the member to be polished which has been polished using the polishing method.

Description

Polishing liquid, polishing method, manufacturing method of component, and manufacturing method of semiconductor component

The disclosure relates to a polishing liquid, a polishing method, a manufacturing method of components, a manufacturing method of semiconductor components, and the like.

In recent years, in the manufacturing steps of electronic devices, the importance of processing technologies for high density, miniaturization, etc. has been increasing. As one of the processing technologies, CMP (Chemical Mechanical Polishing) technology has become an important step in the formation of shallow trench isolation (Shallow Trench Insulation: STI), planarization of pre-metal insulating materials or interlayer insulating materials, Technology required for formation of plugs and embedded metal wiring, etc. As a polishing liquid used for CMP, a polishing liquid containing abrasive grains containing cerium oxide is known (for example, refer to the following patent documents 1 and 2).

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-106994 [Patent Document 2] Japanese Patent Application Laid-Open No. 08-022970

For the polishing liquid that can be used for CMP, it is sometimes necessary to polish the polished member containing copper to remove it as soon as possible. For this grinding liquid, it is necessary to increase the grinding speed of copper.

The purpose of one aspect of the present disclosure is to provide a grinding liquid, which can increase the grinding speed of copper. Another object of the present disclosure is to provide a grinding method using the aforementioned grinding liquid. Another object of the present disclosure is to provide a method for manufacturing a component using the aforementioned grinding method. Another object of the present disclosure is to provide a method for manufacturing a semiconductor device using the aforementioned grinding method.

This disclosure is related to the following [1] to [17] and the like in some aspects. [1] A polishing liquid containing abrasive grains containing cerium oxide and an ammonium salt, and having a pH of 9.00 or higher. [2] The polishing liquid according to [1], wherein the ammonium salt contains ammonium carbonate. [3] The polishing liquid according to [2], wherein the ammonium salt further includes ammonium persulfate. [4] The polishing liquid according to any one of [1] to [3], wherein the content of the ammonium salt is 0.3 to 2% by mass. [5] The polishing liquid according to any one of [1] to [4], which further contains ammonia. [6] The polishing liquid according to any one of [1] to [5], which further contains an ether compound having a hydroxyl group. [7] The polishing liquid according to [6], wherein the ether compound contains an alkoxy alcohol. [8] The polishing liquid according to [7], wherein the alkoxy alcohol contains 3-methoxy-3-methyl-1-butanol. [9] The polishing liquid according to [7] or [8], wherein the content of the alkoxy alcohol is 0.2 to 0.8% by mass based on the total mass of the polishing liquid. [10] The polishing liquid according to any one of [6] to [9], wherein the ether compound includes a compound having two or more hydroxyl groups. [11] The polishing liquid according to any one of [6] to [10], wherein the ether compound contains polyether. [12] The polishing liquid according to [11], wherein the polyether contains polyglycerol. [13] The polishing liquid according to [11] or [12], wherein the content of the polyether is 0.5 to 3% by mass based on the total mass of the polishing liquid. [14] The polishing liquid according to any one of [1] to [13], which has a pH of 9.00 to 11.00. [15] A polishing method for polishing a member to be polished containing copper using the polishing liquid described in any one of [1] to [14]. [16] A method of manufacturing a component using a polished member ground by the grinding method described in [15] to obtain a component. [17] A method of manufacturing a semiconductor device, obtaining a semiconductor device using a polished member polished by the polishing method described in [15]. [Invention effect]

According to an aspect of the present disclosure, a polishing liquid can be provided, which can increase the polishing speed of copper. According to another aspect of the present disclosure, a polishing method using the aforementioned polishing liquid can be provided. According to another aspect of the present disclosure, a method for manufacturing a component using the aforementioned grinding method can be provided. According to another aspect of the present disclosure, a method for manufacturing a semiconductor device using the aforementioned grinding method can be provided. According to another aspect of the present disclosure, an application of a polishing liquid to polishing a component to be polished containing copper can be provided.

Embodiments of the present disclosure will be described below. However, this disclosure is not limited to the following embodiments.

In this specification, the numerical range shown by "-" shows the range which includes the numerical value described before and after "-" as a minimum value and a maximum value, respectively. "More than A" in the numerical range means A and the range exceeding A. "Below A" in the numerical range refers to the range of A and less than A. Within the numerical ranges described step by step in this specification, the upper limit or lower limit of a numerical range of a certain step can be arbitrarily combined with the upper limit or lower limit of a numerical range of another step. Within the numerical range described in this specification, the upper limit or lower limit of the numerical range may be replaced with the value shown in the Examples. "A or B" may include either one of A and B, or both. The materials exemplified in this specification can be used alone or in combination of two or more unless otherwise specified. The content of each component in the composition refers to the total amount of the plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component exist in the composition. The term "membrane" includes not only the structure of the shape formed on the entire surface when viewed from a plan view, but also the structure of the shape formed on a part. The term "step" does not only include independent steps, but even when it cannot be clearly distinguished from other steps, as long as the desired effect of the step is achieved, it is also included in this term. Unless otherwise specified, "alkyl" may be any of linear, branched or cyclic. "Abrasive grain" refers to the aggregation of plural grains, but for convenience, one grain constituting the abrasive grain is sometimes referred to as abrasive grain.

＜Grinding Liquid＞ The polishing solution of this embodiment contains abrasive grains containing cerium oxide and ammonium salt, and has a pH of 9.00 or higher. The polishing liquid of this embodiment can be used as a CMP polishing liquid.

According to the polishing liquid of this embodiment, the copper polishing rate can be increased, and for example, a polishing rate of 0.35 μm/min or higher (preferably 0.40 μm/min or higher) can be obtained in the evaluation method described in the examples described later. The reason for increasing the polishing rate of copper is not necessarily clear, but the present inventors presume as follows. That is, it is presumed that the ammonium salt or the ammonium cation of the ammonium salt forms a complex with copper, and the oxidizing ability of the cerium oxide of the abrasive grain acts to promote the formation of the complex, thereby increasing the copper polishing rate. However, the reason why the effect can be obtained is not limited to this content.

The polishing liquid of this embodiment can be used for polishing a member to be polished containing copper. The polishing liquid of the present embodiment can be used for polishing a member to be polished other than a member to be polished containing copper.

In recent years, 2.1D integrated circuits, 2.5D integrated circuits, 3D integrated circuits, etc. have been developed from the viewpoint of high-speed, low power consumption, and large-capacity electronic devices, and chip-to-chip (chip-on-chip) ), wafer-to-wafer (wafer on wafer), chip-to-wafer (wafer on chip) and other connection steps, and based on WLP (Wafer-Level Packaging: wafer-level packaging), PLP (Panel-Level Packaging: Flat-level packaging) and other semiconductor packaging manufacturing steps are getting more and more attention. In these steps, in order to obtain a good connection surface (here, not only the surface directly connected, but also the surface that becomes the base in the case of connection through other members is also called "connection surface"), the polished member that needs to be planarized On the surface to be polished, resin (such as epoxy resin) and metal material (such as copper) may exist. The polishing liquid of this embodiment can be used for polishing a polished member containing resin (such as epoxy resin) and metal material (such as copper).

The polishing liquid of this embodiment contains the abrasive grain containing cerium oxide. The polishing rate of copper can be increased by using abrasive grains containing cerium oxide. Abrasive grains may contain one or more types of grains. Examples of constituent materials of the abrasive grains other than cerium oxide include inorganic materials such as silicon dioxide (SiO ₂ ), aluminum oxide, zirconium oxide, titanium dioxide, germanium dioxide, and silicon carbide. Alumina may not be contained in the polishing liquid of the present embodiment as a constituent material of abrasive grains and the like. Based on the total mass of the polishing liquid, the content of alumina can be 0.1 mass % or less, less than 0.1 mass %, 0.01 mass % or less, 0.001 mass % or less or substantially 0 mass %.

From the viewpoint of improving the copper polishing speed easily, the content of cerium oxide in the abrasive grains may be 90% by mass based on the entire abrasive grains (the entire abrasive grains contained in the polishing liquid or the entire grains constituting the abrasive grains) More than 93% by mass, more than 95% by mass, more than 95% by mass, more than 98% by mass, more than 99% by mass, more than 99.5% by mass, or more than 99.9% by mass. The abrasive grains may be substantially composed of cerium oxide (a mode in which substantially 100% by mass of the abrasive grain is cerium oxide).

The average particle diameter D50 or D80 of the abrasive grains may be within the following range. The average particle diameters D50 and D80 of the abrasive grains refer to the 50% particle diameter and the 80% particle diameter of the volume-based cumulative distribution, which can be measured by, for example, a laser diffraction particle size distribution meter. The average particle size of the abrasive grains can be adjusted by natural sedimentation, pulverization, dispersion, filtration, etc. For example, the particle size can be adjusted after mixing the components of the polishing liquid.

From the viewpoint of easily improving the grinding speed of copper, the average particle diameter D50 of the abrasive grains can be more than 10nm, more than 50nm, more than 70nm, more than 100nm, more than 150nm, more than 150nm, more than 200nm, more than 250nm, more than 300nm, more than 320nm or Above 340nm. The average particle diameter D50 of the abrasive grains may be 1000 nm or less, 800 nm or less, 600 nm or less, 500 nm or less, 450 nm or less, 400 nm or less, or 350 nm or less from the viewpoint of easily suppressing grinding scratches. From these viewpoints, the average particle diameter D50 of the abrasive grains may be 10 to 1000 nm, 50 to 800 nm, 100 to 500 nm, or 200 to 400 nm.

From the viewpoint of easily increasing the polishing rate of copper, the average particle diameter D80 of the abrasive grains may be 50 nm or more, 100 nm or more, 200 nm or more, 300 nm or more, 350 nm or more, 400 nm or more, 450 nm or more, 500 nm or more, 550 nm or more, or 600 nm or more. From the viewpoint of easily suppressing grinding scratches, the average particle diameter D80 of the abrasive grains may be 1200 nm or less, 1100 nm or less, 1000 nm or less, 900 nm or less, 800 nm or less, 750 nm or less, 700 nm or less, or 650 nm or less. From these viewpoints, the average particle diameter D80 of the abrasive grains may be 50 to 1200 nm, 100 to 1000 nm, 300 to 800 nm, or 500 to 700 nm.

Based on the total mass of the grinding liquid, the content of abrasive grains can be within the following ranges. From the viewpoint of improving the copper grinding speed easily, the content of abrasive grains may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, more than 0.5% by mass, or 0.7% by mass or more, 0.8% by mass or more, 0.9% by mass or more, or 1% by mass or more. From the viewpoint of easily avoiding the increase of the viscosity of the polishing liquid, the aggregation of the abrasive grains, etc., the content of the abrasive grains can be 10% by mass or less, 8% by mass or less, 5% by mass or less, 4% by mass or less, or 3% by mass or less. 2% by mass or less, 1.5% by mass or less, or 1% by mass or less. From these viewpoints, the content of the abrasive grains may be 0.01 to 10% by mass, 0.1 to 5% by mass, 0.5 to 2% by mass, or 0.5 to 1.5% by mass.

The polishing liquid of this embodiment contains an ammonium salt. Ammonium salts are salts of acid components and ammonium cations. The ammonium salt may include at least one selected from the group consisting of ammonium salts of inorganic acids and ammonium salts of organic acids. Ammonium salts may contain ammonium salts other than peroxides, or may contain peroxides (ammonium persulfate, etc.).

Ammonium salts of inorganic acids include ammonium salts of monovalent inorganic acids such as ammonium nitrate, ammonium chloride, and ammonium bromide; ammonium salts of divalent inorganic acids such as ammonium carbonate, ammonium bicarbonate, ammonium sulfate, and ammonium persulfate. Ammonium salts of trivalent inorganic acids such as ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium borate, etc. The ammonium salt may contain ammonium carbonate or ammonium persulfate from the viewpoint of making it easier to increase the polishing rate of copper.

Examples of organic acids in ammonium salts of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-Ethylbutanoic acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glycerol acid, Oxalic acid, malonic acid, succinic acid, 3-methylphthalic acid, 4-methylphthalic acid, 3-aminophthalic acid, 4-aminophthalic acid, 3-nitrophthalic acid Phthalic acid, 4-nitrophthalic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, isophthalic acid, malic acid, tartaric acid, citric acid, para Toluenesulfonic acid, p-phenolsulfonic acid, methanesulfonic acid, lactic acid, itaconic acid, quinalcidic acid, adipic acid, etc. The ammonium salt may contain ammonium acetate from the viewpoint of making it easier to increase the polishing rate of copper.

From the viewpoint of easily increasing the grinding rate of copper, the ammonium salt may include ammonium salts of inorganic acids, ammonium salts of divalent inorganic acids, or at least one selected from the group consisting of ammonium carbonate and ammonium persulfate. A sort of. The ammonium salt may include ammonium salts and peroxides different from peroxides, and may include ammonium carbonate and ammonium persulfate from the viewpoint of improving the polishing rate of copper easily. From the viewpoint of easily increasing the grinding rate of copper, the ammonium salt may contain at least one selected from the group consisting of ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium persulfate, ammonium dihydrogen phosphate, and ammonium acetate. .

The ammonium salt may include compounds having the following molecular weights from the viewpoint of making it easier to increase the polishing rate of copper. The molecular weight can be above 50, above 60, above 70, above 75, above 78, above 80, above 90, above 100, above 110, above 120, above 130, above 140, above 150, above 180, above 200 or above 220 . Molecular weight can be less than 1000, less than 1000, less than 800, less than 500, less than 300, less than 250, less than 230, less than 220, less than 200, less than 180, less than 150, less than 140, less than 130, less than 120, less than 110, less than 100 , less than 90, less than 80, less than 78, less than 75, less than 70 or less than 60. From these viewpoints, the molecular weight can be 50-1000, 70-1000, 80-1000, 50-500, 70-500, 80-500, 50-250, 70-250, 80-250, 50-100, 70 ~100 or 80~100.

From the viewpoint of easily increasing the grinding speed of copper, the content of the ammonium salt different from the peroxide or the content of ammonium carbonate is based on the total mass of the ammonium salt (the total mass of the ammonium salt contained in the polishing liquid). A1 may be within the following range. The content A1 may be more than 0 mass %, 1 mass % or more, 5 mass % or more, 10 mass % or more, 20 mass % or more, 30 mass % or more, 34 mass % or more, 35 mass % or more, 40 mass % or more, 41 mass % or more Mass % or more, 45 mass % or more, 50 mass % or more, 60 mass % or more, 70 mass % or more, 80 mass % or more, 90 mass % or more, 95 mass % or more or 99 mass % or more. The ammonium salt contained in the polishing solution may be substantially composed of ammonium salt or ammonium carbonate different from the peroxide (substantially 100% by mass of the ammonium salt contained in the polishing solution is an ammonium salt different from the peroxide or the form of ammonium carbonate). The content A1 may be 100% by mass or less, less than 100% by mass, 99% by mass or less, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 45% by mass or less. Mass % or less, 41 mass % or less, 40 mass % or less, 35 mass % or less, 34 mass % or less, 30 mass % or less, 20 mass % or less, 10 mass % or less, or 5 mass % or less. From these viewpoints, the content A1 may be more than 0% by mass and not more than 100% by mass, 30 to 100% by mass, 50 to 100% by mass, or 80 to 100% by mass.

When the ammonium salt contains a peroxide, from the viewpoint of easily increasing the copper grinding speed, the total mass of the ammonium salt (the total mass of the ammonium salt contained in the polishing solution) is used as the basis for the peroxide (ammonium salt) The content or the content of ammonium persulfate, the content A2 can be in the following range. The content A2 may be more than 0 mass %, 1 mass % or more, 5 mass % or more, 10 mass % or more, 20 mass % or more, 30 mass % or more, 40 mass % or more, 50 mass % or more, 55 mass % or more, 59 mass % or more Mass % or more, 60 mass % or more, 65 mass % or more, 66 mass % or more, 70 mass % or more, 80 mass % or more, 90 mass % or more, 95 mass % or more, 99 mass % or more or substantially 100 mass % (A state in which the ammonium salt contained in the polishing liquid is substantially composed of peroxide or ammonium persulfate). The content A2 may be 100% by mass or less, less than 100% by mass, 99% by mass or less, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 66% by mass or less, 65% by mass or less, 60% by mass or less. Mass % or less or 59 mass % or less. From these viewpoints, the content A2 may be more than 0% by mass and less than 100% by mass, 50 to 100% by mass, 60 to 100% by mass, more than 0% by mass and less than 100% by mass, and 50% by mass to less than 100% by mass % or more than 60% by mass and less than 100% by mass.

From the viewpoint of easily increasing the grinding speed of copper, as the content of ammonium salt (total amount of compounds corresponding to ammonium salt; the same below), the content of ammonium salt different from peroxide, or the content of ammonium carbonate, grinding Based on the total mass of the liquid, the content B1 can be within the following range. The content B1 may be more than 0 mass %, 0.01 mass % or more, 0.02 mass % or more, 0.05 mass % or more, 0.1 mass % or more, 0.2 mass % or more, 0.3 mass % or more, 0.4 mass % or more, 0.45 mass % or more, 0.5 mass % or more More than 0.5% by mass, more than 0.6% by mass, more than 0.7% by mass, more than 0.8% by mass, more than 0.85% by mass, more than 0.9% by mass, more than 1% by mass, more than 1.1% by mass, more than 1.2% by mass, 1.3% by mass Mass % or more, 1.4 mass % or more, 1.5 mass % or more, or 1.6 mass % or more. The content B1 may be 10% by mass or less, 8% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.8% by mass or less, 1.7% by mass or less, 1.6% by mass or less, 1.5% by mass or less Mass % or less, 1.4 mass % or less, 1.3 mass % or less, 1.2 mass % or less, 1.1 mass % or less, 1 mass % or less, 0.9 mass % or less, 0.85 mass % or less, 0.8 mass % or less, 0.7 mass % or less, 0.6 mass % or less Mass % or less, 0.5 mass % or less, 0.45 mass % or less, 0.4 mass % or less, 0.3 mass % or less, 0.2 mass % or less, 0.1 mass % or less, 0.05 mass % or less, or 0.02 mass % or less. From these viewpoints, the content B1 may be more than 0% by mass and not more than 10% by mass, more than 0% by mass and not more than 5% by mass, more than 0% by mass and not more than 2% by mass, more than 0% by mass and not more than 1% by mass, 0.01-10 mass%, 0.01-5 mass%, 0.01-2 mass%, 0.01-1 mass%, 0.1-10 mass%, 0.1-5 mass%, 0.1-2 mass%, 0.1-1 mass%, 0.3- 10% by mass, 0.3 to 5% by mass, 0.3 to 2% by mass or 0.3 to 1% by mass.

From the viewpoint of easily increasing the grinding speed of copper, when the ammonium salt contains peroxide, the content of peroxide (ammonium salt) or ammonium persulfate is based on the total mass of the polishing liquid, and the content B2 can be within the following range. The content B2 may be more than 0 mass %, 0.01 mass % or more, 0.05 mass % or more, 0.1 mass % or more, 0.2 mass % or more, 0.3 mass % or more, 0.4 mass % or more, 0.5 mass % or more, more than 0.5 mass %, 0.6 mass % or more Mass % or more, 0.65 mass % or more, 0.7 mass % or more, 0.75 mass % or more, or 0.8 mass % or more. The content B2 may be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, 1.2% by mass or less, 1% by mass or less, 0.9% by mass or less, 0.8% by mass or less, 0.75% by mass or less Mass % or less, 0.7 mass % or less, 0.65 mass % or less, or 0.6 mass % or less. From these viewpoints, the content B2 may be more than 0% by mass and not more than 5% by mass, 0.01 to 5% by mass, 0.1 to 5% by mass, 0.5 to 5% by mass, more than 0% by mass to not more than 1% by mass, and 0.01 to 5% by mass. 1% by mass, 0.1 to 1% by mass or 0.5 to 1% by mass.

From the viewpoint of improving the copper polishing rate easily, the content C1 of the content of ammonium salt, ammonium salt other than peroxide, or ammonium carbonate can be within the following range with respect to 100 parts by mass of abrasive grains. The content C1 may be more than 0 parts by mass, 1 part by mass or more, 2 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more. More than 60 parts by mass, more than 70 parts by mass, more than 80 parts by mass, more than 85 parts by mass, more than 90 parts by mass, more than 100 parts by mass, more than 110 parts by mass, more than 120 parts by mass, more than 130 parts by mass, 140 parts by mass More than 150 parts by mass or more than 160 parts by mass. Content C1 can be 1000 mass parts or less, 800 mass parts or less, 500 mass parts or less, 400 mass parts or less, 300 mass parts or less, 200 mass parts or less, 180 mass parts or less, 170 mass parts or less, 160 mass parts or less, 150 mass parts or less Less than 140 parts by mass, less than 130 parts by mass, less than 120 parts by mass, less than 110 parts by mass, less than 100 parts by mass, less than 90 parts by mass, less than 85 parts by mass, less than 80 parts by mass, less than 70 parts by mass, 60 parts by mass Not more than 50 parts by mass, not more than 45 parts by mass, not more than 40 parts by mass, not more than 30 parts by mass, not more than 20 parts by mass, not more than 10 parts by mass, not more than 5 parts by mass, or not more than 2 parts by mass. From these viewpoints, the content C1 may be more than 0 parts by mass and not more than 1000 parts by mass, more than 0 parts by mass and not more than 500 parts by mass, more than 0 parts by mass and not more than 200 parts by mass, more than 0 parts by mass and not more than 100 parts by mass, 1-1000 parts by mass, 1-500 parts by mass, 1-200 parts by mass, 1-100 parts by mass, 10-1000 parts by mass, 10-500 parts by mass, 10-200 parts by mass, 10-100 parts by mass, 30- 1000 parts by mass, 30 to 500 parts by mass, 30 to 200 parts by mass, or 30 to 100 parts by mass.

From the viewpoint of easily increasing the grinding speed of copper, when the ammonium salt contains a peroxide, as the content of the peroxide (ammonium salt) or the content of ammonium persulfate, the content C2 can be as follows with respect to 100 parts by mass of the abrasive grains. within the stated range. The content C2 may exceed 0 parts by mass, 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 65 parts by mass or more. More than 70 parts by mass, more than 75 parts by mass, or more than 80 parts by mass. Content C2 can be 500 mass parts or less, 400 mass parts or less, 300 mass parts or less, 200 mass parts or less, 150 mass parts or less, 120 mass parts or less, 100 mass parts or less, 90 mass parts or less, 80 mass parts or less, 75 Parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less. From these viewpoints, the content C2 may be more than 0 parts by mass and not more than 500 parts by mass, 1 to 500 parts by mass, 10 to 500 parts by mass, 50 to 500 parts by mass, more than 0 parts by mass to not more than 100 parts by mass, 1 to 500 parts by mass, 100 parts by mass, 10 to 100 parts by mass or 50 to 100 parts by mass.

(water) The polishing liquid of this embodiment may contain water. Water may be contained as the remainder after removing other constituent components from the polishing liquid. Based on the total mass of the polishing liquid, the content of water may be within the following ranges. The water content may be 90% by mass or more, 91% by mass or more, 92% by mass or more, 93% by mass or more, 94% by mass or more, 94.5% by mass or more, 95% by mass or more, 95.5% by mass or more, 96% by mass or more, 97 mass % or more or 98 mass % or more. The water content may be less than 100% by mass, 99% by mass or less, 98% by mass or less, 97% by mass or less, 96% by mass or less, or 95.5% by mass or less. From these viewpoints, the content of water may be 90% by mass to less than 100% by mass, 90 to 99% by mass, or 95 to 99% by mass.

(additive) The polishing solution of this embodiment may contain abrasive grains, ammonium salt, and components other than water. Examples of such components include ammonia, ether compounds having a hydroxyl group, ether compounds not having a hydroxyl group, acid components, preservatives, alkaline hydroxides, peroxides, organic solvents, surfactants, antifoaming agents, etc. . The polishing liquid of this embodiment may not contain at least one of these components.

The polishing liquid of this embodiment may contain ammonia. It is presumed that ammonia forms a complex with copper, and the polishing rate of copper tends to increase.

From the viewpoint of making it easier to increase the polishing rate of copper, the content of ammonia may be within the following range based on the total mass of the polishing liquid. The content of ammonia may be more than 0 mass %, 0.01 mass % or more, 0.03 mass % or more, 0.05 mass % or more, 0.08 mass % or more, 0.1 mass % or more, 0.12 mass % or more, 0.15 mass % or more, 0.2 mass % or more, 0.25% by mass or more or 0.3% by mass or more. The content of ammonia may be 5 mass % or less, 4 mass % or less, 3 mass % or less, 2 mass % or less, 1.5 mass % or less, 1 mass % or less, 0.8 mass % or less, 0.6 mass % or less, 0.5 mass % or less, 0.4% by mass or less, 0.3% by mass or less, 0.2% by mass or less, or 0.15% by mass or less. From these viewpoints, the content of ammonia may be more than 0% by mass and not more than 5% by mass, 0.01 to 5% by mass, 0.1 to 5% by mass, 0.2 to 5% by mass, more than 0% by mass to less than 2% by mass, 0.01 ～2 mass %, 0.1～2 mass %, 0.2～2 mass %, more than 0 mass % and 0.5 mass % or less, 0.01～0.5 mass %, 0.1～0.5 mass %, or 0.2～0.5 mass %.

From the viewpoint of making it easier to increase the polishing rate of copper, the content of ammonia may be within the following range with respect to 100 parts by mass of abrasive grains. The ammonia content may be more than 0 parts by mass, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 8 parts by mass or more, 10 parts by mass or more, 12 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more or 30 parts by mass or more. The content of ammonia may be less than 500 parts by mass, less than 400 parts by mass, less than 300 parts by mass, less than 200 parts by mass, less than 150 parts by mass, less than 100 parts by mass, less than 80 parts by mass, less than 60 parts by mass, or less than 50 parts by mass, Less than 50 parts by mass, 40 parts by mass or less, 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less. From these viewpoints, the ammonia content may be more than 0 parts by mass and not more than 500 parts by mass, 1 to 500 parts by mass, 10 to 500 parts by mass, 20 to 500 parts by mass, more than 0 parts by mass and not more than 200 parts by mass, 1 -200 parts by mass, 10-200 parts by mass, 20-200 parts by mass, more than 0 parts by mass and less than 50 parts by mass, 1-50 parts by mass, 10-50 parts by mass, or 20-50 parts by mass.

The content of ammonia may be in the following range with respect to 100 parts by mass of the ammonium salt from the viewpoint of making it easier to increase the polishing rate of copper. The ammonia content may be more than 0 parts by mass, 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 36 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 80 parts by mass or more, 100 parts by mass or more, 150 parts by mass or more, 200 parts by mass or more, 300 parts by mass or more, 500 parts by mass or more, 1000 parts by mass or more or 1500 parts by mass or more. The content of ammonia may be less than 2000 parts by mass, less than 1500 parts by mass, less than 1000 parts by mass, less than 500 parts by mass, less than 300 parts by mass, less than 200 parts by mass, less than 150 parts by mass, less than 100 parts by mass, or less than 80 parts by mass, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 36 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, 25 parts by mass or less, or 20 parts by mass or less. From these viewpoints, the content of ammonia may be more than 0 parts by mass and not more than 2000 parts by mass, 10 to 2000 parts by mass, 100 to 2000 parts by mass, 300 to 2000 parts by mass, more than 0 parts by mass and not more than 1500 parts by mass, 10 -1500 parts by mass, 100-1500 parts by mass, 300-1500 parts by mass, or 1-200 parts by mass.

The polishing liquid of this embodiment may contain an ether compound (hereinafter referred to as "ether compound A" depending on the case) having a hydroxyl group. The ether compound having a hydroxyl group is a compound having at least one hydroxyl group and at least one ether group. The "ether group" in ether compound A does not include the "-O-" structure in hydroxyl (hydroxyl), carboxyl, carboxylate, ester, sulfo and phosphoric acid groups. The hydroxyl group does not include the OH group contained in the carboxyl group, the sulfo group and the phosphoric acid group.

From the viewpoint of making it easier to increase the polishing rate of copper, the ether compound A may contain a compound in which the number of hydroxyl groups is within the following range. The number of hydroxyl groups is 1 or more, may be 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 8 or more, 9 or more, 10 or more, 11 or more or 12 or more. The number of hydroxyl groups may be 20 or less, 15 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 6 or less, 5 or less, 4 or less, 3 or less or 2 or less. From these viewpoints, the number of hydroxyl groups may be 1-20, 1-10, 1-5, 1-3 or 1-2. From the viewpoint of easily improving the copper grinding rate, the ether compound A may include a compound having one hydroxyl group, a compound having two or more hydroxyl groups, or a compound having one hydroxyl group and a compound having two or more hydroxyl groups. Hydroxyl compounds.

The ether compound A may contain a compound in which the number of ether groups falls within the following range from the viewpoint of making it easier to increase the polishing rate of copper. The number of ether groups is 1 or more, may be 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 8 or more or 9 or more. The number of ether groups can be 20 or less, 15 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 6 or less, 5 or less, 4 or less, 3 or less or 2 or less. From these viewpoints, the number of ether groups may be 1-20, 1-10, 1-5, 1-3 or 1-2. From the viewpoint of easily increasing the polishing rate of copper, the ether compound A may include a compound having one ether group, or may include a compound having two or more ether groups, or may include a compound having one ether group and a compound having two or more ether groups. Compounds with more than one ether group.

The ether compound A may contain an alkoxy alcohol from the viewpoint of making it easier to increase the copper polishing rate. Examples of alkoxy alcohols include 2-methoxyethanol, 2-ethoxyethanol, 2-(2-methoxy)ethoxyethanol, and 2-(2-butoxyethoxy)ethanol , 2-propoxyethanol, 2-butoxyethanol, 3-methoxy-3-methyl-1-butanol, 2-(methoxymethoxy)ethanol, 2-isopropoxyethanol , 2-butoxyethanol, 2-isoamyloxyethanol, 1-propoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1 -butanol, 3-methoxy-3-methylbutanol, 1-methoxy-2-butanol, glycol monoether, and the like. The alkoxy alcohol may include a compound having an alkoxy group having 1-5, 1-4, 1-3, 1-2, or 2-3 carbon atoms from the viewpoint of easily increasing the polishing rate of copper. The alkoxy alcohol may include 1-propoxy-2-propanol, or may include 3-methoxy-3-methyl-1-butanol from the viewpoint of improving the polishing rate of copper easily.

The ether compound A may contain a polyether, or may contain an alkoxy alcohol and a polyether from the viewpoint of making it easier to increase the polishing rate of copper. Examples of polyethers include polyglycerol, polysaccharides, polyalkylene glycols, polyoxypropylene polyglycerol ethers, polyoxyethylene polyglycerol ethers, 1,4-bis(2-hydroxyethoxy) Benzene, 2,2-bis(4-polyoxyethyleneoxyphenyl)propane, 2,2-bis(4-polyoxypropyleneoxyphenyl)propane, ethylene glycol monophenyl ether, diethylene glycol mono Phenyl ether, polyoxyalkylene monophenyl ether, propylene glycol monophenyl ether, polyoxypropylene monomethyl phenyl ether, polyethylene glycol monomethyl ether, neopentylthritol polyoxyethylene ether, ethylene glycol monoene Propyl ether, polyoxyethylene monoallyl ether, alkyl glucoside, etc. As polyethers, compounds other than alkoxy alcohols can be used. Polyglycerol may be included in the polyether from the viewpoint of making it easier to increase the polishing rate of copper.

The ether compound A may contain polyglycerol in which the average degree of polymerization of glycerol is in the following range from the viewpoint of making it easier to increase the polishing rate of copper. The average degree of polymerization may be 3 or more, 4 or more, 5 or more, 8 or more or 10 or more. The average degree of polymerization may be 100 or less, 50 or less, 30 or less, 20 or less, 15 or less, 12 or less, or 10 or less. From these viewpoints, the average degree of polymerization may be 3-100, 5-50, 8-20, 5-15 or 8-15.

The ether compound A may contain polyglycerol having a hydroxyl value within the following range from the viewpoint of making it easier to increase the polishing rate of copper. The hydroxyl value may be above 100, above 200, above 300, above 400, above 500, above 600, above 700, above 800, above 850 or above 870. The hydroxyl value may be 2000 or less, 1500 or less, 1200 or less, 1100 or less, 1000 or less, 950 or less, 930 or less, or 910 or less. From these viewpoints, the hydroxyl value may be 100-2000, 300-1500, 500-1200 or 800-1000.

The ether compound A may include a compound having one hydroxyl group and one ether group from the viewpoint of making it easier to increase the polishing rate of copper. From the viewpoint of easily increasing the grinding rate of copper, the ether compound A may include a compound having an ether group that bonds an alkyl group having a hydroxyl group as a substituent to an unsubstituted alkyl group, and the compound may have 1 A compound with a hydroxyl group and an ether group.

The ether compound A may contain compounds having the following molecular weights from the viewpoint of making it easier to increase the polishing rate of copper. The molecular weight can be above 50, above 80, above 100, above 110, above 115, above 118, above 120, above 150, above 190, above 200, above 200, above 300, above 500, above 700 or above 750. The molecular weight can be less than 3000, less than 2000, less than 1500, less than 1200, less than 1000, less than 800, less than 750, less than 700, less than 500, less than 300, less than 200, less than 200, less than 190, less than 150 or less than 120. From these viewpoints, the molecular weight may be 50-3000, 80-1000, 100-500, 100-200, or 100 or more and less than 200. The ether compound A may comprise, for example, alkoxy alcohols with a molecular weight of less than 200.

When the ether compound A is a polymer, a weight average molecular weight (Mw) can be used as the above-mentioned molecular weight. For example, the weight average molecular weight can be measured under the following conditions using gel permeation chromatography (GPC: Gel Permeation Chromatography:). [condition] Sample: 20μL Standard polyethylene glycol: manufactured by Polymer Laboratories Ltd. Standard polyethylene glycol (molecular weight: 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, and 23000) Detector: Manufactured by Showa Denko K.K., RI-monitor, product name "Syodex-RI SE-61" Pump: Manufactured by Hitachi, Ltd., product name: "L-6000" Column: Manufactured by Showa Denko K.K., used by connecting product names "GS-220HQ" and "GS-620HQ" in sequence Eluent: 0.4mol/L sodium chloride aqueous solution Measuring temperature: 30°C Flow rate: 1.00mL/min Measurement time: 45min

From the viewpoint of easily increasing the polishing rate of copper, the total mass of the ether compound (the total mass of the ether compound contained in the polishing liquid) or the total mass of the ether compound A (the total mass of the ether compound A contained in the polishing liquid) is Based on this, the content of the alkoxy alcohol may be within the following range. The content of the alkoxy alcohol may be more than 0 mass %, 5 mass % or more, 8 mass % or more, 10 mass % or more, 12 mass % or more, 15 mass % or more, 18 mass % or more, 20 mass % or more, 23 mass % or more % or more, 24 mass % or more, 25 mass % or more, 30 mass % or more, 35 mass % or more, 40 mass % or more, 45 mass % or more, 50 mass % or more, more than 50 mass %, 55 mass % or more, 60 mass % % or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more or substantially 100% by mass ( The ether compound or ether compound A contained in the polishing liquid is an aspect consisting essentially of alkoxy alcohol). The content of the alkoxy alcohol may be 100 mass % or less, less than 100 mass %, 95 mass % or less, 90 mass % or less, 85 mass % or less, 80 mass % or less, 75 mass % or less, 70 mass % or less, 65 mass % or less % or less, 60 mass % or less, 55 mass % or less, 50 mass % or less, less than 50 mass %, 45 mass % or less, 40 mass % or less, 35 mass % or less, 30 mass % or less, 25 mass % or less, or 24 mass % %the following. From these viewpoints, the content of the alkoxy alcohol may be more than 0% by mass and not more than 100% by mass, 5 to 100% by mass, 5 to 95% by mass, 5 to 50% by mass, 5 to 40% by mass, 20 to 100% by mass, 20 to 95% by mass, 20 to 50% by mass, or 20 to 40% by mass.

From the viewpoint of easily increasing the grinding speed of copper, as the content of polyether or polyglycerol, the total mass of ether compound (the total mass of ether compound contained in the grinding liquid) or the total mass of ether compound A (grinding Based on the total mass of the ether compound A contained in the liquid), the content D can be within the following range. The content D may be more than 0 mass %, 5 mass % or more, 10 mass % or more, 15 mass % or more, 20 mass % or more, 25 mass % or more, 30 mass % or more, 35 mass % or more, 40 mass % or more, 45 mass % or more. Mass % or more, 50 mass % or more, more than 50 mass %, 55 mass % or more, 60 mass % or more, 65 mass % or more, 70 mass % or more, 75 mass % or more or 76 mass % or more. The content D may be 100 mass % or less, less than 100 mass %, 95 mass % or less, 92 mass % or less, 90 mass % or less, 88 mass % or less, 85 mass % or less, 82 mass % or less, 80 mass % or less, 77 mass % or less. Mass % or less or 76 mass % or less. From these viewpoints, the content D may be more than 0% by mass and not more than 100% by mass, more than 0% by mass and not more than 95% by mass, 5 to 95% by mass, 50 to 95% by mass, 60 to 95% by mass, and more than 0% by mass. % by mass and less than 80% by mass, 5 to 80% by mass, 50 to 80% by mass, or 60 to 80% by mass.

The content of the ether compound A may be within the following range on the basis of the total mass of the polishing liquid from the viewpoint of easily increasing the polishing rate of copper. The content of the ether compound A may be more than 0% by mass, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.08% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, and 0.8% by mass More than 1% by mass, more than 1% by mass, more than 1.1% by mass, more than 1.2% by mass, more than 1.3% by mass, more than 1.31% by mass, more than 1.32% by mass, or more than 1.33% by mass. The content of the ether compound A may be 10% by mass or less, 8% by mass or less, 5% by mass or less, 3% by mass or less, 2% by mass or less, 1.8% by mass or less, 1.7% by mass or less, 1.6% by mass or less, or 1.5% by mass Less than, 1.4 mass % or less, 1.35 mass % or less, 1.33 mass % or less, 1.32 mass % or less, or 1.31 mass % or less. From these viewpoints, the content of the ether compound A may be more than 0% by mass and not more than 10% by mass, 0.1 to 10% by mass, 0.5 to 10% by mass, 1 to 10% by mass, more than 0% by mass to 5% by mass or less , 0.1 to 5% by mass, 0.5 to 5% by mass, 1 to 5% by mass, more than 0% by mass and less than 3% by mass, 0.1 to 3% by mass, 0.5 to 3% by mass, or 1 to 3% by mass.

From the viewpoint of making it easier to increase the polishing rate of copper, the content of the alkoxy alcohol may be within the following range based on the total mass of the polishing liquid. The content of the alkoxy alcohol may be more than 0% by mass, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.08% by mass or more, 0.1% by mass or more, 0.15% by mass or more, 0.2% by mass or more, and 0.25% by mass % or more, 0.3 mass % or more, 0.31 mass % or more, 0.33 mass % or more, 0.35 mass % or more, 0.4 mass % or more, 0.45 mass % or more, 0.5 mass % or more, 0.55 mass % or more, 0.6 mass % or more, 0.65 mass % or more % or more, 0.7 mass % or more, 0.8 mass % or more or 1 mass % or more. The content of the alkoxy alcohol may be 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.8% by mass or less, 0.7% by mass or less, 0.65% by mass or less, 0.6% by mass or less, 0.55% by mass or less, or 0.5% by mass % or less, 0.45 mass % or less, 0.4 mass % or less, 0.35 mass % or less, 0.33 mass % or less, or 0.31 mass % or less. From these viewpoints, the content of the alkoxy alcohol may be more than 0% by mass and not more than 5% by mass, 0.01 to 5% by mass, 0.1 to 5% by mass, 0.2 to 5% by mass, more than 0% by mass to 1% by mass Less than 0.01 to 1% by mass, 0.1 to 1% by mass, 0.2 to 1% by mass, more than 0% by mass and less than 0.8% by mass, 0.01 to 0.8% by mass, 0.1 to 0.8% by mass, 0.2 to 0.8% by mass, more than 0 % by mass and less than 0.5% by mass, 0.01 to 0.5% by mass, 0.1 to 0.5% by mass, or 0.2 to 0.5% by mass.

From the viewpoint of easily increasing the polishing rate of copper, the content E of the polyether or polyglycerol may be within the following range based on the total mass of the polishing liquid. The content E may be more than 0 mass %, 0.01 mass % or more, 0.05 mass % or more, 0.1 mass % or more, 0.3 mass % or more, 0.5 mass % or more, 0.6 mass % or more, 0.8 mass % or more, 0.9 mass % or more or 1 Mass% or more. The content E may be 10% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, or 1% by mass or less. Mass% or less. From these viewpoints, the content E may be more than 0% by mass and not more than 10% by mass, 0.01 to 10% by mass, 0.1 to 5% by mass, 0.5 to 3% by mass, or 0.5 to 2% by mass.

The content of the ether compound A may be in the following range with respect to 100 parts by mass of abrasive grains from the viewpoint of making it easier to increase the polishing rate of copper. The content of the ether compound A may be more than 0 parts by mass, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 8 parts by mass or more, 10 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, or 80 parts by mass More than, 100 parts by mass or more, more than 100 parts by mass, 110 parts by mass or more, 120 parts by mass or more, 130 parts by mass or more, 131 parts by mass or more, 132 parts by mass or more, or 133 parts by mass or more. The content of the ether compound A may be not more than 1000 parts by mass, not more than 800 parts by mass, not more than 500 parts by mass, not more than 300 parts by mass, not more than 200 parts by mass, not more than 180 parts by mass, not more than 170 parts by mass, not more than 160 parts by mass, or not more than 150 parts by mass or less, 140 parts by mass or less, 135 parts by mass or less, 133 parts by mass or less, 132 parts by mass or less, or 131 parts by mass or less. From these viewpoints, the content of the ether compound A may be more than 0 parts by mass and not more than 1000 parts by mass, 10 to 1000 parts by mass, 50 to 1000 parts by mass, 100 to 1000 parts by mass, more than 0 parts by mass and not more than 500 parts by mass , 10 to 500 parts by mass, 50 to 500 parts by mass, 100 to 500 parts by mass, more than 0 parts by mass and less than 300 parts by mass, 10 to 300 parts by mass, 50 to 300 parts by mass or 100 to 300 parts by mass.

From the viewpoint of making it easier to increase the polishing rate of copper, the content of the alkoxy alcohol may be within the following range with respect to 100 parts by mass of abrasive grains. The content of the alkoxy alcohol may be more than 0 parts by mass, 1 or more parts by mass, 3 or more parts by mass, 5 or more parts by mass, 8 or more parts by mass, 10 or more parts by mass, 15 or more parts by mass, 20 or more parts by mass, and 25 or more parts by mass More than 30 parts by mass, more than 31 parts by mass, more than 33 parts by mass, more than 35 parts by mass, more than 40 parts by mass, more than 45 parts by mass, more than 50 parts by mass, more than 55 parts by mass, more than 60 parts by mass, 65 parts by mass More than 70 parts by mass, more than 80 parts by mass or more than 100 parts by mass. The content of the alkoxy alcohol may be not more than 500 parts by mass, not more than 300 parts by mass, not more than 100 parts by mass, not more than 80 parts by mass, not more than 70 parts by mass, not more than 65 parts by mass, not more than 60 parts by mass, not more than 55 parts by mass, and not more than 50 parts by mass Not more than 45 parts by mass, not more than 40 parts by mass, not more than 35 parts by mass, not more than 33 parts by mass, or not more than 31 parts by mass. From these viewpoints, the content of the alkoxy alcohol may be more than 0 parts by mass and not more than 500 parts by mass, 1 to 500 parts by mass, 10 to 500 parts by mass, 20 to 500 parts by mass, more than 0 parts by mass to 100 parts by mass Less than 1 to 100 parts by mass, 10 to 100 parts by mass, 20 to 100 parts by mass, more than 0 parts by mass and less than 80 parts by mass, 1 to 80 parts by mass, 10 to 80 parts by mass, 20 to 80 parts by mass, more than 0 Parts by mass and less than 50 parts by mass, 1 to 50 parts by mass, 10 to 50 parts by mass, or 20 to 50 parts by mass.

From the viewpoint of making it easier to increase the polishing rate of copper, as the content of polyether or polyglycerol, the content F may be within the following range with respect to 100 parts by mass of abrasive grains. The content F may be more than 0 parts by mass, 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, or 100 parts by mass parts by mass or more. The content F may be less than 1000 parts by mass, less than 800 parts by mass, less than 700 parts by mass, less than 600 parts by mass, less than 500 parts by mass, less than 400 parts by mass, less than 300 parts by mass, less than 200 parts by mass, less than 150 parts by mass or less than 100 parts by mass Parts by mass or less. From these viewpoints, the content F may be more than 0 parts by mass and not more than 1000 parts by mass, 1 to 1000 parts by mass, 10 to 500 parts by mass, 50 to 300 parts by mass, or 50 to 200 parts by mass.

The content of the ether compound A may be in the following range with respect to 100 parts by mass of the ammonium salt from the viewpoint of making it easier to increase the polishing rate of copper. The content of the ether compound A may be more than 0 parts by mass, 10 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, 100 parts by mass or more, 110 parts by mass or more, or 120 parts by mass More than 130 parts by mass, 140 parts by mass, 150 parts by mass, 155 parts by mass, 160 parts by mass, 180 parts by mass, 200 parts by mass, 250 parts by mass, 300 parts by mass, 315 parts by mass More than 320 parts by mass, 350 parts by mass, 400 parts by mass, 500 parts by mass, 600 parts by mass, 700 parts by mass, 800 parts by mass, 1000 parts by mass, 2000 parts by mass or 5000 parts by mass above. The content of the ether compound A may be not more than 8000 parts by mass, not more than 5000 parts by mass, not more than 2000 parts by mass, not more than 1000 parts by mass, not more than 800 parts by mass, not more than 700 parts by mass, not more than 600 parts by mass, not more than 500 parts by mass, or not more than 400 parts by mass Less than 350 parts by mass, less than 320 parts by mass, less than 315 parts by mass, less than 300 parts by mass, less than 250 parts by mass, less than 200 parts by mass, less than 180 parts by mass, less than 160 parts by mass, less than 155 parts by mass, 150 parts by mass Less than or equal to 140 parts by mass, less than 130 parts by mass, less than 120 parts by mass, less than 110 parts by mass, less than 100 parts by mass, or less than 80 parts by mass. From these viewpoints, the content of the ether compound A may be more than 0 parts by mass and not more than 8000 parts by mass, 10 to 8000 parts by mass, 100 to 8000 parts by mass, more than 0 parts by mass and not more than 1000 parts by mass, and 10 to 1000 parts by mass , 100 to 1000 parts by mass, more than 0 parts by mass and less than 200 parts by mass, 10 to 200 parts by mass or 100 to 200 parts by mass.

The content of the alkoxy alcohol may be in the following range with respect to 100 parts by mass of the ammonium salt from the viewpoint of making it easier to increase the polishing rate of copper. The content of the alkoxy alcohol may be more than 0 parts by mass, 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, and 35 parts by mass More than 38 parts by mass, more than 40 parts by mass, more than 45 parts by mass, more than 50 parts by mass, more than 55 parts by mass, more than 60 parts by mass, more than 65 parts by mass, more than 70 parts by mass, more than 75 parts by mass, and more than 80 parts by mass More than 90 parts by mass, more than 100 parts by mass, more than 150 parts by mass, more than 200 parts by mass, more than 300 parts by mass, more than 500 parts by mass or more than 1000 parts by mass. The content of the alkoxy alcohol may be 2000 parts by mass or less, 1000 parts by mass or less, 500 parts by mass or less, 300 parts by mass or less, 200 parts by mass or less, 150 parts by mass or less, 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass Less than 75 parts by mass, Less than 70 parts by mass, Less than 65 parts by mass, Less than 60 parts by mass, Less than 55 parts by mass, Less than 50 parts by mass, Less than 45 parts by mass, Less than 40 parts by mass, Less than 38 parts by mass, Less than 35 parts by mass Parts or less, 30 parts by mass or less, 25 parts by mass or less, or 20 parts by mass or less. From these viewpoints, the content of the alkoxy alcohol may be more than 0 parts by mass and not more than 2000 parts by mass, more than 0 parts by mass and not more than 1000 parts by mass, more than 0 parts by mass and not more than 200 parts by mass, 1 to 2000 parts by mass, 1 to 1000 parts by mass, 1 to 200 parts by mass, 50 to 2000 parts by mass, 50 to 1000 parts by mass, or 50 to 200 parts by mass.

From the viewpoint of making it easier to increase the polishing rate of copper, as the content of polyether or the content of polyglycerol, the content G may be within the following range with respect to 100 parts by mass of the ammonium salt. The content G may be more than 0 parts by mass, 10 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, 100 parts by mass or more, 110 parts by mass or more, 115 parts by mass or more. More than 120 parts by mass, more than 150 parts by mass, more than 180 parts by mass, more than 200 parts by mass, more than 230 parts by mass, more than 250 parts by mass, more than 300 parts by mass, more than 400 parts by mass, more than 500 parts by mass, 600 parts by mass More than 800 parts by mass, more than 1000 parts by mass, more than 2000 parts by mass or more than 5000 parts by mass. The content G may be 8000 parts by mass or less, 5000 parts by mass or less, 2000 parts by mass or less, 1000 parts by mass or less, 800 parts by mass or less, 600 parts by mass or less, 500 parts by mass or less, 400 parts by mass or less, 300 parts by mass or less, 250 parts by mass or less. Less than 230 parts by mass, less than 200 parts by mass, less than 180 parts by mass, less than 150 parts by mass, less than 120 parts by mass, less than 115 parts by mass, less than 110 parts by mass, less than 100 parts by mass, less than 90 parts by mass, 80 parts by mass Parts by mass or less or 60 parts by mass or less. From these viewpoints, the content G may be more than 0 parts by mass and not more than 8000 parts by mass, more than 0 parts by mass and not more than 1000 parts by mass, more than 0 parts by mass and not more than 300 parts by mass, 10 to 8000 parts by mass, or 10 to 1000 parts by mass Parts, 10-300 parts by mass, 100-8000 parts by mass, 100-1000 parts by mass or 100-300 parts by mass.

The content of the alkoxy alcohol may be in the following range with respect to 100 parts by mass of polyether or 100 parts by mass of polyglycerol from the viewpoint of making it easier to increase the polishing rate of copper. The content of the alkoxy alcohol may be more than 0 parts by mass, 1 or more parts by mass, 3 or more parts by mass, 5 or more parts by mass, 8 or more parts by mass, 10 or more parts by mass, 15 or more parts by mass, 20 or more parts by mass, and 25 or more parts by mass More than 30 parts by mass, more than 31 parts by mass or more than 33 parts by mass. The content of the alkoxy alcohol may be not more than 1000 parts by mass, not more than 800 parts by mass, not more than 700 parts by mass, not more than 600 parts by mass, not more than 500 parts by mass, not more than 400 parts by mass, not more than 300 parts by mass, not more than 200 parts by mass, or not more than 150 parts by mass Not more than 120 parts by mass, not more than 100 parts by mass, not more than 80 parts by mass, not more than 70 parts by mass, not more than 60 parts by mass, not more than 50 parts by mass, not more than 40 parts by mass, not more than 35 parts by mass, not more than 33 parts by mass, or not more than 31 parts by mass servings or less. From these viewpoints, the content of the alkoxy alcohol may be more than 0 parts by mass and not more than 1000 parts by mass, 1 to 1000 parts by mass, 10 to 1000 parts by mass, more than 0 parts by mass and not more than 200 parts by mass, and 1 to 200 parts by mass Parts, 10 to 200 parts by mass, more than 0 parts by mass and less than 100 parts by mass, 1 to 100 parts by mass, 10 to 100 parts by mass, more than 0 parts by mass and less than 50 parts by mass, 1 to 50 parts by mass or 10 to 50 parts by mass share.

In the polishing liquid of this embodiment, as the ether compound A, xanthan gum may not be contained. Based on the total mass of the polishing liquid, the content of xanthan gum may be 0.5 mass % or less, less than 0.5 mass %, 0.1 mass % or less, 0.01 mass % or less or substantially 0 mass %.

The polishing solution of this embodiment may contain acid components (excluding compounds corresponding to ammonium salts). It is presumed that the copper polishing rate is easily increased by forming a complex between the acid component and copper, and by dissolving the copper with the acid component. In the polishing liquid of this embodiment, an organic acid component may be contained as an acid component, and an inorganic acid component may be contained.

Examples of the organic acid component include organic acids (excluding amino acids), organic acid esters, organic acid salts, amino acids, amino acid esters, and amino acid salts. Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylbutanoic acid, valeric acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glycerol acid, oxalic acid, malonic acid, succinic acid, 3 -Methylphthalic acid, 4-methylphthalic acid, 3-aminophthalic acid, 4-aminophthalic acid, 3-nitrophthalic acid, 4-nitrophthalic acid Dicarboxylic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, isophthalic acid, malic acid, tartaric acid, citric acid, p-toluenesulfonic acid, p-phenolsulfonic acid, methyl Sulfonic acid, lactic acid, itaconic acid, quinaldixic acid, adipic acid, etc. Examples of organic acid esters include esters of the aforementioned organic acids. Examples of organic acid salts include alkali metal salts, alkaline earth metal salts, halides, and the like of the aforementioned organic acids. Examples of amino acids include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, and isoleucine. acid, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, etc. Examples of amino acid esters include esters of the aforementioned amino acids. Examples of amino acid salts include alkali metal salts of the aforementioned organic acids, and the like. From the point of view of further improving the copper grinding rate, the organic acid component may contain at least one selected from the group consisting of organic acids different from amino acids and amino acids, and may also contain malic acid and glycerin. At least one of the group consisting of amino acids.

Examples of the inorganic acid component include inorganic acids, metal salts of inorganic acids (alkali metal salts, alkaline earth metal salts, etc.), and the like. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, chromic acid and the like.

From the viewpoint of making it easier to increase the copper polishing rate, the content of the organic acid different from the amino acid may be within the following range based on the total mass of the polishing liquid. The content of the organic acid different from the amino acid may be more than 0% by mass, 0.001% by mass or more, 0.003% by mass or more, 0.005% by mass or more, 0.008% by mass or more, or 0.01% by mass or more. The content of organic acids different from amino acids may be 1% by mass or less, 0.5% by mass or less, 0.1% by mass or less, 0.08% by mass or less, 0.05% by mass or less, 0.03% by mass or less, 0.02% by mass or less, or 0.01% by mass the following. From these viewpoints, the content of organic acids different from amino acids may be more than 0% by mass and not more than 1% by mass, 0.001 to 1% by mass, 0.001 to 0.1% by mass, 0.005 to 0.1% by mass, or 0.001 to 0.05% by mass %.

From the viewpoint of easily increasing the copper polishing rate, the content H of the content of the acid component or the content of the organic acid component may be within the following range based on the total mass of the polishing liquid. The content H may be more than 0% by mass, 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, or 0.41% by mass or more. The content H may be 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.8% by mass or less, 0.6% by mass or less, 0.5% by mass or less, 0.45% by mass or less, 0.41% by mass or less, or 0.4% by mass or less. From these viewpoints, the content H may be more than 0% by mass and not more than 2% by mass, 0.01 to 2% by mass, 0.1 to 2% by mass, 0.01 to 1% by mass, or 0.1 to 1% by mass.

The polishing liquid of this embodiment may contain an antiseptic (an antiseptic for metal materials) as a compound having an antiseptic effect on metal materials. The anticorrosion agent forms a protective film on the metal material, thereby easily suppressing the etching of the metal material and reducing the roughness of the surface to be polished.

The preservative may contain at least A sort of. "Compound" is a general term for compounds having a skeleton thereof, for example, "triazole compound" means a compound having a triazole skeleton. From the viewpoint of easily obtaining an appropriate antiseptic effect, the preservative may contain at least one selected from the group consisting of triazole compounds, pyridine compounds, imidazole compounds, tetrazole compounds, triazine compounds, and hexamethylenetetramine, A triazole compound may also be included, and a benzotriazole compound may also be included.

Examples of triazole compounds include 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, benzotriazole, 1-hydroxy Benzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxy-1H-benzotriazole, 4- Carboxy-1H-benzotriazole methyl ester (1H-benzotriazole-4-carboxylic acid methyl ester), 4-carboxy-1H-benzotriazole butyl ester (1H-benzotriazole-4-carboxylic acid methyl ester) butyl ester), 4-carboxy-1H-benzotriazole octyl ester (1H-benzotriazole-4-carboxylate octyl ester), 5-hexylbenzotriazole, [1,2,3-benzotriazole Base-1-methyl][1,2,4-triazolyl-1-methyl][2-ethylhexyl]amine, tolyltriazole, naphthotriazole, bis[(1-benzotriazole base) methyl]phosphonic acid, 3H-1,2,3-triazolo[4,5-b]pyridin-3-ol, 1H-1,2,3-triazolo[4,5-b] Pyridine, 1-acetyl-1H-1,2,3-triazolo[4,5-b]pyridine, 1,2,4-triazolo[1,5-a]pyrimidine, 2-methyl -5,7-diphenyl-[1,2,4]triazolo[1,5-a]pyrimidine, 2-methylsulfanyl-5,7-diphenyl-[1,2,4 ]triazolo[1,5-a]pyrimidine, 2-methylsulfanyl-5,7-diphenyl-4,7-dihydro-[1,2,4]triazolo[1,5 -a] pyrimidine and the like. Compounds having a triazole skeleton and other skeletons in one molecule are classified as triazole compounds. The polishing liquid of this embodiment may contain a triazole compound having a hydroxyl group or may contain 1-hydroxybenzotriazole from the viewpoint of easily obtaining an appropriate antiseptic effect.

From the viewpoint of easily obtaining a suitable antiseptic effect, as the content of the preservative, the content of the triazole compound or the content of the benzotriazole compound, based on the total mass of the polishing liquid, the content I can be within the following range. The content I may be more than 0% by mass, 0.001% by mass or more, 0.003% by mass or more, 0.005% by mass or more, 0.008% by mass or more, 0.01% by mass or more, 0.02% by mass or more, 0.025% by mass or more, or 0.03% by mass or more. The content I may be 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.3% by mass or less, 0.1% by mass or less, 0.08% by mass or less, 0.05% by mass or less, 0.04% by mass or less, 0.03% by mass or less Mass % or less, 0.025 mass % or less, 0.02 mass % or less, 0.01 mass % or less, or 0.008 mass % or less. From these viewpoints, the content I may be more than 0% by mass and not more than 2% by mass, 0.001 to 2% by mass, 0.005 to 2% by mass, 0.01 to 2% by mass, more than 0% by mass to 1% by mass, or 0.001 to 2% by mass. 1% by mass, 0.005 to 1% by mass, 0.01 to 1% by mass, more than 0% by mass and less than 0.1% by mass, 0.001 to 0.1% by mass, 0.005 to 0.1% by mass, or 0.01 to 0.1% by mass.

The polishing solution of this embodiment may contain alkaline hydroxide. By using alkali hydroxide, it is easy to increase the polishing rate of copper. Examples of the alkaline hydroxide include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides; tetramethylammonium hydroxide (TMAH) and the like.

From the viewpoint of making it easier to increase the polishing rate of copper, the content of the alkali hydroxide may be within the following range on the basis of the total mass of the polishing liquid. The content of the alkaline hydroxide may be more than 0 mass %, 0.01 mass % or more, 0.05 mass % or more, 0.1 mass % or more, 0.15 mass % or more, 0.2 mass % or more, 0.25 mass % or more, 0.3 mass % or more, 0.35 mass % or more Mass % or more, 0.36 mass % or more, 0.4 mass % or more, 0.45 mass % or more, or 0.48 mass % or more. The content of the alkaline hydroxide may be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.8% by mass or less, 0.6% by mass or less, 0.5% by mass or less, 0.48% by mass or less Mass % or less, 0.45 mass % or less, 0.4 mass % or less, 0.36 mass % or less, 0.35 mass % or less, 0.3 mass % or less, or 0.25 mass % or less. From these viewpoints, the content of the alkali hydroxide may be more than 0% by mass and not more than 5% by mass, 0.01 to 5% by mass, 0.1 to 5% by mass, more than 0% by mass and not more than 1% by mass, 0.01 to 1% by mass % by mass or 0.1 to 1% by mass.

The polishing solution of this embodiment may contain a peroxide that does not correspond to the above-mentioned ammonium salt, or may not contain the peroxide. Examples of peroxides include potassium persulfate, hydrogen peroxide, iron nitrate, iron sulfate, ozone, hypochlorous acid, hypochlorite, potassium periodate, and peracetic acid. The polishing liquid of this embodiment may not contain hydrogen peroxide. Based on the total mass of the polishing liquid, the content of peroxide or hydrogen peroxide can be 0.1 mass % or less, less than 0.1 mass %, 0.01 mass % or less, 0.001 mass % or less or substantially 0 mass %.

The polishing liquid of this embodiment may contain an organic solvent (an organic solvent that does not correspond to the ether compound A) from the viewpoint of easily increasing the polishing rate of copper. Examples of organic solvents include alcohols (monohydric alcohols and polyhydric alcohols), carbonates, lactones, and the like. Examples of the monohydric alcohol include methanol, ethanol, propanol (for example, 2-propanol), butanol, pentanol, octanol and the like. Examples of the polyhydric alcohol include diols such as methylene glycol, ethylene glycol, propylene glycol, butanediol (for example, 1,3-butanediol), and hexanediol; glycerin; and the like. Examples of carbonate esters include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. As lactone, propiolactone, butyrolactone, etc. are mentioned. From the viewpoint of easily improving the grinding rate of copper, the organic solvent may contain alcohol, may also contain monohydric alcohol, may also contain propanol, may also contain polyhydric alcohol, and may also contain a solvent selected from methylene glycol, ethylene glycol, propylene glycol, At least one of the group consisting of butanediol and hexanediol.

From the viewpoint of making it easier to increase the polishing rate of copper, the content of the organic solvent may be within the following range based on the total mass of the polishing liquid. The content of the organic solvent may be more than 0 mass %, 0.1 mass % or more, 0.3 mass % or more, 0.5 mass % or more, 0.6 mass % or more, 0.7 mass % or more, 0.8 mass % or more, 1 mass % or more, 1.2 mass % or more Or 1.3% by mass or more. The content of the organic solvent may be 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1.5% by mass or less . From these viewpoints, the content of the organic solvent may be more than 0% by mass and not more than 20% by mass, 0.1 to 20% by mass, 1 to 20% by mass, more than 0% by mass and not more than 5% by mass, 0.1 to 5% by mass, or 1 to 5% by mass.

The polishing liquid of this embodiment may not contain dihydroxyethylglycine, amino polycarboxylic acid and non-metallic salt of amino polycarboxylic acid. Based on the total mass of the polishing liquid, the content (total amount) of dihydroxyethylglycine, amino polycarboxylic acid and non-metallic salt of amino polycarboxylic acid can be 0.05% by mass or less, less than 0.05% by mass, 0.01 mass % or less, 0.001 mass % or less, or substantially 0 mass %.

The polishing liquid of this embodiment may not contain a compound having a monomer unit of an unsaturated carboxylic acid, and may not contain a polycarboxylic acid-based polymer dispersant. Based on the total mass of the grinding liquid, the content of the compound with unsaturated carboxylic monomer units or the content of the polycarboxylic acid polymer dispersant can be less than 0.0005 mass%, less than 0.0005 mass%, and less than 0.0001 mass%, 0.00001% by mass or substantially 0% by mass.

(pH) From the viewpoint of improving the polishing rate of copper, the pH of the polishing liquid of this embodiment is 9.00 or more. From the viewpoint of increasing the polishing rate of copper and adjusting the polishing rate, the pH of the polishing liquid according to the present embodiment may be within the following range. The pH of the grinding liquid can be above 9.10, above 9.15, above 9.20, above 9.25, above 9.30, above 9.35, above 9.40, above 9.45, above 9.50, above 9.55, above 9.60, above 9.65, above 9.70, above 9.75, above 9.80 , above 9.85, above 9.90, above 9.95, above 10.00, above 10.00, above 10.05, above 10.10, above 10.20, above 10.30, above 10.50 or above 10.80. The pH of the polishing liquid can be below 13.00, below 12.50, below 12.00, below 11.50, below 11.00, below 10.50, below 10.10, below 10.05, below 10.00, below 9.95, below 9.90, below 9.85, below 9.80, below 9.75, below 9.70 , less than 9.65, less than 9.60, less than 9.55, less than 9.50, less than 9.45, less than 9.40, less than 9.35, less than 9.30, less than 9.25, less than 9.20 or less than 9.15. From these viewpoints, the pH of the polishing liquid can be 9.00-13.00, 9.00-12.00, 9.00-11.00, 9.00-10.00, 9.30-13.00, 9.30-12.00, 9.30-11.00, 9.30-10.00, 9.50-13.00, 9.50- 12.00, 9.50 to 11.00 or 9.50 to 10.00. The pH of the polishing liquid can be adjusted by the aforementioned ammonium salt, ammonia, acid components, alkaline hydroxide, and the like.

The pH of the polishing liquid in this embodiment can be measured with a pH meter (for example, model number: PHL-40 manufactured by DKK-TOA CORPORATION). For example, after using phthalate pH buffer (pH: 4.01) and neutral phosphate pH buffer (pH: 6.86) as the standard buffer and performing 2-point calibration on the pH meter, the electrodes of the pH meter The polishing solution was put in, and the value after stabilizing for 2 minutes or more was measured. At this time, the liquid temperatures of the standard buffer solution and the polishing solution were both set to 25°C.

(preservation form) The polishing liquid of this embodiment is used as a storage liquid for polishing liquid, and can be stored with a reduced amount of water than when used. The stock liquid for polishing liquid is a stock liquid for obtaining the polishing liquid, and the polishing liquid is obtained by diluting the stock liquid for polishing liquid with water before or during use. The dilution factor is, for example, 1.5 times or more.

The polishing liquid of this embodiment may be stored as a one-liquid type polishing liquid containing at least abrasive grains and ammonium salt, or may be stored as a multiple-liquid type polishing liquid having a slurry (first liquid) and an additive liquid (second liquid). In the multi-liquid type polishing liquid, the constituent components of the polishing liquid are divided into a slurry and an additive liquid so that the slurry and the additive liquid are mixed to form a polishing liquid. The slurry contains at least abrasive grains and water, for example. The additive liquid contains at least an ammonium salt and water, for example. Abrasive grains, ammonium salts, and components other than water may be contained in the slurry and the additive liquid in the additive liquid. The components of the polishing liquid can be stored in three or more liquids. In the multi-liquid type polishing liquid, the slurry and the additive liquid can be mixed before or during polishing to prepare the polishing liquid. The slurry and the additive liquid in the multi-liquid type polishing liquid are separately supplied to the grinding table, and the slurry and the additive liquid can be mixed on the grinding table to prepare the polishing liquid.

＜Grinding method＞ The polishing method of the present embodiment includes a polishing step of polishing a member to be polished containing copper using the polishing liquid of the present embodiment. In the polishing step, the polished surface of the polished member can be polished, and the polished surface where copper exists can be polished. In the grinding step, at least a part of copper in the member to be polished can be ground and removed. The member to be polished may contain resin and metal materials (such as copper). In the polishing step, the surface to be polished where the resin and the metal material exist can be polished. The polishing liquid used in the grinding step may be the above-mentioned one-liquid type polishing liquid, or may be a polishing liquid obtained by diluting the storage liquid for polishing liquid with water, or may be obtained by mixing the above-mentioned multiple liquid type polishing liquid. Slurry and slurry obtained by adding liquid. The member to be polished is not particularly limited, and may be a wafer (such as a semiconductor wafer) or a wafer (such as a semiconductor wafer). The member to be polished may be a wiring board or a circuit board.

＜Manufacturing method, etc.＞ The manufacturing method of the module of this embodiment has the module manufacturing process which uses the to-be-polished member (substrate) polished by the grinding method of this embodiment, and obtains a module. The device of this embodiment is a device obtained by the manufacturing method of the device of this embodiment. The components of this embodiment are not particularly limited, but may be electronic components (such as semiconductor packages and other semiconductor components), wafers (such as semiconductor wafers), or chips (such as semiconductor chips). As an aspect of the manufacturing method of the component of this embodiment, in the manufacturing method of the electronic component of this embodiment, the electronic component is obtained using the member to be polished polished by the grinding method of this embodiment. As an aspect of the manufacturing method of the device of the present embodiment, in the manufacturing method of the semiconductor device of the present embodiment, a semiconductor device (for example, a semiconductor package) is obtained using a member to be polished polished by the polishing method of the present embodiment. The manufacturing method of the module of the present embodiment may include a polishing step of polishing the member to be polished by the polishing method of the present embodiment before the manufacturing step of the module.

In the manufacturing method of the module of the present embodiment, as one aspect of the manufacturing step of the module, a singulation step of singulating the member to be polished (substrate) polished by the polishing method of the present embodiment into pieces may be provided. The singulation step may be, for example, a step of dicing a wafer (such as a semiconductor wafer) polished by the polishing method of this embodiment to obtain wafers (such as a semiconductor wafer). As an aspect of the manufacturing method of the component of the present embodiment, the manufacturing method of the electronic component of the present embodiment may include obtaining an electronic component (such as a semiconductor) by singulating the member to be polished polished by the grinding method of the present embodiment components) steps. As an aspect of the manufacturing method of the device of the present embodiment, the manufacturing method of the semiconductor device of the present embodiment may include the step of obtaining a semiconductor device (such as a semiconductor device) by singulating the member to be polished polished by the grinding method of the present embodiment package) steps.

In the manufacturing method of the component of this embodiment, as an aspect of the component manufacturing step, there may be a step of connecting (for example, electrically connecting) the polished member (substrate) polished by the polishing method of this embodiment to other connected bodies. . The connected body connected to the polished member ground by the grinding method of the present embodiment is not particularly limited, and may be the ground member ground by the grinding method of the present embodiment, or may be ground by the grinding method of the present embodiment The connected body is different from the ground member. In the connecting step, the polished member and the connected body may be directly connected (the polished member and the connected body are connected in a state of contact), or the polished member and the connected body may be connected through other members (conductive members, etc.). The connection step can be performed before the singulation step, after the singulation step, or before and after the singulation step.

The connecting step may be a step of connecting the ground surface of the ground member ground by the grinding method of this embodiment and the connected body, or it may be a step of connecting the ground surface of the ground member ground by the grinding method of this embodiment and the connected body. Steps for connecting surfaces of bodies. The connection surface of the member to be polished may be the surface to be polished by the polishing method of this embodiment. Through the connecting step, a connected body including a member to be polished and a connected body can be obtained. In the connecting step, when the connecting surface of the member to be polished has a metal portion, the object to be connected may be brought into contact with the metal portion. In the connecting step, when the connecting surface of the member to be polished has a metal part and the connecting surface of the object to be connected has a metal part, the metal parts may be brought into contact with each other. The metal part may contain copper.

The device of this embodiment (for example, an electronic device such as a semiconductor device) has at least one selected from the group consisting of a polished member polished by the polishing method of this embodiment, and a component of this embodiment. [Example]

Hereinafter, although this indication is demonstrated concretely based on an Example, this indication is not limited to this Example.

＜Preparation of polishing liquid＞ By mixing each component of Tables 1 to 4 and distilled water, polishing liquids having the compositions shown in each table were obtained. Each table shows the content (unit: mass %) of each component based on the total mass of the polishing liquid, and the remainder is distilled water. As abrasive grains, cerium oxide particles (manufactured by Showa Denko Materials co., Ltd., product name: HS-8005) or colloidal silica (manufactured by Fuso Chemical Co., Ltd., product name: PL-3) were used . The content of colloidal silica is the content of silica particles as solid content. "MMB" refers to 3-methoxy-3-methyl-1-butanol, and "HBTA" refers to 1-hydroxybenzotriazole. As polyglycerol, a product name "PGL750" (glycerol decamer, weight average molecular weight: 750, hydroxyl value: 870 to 910) manufactured by Sakamoto Yakuhin kogyo Co., Ltd. was used.

<Average grain size of abrasive grains> Using "Microtrac MT3300EXII" manufactured by Microtrac Inc., the average particle diameter of the abrasive grains in the polishing liquid of each example was determined. In each example, the average particle diameter D50 was 341 nm, and the average particle diameter D80 was 609 nm.

＜pH of polishing liquid＞ The pH of the polishing liquid was measured using a pH meter (model: PHL-40 manufactured by DKK-TOA CORPORATION). Phthalate pH buffer (pH: 4.01) and neutral phosphate pH buffer (pH: 6.86) are used as standard buffers and after 2-point calibration of the pH meter, put the electrode of the pH meter into the As for the polishing liquid, the value after stabilizing for 2 minutes or more was measured. The results are shown in each table.

<Polishing Evaluation> As a substrate for evaluating the polishing rate of copper, a substrate having a copper film formed on a φ300 mm silicon wafer was prepared. In a lapping device (manufactured by Applied Materials, Inc., product name: Reflexion LK), a substrate was mounted on a substrate mounting holder to which an adsorption pad was attached. On the platform to which the pad made of porous polyurethane resin was attached, a holder was mounted so that the surface to be polished faced the pad. The aforementioned polishing liquid was supplied onto the pad at a supply rate of 350 mL/min, and the substrate was pressed against the pad with a polishing load of 4 psi. At this time, grinding was performed by rotating the platform at 147 min ^-1 and the holder at 153 min ^-1 for 1 minute. The ground substrate was sufficiently washed with pure water and then dried. Using a metal film thickness measuring device (manufactured by Hitachi Kokusai Electric Inc., product name: VR-120/08S), the film thickness change before and after polishing of the copper film was measured to obtain the copper polishing rate (Cu-RR). The thicknesses of 65 points arranged at equal intervals on a line (diameter) passing through the center of the substrate were measured, and the average value was taken as the thickness of the copper film. The results are shown in each table.

It was confirmed that in each example, compared with Comparative Example 1 not using abrasive grains containing cerium oxide, Comparative Examples 2 and 3 not using ammonium salt, and Comparative Examples 4 and 5 in which the pH was not 9.00 or higher, excellent performance was obtained. Grinding speed.

[Table 1] Example 1 2 3 4 5 6 7 8 9 10 11 12 composition Cerium oxide particles 1 1 1 1 1 1 1 1 1 1 1 1 ammonium carbonate 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 ammonia 0.30 MMB 0.333 0.333 0.333 0.333 0.333 0.333 0.305 Polyglycerol 1 1 1 1 1 1 1 1-propoxy-2-propanol 1.333 Hexylene glycol 1.333 1,3-Butanediol 1.333 2-propanol 1.333 malic acid 0.01 Glycine 0.4 HBTA 0.010 0.008 0.025 Potassium hydroxide 0.48 0.24 0.48 0.48 pH 9.93 9.39 9.24 9.70 10.50 9.56 9.13 9.79 9.81 9.86 9.84 9.87 Cu-RR[μm/min] 0.64 0.90 0.75 0.68 0.62 0.58 0.61 0.76 0.76 0.75 0.64 0.49

[Table 2] Example 13 14 15 16 17 18 19 composition Cerium oxide particles 1 1 1 1 1 1 1 ammonium carbonate 0.42 0.42 0.42 0.42 0.42 1.69 1.69 Ammonium persulfate 0.60 0.80 ammonia 0.15 MMB 0.333 0.333 0.305 0.305 0.305 0.333 0.333 Polyglycerol 1 1 1 1 1 1 1 malic acid 0.01 0.01 0.01 0.01 0.01 0.01 Glycine 0.4 0.4 0.4 0.4 0.4 0.4 0.4 HBTA 0.025 0.025 0.025 Potassium hydroxide 0.48 0.48 0.48 0.48 0.48 0.48 0.48 pH 9.89 10.10 9.82 9.41 9.33 9.47 9.52 Cu-RR[μm/min] 0.40 0.65 0.40 1.08 1.32 0.56 0.42

[table 3] Example 20 twenty one twenty two twenty three twenty four 25 26 27 28 29 composition Cerium oxide particles 1 1 1 1 1 1 1 1 1 1 Ammonium persulfate 0.80 0.80 Ammonium acetate 0.02 0.02 1.36 ammonium bicarbonate 1.39 ammonium sulfate 1.16 0.10 ammonium chloride 0.94 Ammonium dihydrogen phosphate 1.16 0.10 ammonia 0.15 0.30 0.30 0.30 0.30 MMB 0.333 0.333 0.333 0.333 0.333 0.333 0.333 0.333 0.333 Polyglycerol 1 1 1 1 1 1 1 1 1 malic acid 0.01 Glycine 0.4 HBTA 0.030 0.008 0.008 0.008 0.008 Potassium hydroxide 0.48 0.48 0.48 0.48 0.48 0.48 pH 9.97 10.67 10.89 9.61 9.30 9.47 10.36 9.51 9.71 10.24 Cu-RR[μm/min] 1.22 1.21 0.40 0.44 0.63 0.84 0.41 0.45 0.64 0.40

[Table 4] comparative example 1 2 3 4 5 composition Cerium oxide particles 1 1 1 1 Colloidal silica 1 ammonium carbonate 0.42 1.69 ammonium bicarbonate 0.70 MMB 0.333 0.333 0.333 0.333 0.333 Polyglycerol 1 1 1 1 malic acid 0.01 0.01 0.01 0.01 Glycine 0.4 0.4 0.4 HBTA 0.008 Potassium hydroxide 0.48 0.48 0.48 pH 9.82 12.16 12.92 8.56 7.99 Cu-RR[μm/min] 0.31 0.09 0.06 0.26 0.31

Claims (17)

A grinding liquid containing abrasive grains comprising cerium oxide and ammonium salt, And the pH is 9.00 or more. The polishing liquid as described in claim item 1, wherein The aforementioned ammonium salt includes ammonium carbonate. The grinding liquid as described in claim 2, wherein The aforementioned ammonium salt further includes ammonium persulfate. The polishing liquid as described in claim item 1, wherein Content of the said ammonium salt is 0.3-2 mass %. The polishing liquid according to claim 1, which further contains ammonia. The polishing liquid according to claim 1, further comprising an ether compound having a hydroxyl group. The polishing liquid as described in claim 6, wherein The aforementioned ether compounds include alkoxy alcohols. The grinding liquid as described in claim item 7, wherein The aforementioned alkoxy alcohols include 3-methoxy-3-methyl-1-butanol. The grinding liquid as described in claim item 7, wherein Based on the total mass of the polishing liquid, the content of the aforementioned alkoxy alcohol is 0.2-0.8% by mass. The polishing liquid as described in claim 6, wherein The aforementioned ether compound includes a compound having two or more hydroxyl groups. The grinding liquid as described in claim item 7, wherein The aforementioned ether compound further includes polyether. The polishing liquid as described in claim item 11, wherein The aforementioned polyether contains polyglycerol. The polishing liquid as described in claim item 11, wherein Based on the total mass of the polishing liquid, the content of the aforementioned polyether is 0.5-3% by mass. The polishing liquid as described in Claim 1 has a pH of 9.00-11.00. A grinding method, using the grinding liquid described in any one of Claims 1 to 14, to grind a component to be ground containing copper. A method of manufacturing a component, using a polished member ground by the grinding method described in claim 15 to obtain the component. A method of manufacturing a semiconductor device, using a polished member polished by the grinding method described in claim 15 to obtain a semiconductor device.