WO2023032028A1 - Polishing solution, polishing method, method for producing semiconductor component, and method for producing joined body - Google Patents

Abstract

The present invention provides a polishing solution that contains an ammonium salt and abrasive grains containing cerium oxide, and that has a pH of 9.00 or greater. The present invention provides a polishing method for polishing, using this polishing solution, a member to be polished that contains copper. The present invention provides a method for producing a semiconductor component, in which a semiconductor component is obtained by dicing a member to be polished that has been polished by the polishing method. The present invention provides a method for producing a joined body, in which a joining surface of a body to be joined is joined with a joining surface of a member to be polished that has been polished by the polishing method, or a joining surface of a semiconductor component obtained by the method for producing a semiconductor component.

Description

Polishing liquid, polishing method, semiconductor component manufacturing method, and joined body manufacturing method

The present disclosure relates to a polishing liquid, a polishing method, a semiconductor component manufacturing method, a bonded body manufacturing method, and the like.

In the manufacturing process of electronic devices in recent years, the importance of processing technology for increasing density and miniaturization is increasing. CMP (Chemical Mechanical Polishing) technology, which is one of the processing technologies, is used in the manufacturing process of electronic devices to form shallow trench isolation (shallow trench isolation: STI), premetal insulating material or interlayer It is an essential technology for flattening insulating materials, forming plugs or embedded metal wiring, and the like. As a polishing liquid used for CMP, a polishing liquid containing abrasive grains containing cerium oxide is known (see, for example, Patent Documents 1 and 2 below).

JP-A-10-106994 Japanese Patent Application Laid-Open No. 08-022970

For polishing liquids that can be used for CMP, there are cases where it is required to quickly remove copper-containing members by polishing them. Such a polishing liquid is required to improve the polishing rate of copper.

An object of one aspect of the present disclosure is to provide a polishing liquid capable of improving the polishing rate of copper. Another aspect of the present disclosure aims to provide a polishing method using the polishing liquid. Another aspect of the present disclosure aims to provide a method for manufacturing a semiconductor component using the polishing method. Another aspect of the present disclosure aims to provide a bonded body manufacturing method using the polishing method or the semiconductor component manufacturing method.

One aspect of the present disclosure provides a polishing liquid containing abrasive grains containing cerium oxide and an ammonium salt, and having a pH of 9.00 or higher.

Another aspect of the present disclosure provides a polishing method for polishing a copper-containing member to be polished using the polishing liquid described above.

According to such a polishing liquid and polishing method, it is possible to improve the polishing rate of copper.

Another aspect of the present disclosure provides a method for manufacturing a semiconductor component, which obtains a semiconductor component by singulating the member to be polished that has been polished by the above-described polishing method.

Another aspect of the present disclosure is a bonding surface of a member to be polished polished by the above-described polishing method, or a bonding surface of a semiconductor component obtained by the above-described method for manufacturing a semiconductor component, and a bonding surface of the object to be bonded. To provide a method for manufacturing a joined body, which joins and.

According to one aspect of the present disclosure, it is possible to provide a polishing liquid capable of improving the polishing rate of copper. According to another aspect of the present disclosure, it is possible to provide a polishing method using the polishing liquid. According to another aspect of the present disclosure, it is possible to provide a method of manufacturing a semiconductor component using the polishing method. According to another aspect of the present disclosure, it is possible to provide a method for manufacturing a bonded body using the polishing method or the method for manufacturing a semiconductor component. According to another aspect of the present disclosure, it is possible to provide an application of the polishing liquid for polishing a member to be polished containing copper.

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

In this specification, a numerical range indicated using "-" indicates a range that includes the numerical values before and after "-" as the minimum and maximum values, respectively. "A or more" in a numerical range means A and a range exceeding A. "A or less" in a numerical range means A and a range less than A. In the numerical ranges described stepwise in this specification, the upper limit value or lower limit value of the numerical range in one step can be arbitrarily combined with the upper limit value or lower limit of the numerical range in another step. In the numerical ranges described herein, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples. "A or B" may include either A or B, or may include both. The materials exemplified in this specification can be used singly or in combination of two or more unless otherwise specified. The content of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. An "alkyl group" may be linear, branched or cyclic, unless otherwise specified. "Abrasive grain" means an aggregate of a plurality of grains, but for the sake of convenience, one grain that constitutes the abrasive grain may be called an abrasive grain.

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

According to the polishing liquid according to the present embodiment, it is possible to improve the polishing rate of copper, and the polishing rate is 0.35 μm / min or more (for example, 0.40 μm / min or more) in the evaluation method described in the examples below. polishing rate can be obtained. The reason why the polishing rate of copper is improved is not necessarily clear, but the present inventor presumes that it is as follows. That is, the ammonium salt or the ammonium cation of the ammonium salt forms a complex with copper, and the oxidizing power of the cerium oxide of the abrasive grains acts to promote the formation of this complex, thereby increasing the polishing rate of copper. expected to improve. However, the factor for obtaining the effect is not limited to the content.

The polishing liquid according to this embodiment can be used for polishing a member to be polished containing copper. The polishing liquid according to the present embodiment may be used for polishing a member to be polished other than the member to be polished containing copper. In recent years, three-dimensional integration technology for semiconductor chips has been developed from the viewpoint of increasing the speed, reducing power consumption, and increasing the capacity of electronic devices. Demand for chip bonding by wafer is increasing. A resin (for example, epoxy resin) as a sealing material and a metal (for example, copper) as a wiring material may be present on the bonding surface. The polishing liquid according to this embodiment may be used to polish a member to be polished containing resin (eg, epoxy resin) and metal (eg, copper).

The polishing liquid according to this embodiment contains abrasive grains containing cerium oxide. By using abrasive grains containing cerium oxide, the polishing rate of copper can be improved. Abrasive grains may comprise one or more types of particles. Inorganic materials such as silica (SiO ₂ ), alumina, zirconia, titania, germania, silicon carbide, etc., can be cited as constituent materials of abrasive grains other than cerium oxide. The polishing liquid according to this embodiment may not contain alumina as abrasive grains. The content of alumina is 0.1% by mass or less, less than 0.1% by mass, 0.01% by mass or less, 0.001% by mass or less, or substantially 0% by mass, based on the total mass of the polishing liquid. %.

The content of cerium oxide in the abrasive grains is based on the entire abrasive grains (the entire abrasive grains contained in the polishing liquid, or the entire grain that constitutes the abrasive grains) from the viewpoint of easily improving the polishing rate of copper. As, 90% by mass or more, 93% by mass or more, 95% by mass or more, more than 95% by mass, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, or 99.9% by mass or more good. The abrasive grains may be in an aspect in which the abrasive grains are substantially made of cerium oxide (an aspect in which substantially 100 mass % of the abrasive grains are cerium oxide).

The average particle diameters D50 and D80 of the abrasive grains may be within the following ranges from the viewpoint of easily improving the polishing rate of copper. The average particle diameters D50 and D80 of the abrasive grains mean the 50% and 80% particle diameters of the volume-based cumulative distribution, and can be measured by, for example, a laser diffraction particle size distribution meter. The average grain size of abrasive grains can be measured, for example, with a laser diffraction grain 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 adjustment may be performed after mixing the components of the polishing liquid.

The average grain size D50 of the abrasive grains may be 10 nm or more, 50 nm or more, 100 nm or more, 150 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 320 nm or more, or 340 nm or more. The average grain size 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 these points of view, the average grain size D50 of the abrasive grains may be 10 to 1000 nm.

The average grain size 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. The average grain size 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 points of view, the average grain size D80 of the abrasive grains may be 50 to 1200 nm.

The content of abrasive grains may be within the following range based on the total mass of the polishing liquid, from the viewpoint of easily improving the polishing rate of copper. The content of abrasive grains is 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, 0.7% by mass or more, 0 0.8% by mass or more, 0.9% by mass or more, or 1% by mass or more. The abrasive content 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, or 1% by mass or less. From these points of view, the content of abrasive grains may be 0.01 to 10% by mass, 0.1 to 5% by mass, or 0.5 to 2% by mass.

The polishing liquid according to this embodiment contains an ammonium salt. Ammonium salts are salts of acid moieties and ammonium cations. The ammonium salt may contain at least one selected from the group consisting of inorganic acid ammonium salts and organic acid ammonium salts. Ammonium salts may include ammonium salts that are different from peroxides and may include peroxides (such as ammonium persulfate).

Examples of 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 sulfate and ammonium persulfate; ammonium salts of trivalent inorganic acids such as ammonium acid; Ammonium salts may include ammonium carbonate and may include ammonium persulfate.

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-ethylbutyric acid, and 4-methylpentanoic acid. , n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric 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, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, isophthalic acid, malic acid, tartaric acid, citric acid, p -toluenesulfonic acid, p-phenolsulfonic acid, methylsulfonic acid, lactic acid, itaconic acid, maleic acid, quinaldic acid, adipic acid, pimelic acid and the like.

The ammonium salt may contain an ammonium salt of an inorganic acid, may contain an ammonium salt of a divalent inorganic acid, and is at least selected from the group consisting of ammonium carbonate and ammonium persulfate, from the viewpoint of easily improving the polishing rate of copper. may contain one The ammonium salt may include an ammonium salt different from a peroxide and a peroxide, and may include ammonium carbonate and ammonium persulfate, from the viewpoint of easily improving the polishing rate of copper.

As the content of the ammonium salt different from the peroxide or the content of the ammonium carbonate, the content A1 is the total mass of the ammonium salt (the ammonium salt The following range may be based on the total mass of Content A1 is more than 0% by mass, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 34% by mass or more, 35% by mass or more, 40% by mass or more, 41% by mass or more, 45% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more . The ammonium salt contained in the polishing liquid is substantially an ammonium salt different from peroxide or ammonium carbonate. ammonium salt different from or ammonium carbonate). The content A1 is 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, It may be 45% by mass or less, 41% by mass or less, 40% by mass or less, 35% by mass or less, or 34% by mass or less. From these points of view, the content A1 may be more than 0% by mass and 100% by mass or less.

When the ammonium salt contains a peroxide, the content A2 of the content of the peroxide (ammonium salt) or the content of ammonium persulfate is the total mass of the ammonium salt (the total amount of the ammonium salt contained in the polishing liquid). mass) as a reference, it may be in the following range. The content A2 is more than 0% by mass, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more from the viewpoint of easily improving the polishing rate of copper. , 50% by mass or more, 55% by mass or more, 59% by mass or more, 60% by mass or more, 65% by mass or more, or 66% by mass or more. The content A2 is 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, or 66% by mass from the viewpoint of easily improving the copper polishing rate. % or less. The content A2 may be 65% by mass or less, 60% by mass or less, or 59% by mass or less. From these points of view, the content A2 may be more than 0% by mass and less than 100% by mass.

The content of ammonium salts (the total amount of compounds corresponding to ammonium salts; the same shall apply hereinafter), the content of ammonium salts different from peroxides, or the content of ammonium carbonate, the content B1 is the total amount of the polishing liquid. It may be in the following range on the basis of mass. The content B1 is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, and 0.3% by mass or more from the viewpoint of easily improving the copper polishing rate. , 0.4% by mass or more, 0.45% by mass or more, 0.5% by mass or more, 0.6% by mass or more, 0.7% by mass or more, 0.8% by mass or more, or 0.85% by mass or more. Content B1 is 0.9% by mass or more, 1% by mass or more, 1.1% by mass or more, 1.2% by mass or more, 1.3% by mass or more, 1.4% by mass or more, 1.5% by mass or more, or 1.6% by mass or more. The content B1 is 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 1.8% by mass from the viewpoint of easily improving the polishing rate of copper. % or less, 1.7 mass% or less, 1.6 mass% or less, 1.5 mass% or less, 1.4 mass% or less, 1.3 mass% or less, 1.2 mass% or less, 1.1 mass% Below, it may be 1% by mass or less, 0.9% by mass or less, or 0.85% by mass or less. The content B1 may be 0.8% by mass or less, 0.7% by mass or less, 0.6% by mass or less, 0.5% by mass or less, or 0.45% by mass or less. From these points of view, the content B1 may be 0.01 to 10% by mass, 0.1 to 5% by mass, or 0.3 to 2% by mass.

When the ammonium salt contains a peroxide, the content of the peroxide (ammonium salt) or the content of ammonium persulfate, B2, may be in the following ranges based on the total mass of the polishing liquid. . The content B2 is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, and 0.3% by mass or more from the viewpoint of easily improving the copper polishing rate. , 0.4% by mass or more, 0.5% by mass or more, 0.6% by mass or more, 0.65% by mass or more, 0.7% by mass or more, 0.75% by mass or more, or 0.8% by mass or more. The content B2 is 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, from the viewpoint of easily improving the polishing rate of copper. It may be 1% by mass or less, 0.9% by mass or less, or 0.8% by mass or less. The content B2 may be 0.75% by mass or less, 0.7% by mass or less, 0.65% by mass or less, or 0.6% by mass or less. From these points of view, the content B2 may be 0.01 to 5% by mass.

As the ammonium salt content, the content of the ammonium salt different from the peroxide, or the content of the ammonium carbonate, the content C1 may be within the following range with respect to 100 parts by mass of the abrasive grains. The content C1 is 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, or 45 parts by mass or more from the viewpoint of easily improving the copper polishing rate. , 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, or 85 parts by mass or more. The content C1 may be 90 parts by mass or more, 100 parts by mass or more, 110 parts by mass or more, 120 parts by mass or more, 130 parts by mass or more, 140 parts by mass or more, 150 parts by mass or more, or 160 parts by mass or more. . The content C1 is 1000 parts by mass or less, 800 parts by mass or less, 500 parts by mass or less, 400 parts by mass or less, 300 parts by mass or less, 200 parts by mass or less, or 180 parts by mass or less from the viewpoint of easily improving the copper polishing rate. , 170 parts by mass or less, 160 parts by mass or less, 150 parts by mass or less, 140 parts by mass or less, 130 parts by mass or less, 120 parts by mass or less, 110 parts by mass or less, 100 parts by mass or less, 90 parts by mass or less, or 85 parts by mass It can be less than part. The content C1 may be 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, or 45 parts by mass or less. From these points of view, the content C1 may be 1 to 1000 parts by mass.

When the ammonium salt contains a peroxide, the content of the peroxide (ammonium salt) or the content of ammonium persulfate C2 may be in the following range with respect to 100 parts by mass of the abrasive grains . The content C2 is 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, or 50 parts by mass or more from the viewpoint of easily improving the polishing rate of copper. , 60 parts by mass or more, 65 parts by mass or more, 70 parts by mass or more, 75 parts by mass or more, or 80 parts by mass or more. The content C2 is 500 parts by mass or less, 400 parts by mass or less, 300 parts by mass or less, 200 parts by mass or less, 150 parts by mass or less, 120 parts by mass or less, or 100 parts by mass or less from the viewpoint of easily improving the copper polishing rate. , 90 parts by mass or less, or 80 parts by mass or less. The content C2 may be 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 points of view, the content C2 may be 1 to 500 parts by mass.

(water)
The polishing liquid according to this embodiment may contain water. Water may be contained as the remainder after removing other constituents from the polishing liquid. The content of water may be within the following ranges based on the total mass of the polishing liquid. The water content is 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, Alternatively, it may be 96% by mass or more. The water content may be less than 100 wt%, 99 wt% or less, 98 wt% or less, 97 wt% or less, 96 wt% or less, or 95.5 wt% or less. From these points of view, the content of water may be 90% by mass or more and less than 100% by mass.

(Additive)
The polishing liquid according to this embodiment may contain components other than abrasive grains, ammonium salt, and water. Such components include ammonia, ether compounds having a hydroxyl group, acid components, anticorrosive agents, basic hydroxides, surfactants, antifoaming agents and the like. The polishing liquid according to this embodiment may not contain at least one of these components.

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

The content of ammonia may be within the following range based on the total mass of the polishing liquid, from the viewpoint of easily improving the polishing rate of copper. The content of ammonia is 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, 0.12% by mass or more, or It may be 0.15% by mass or more. The content of ammonia is 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, 0.5% by mass or less, and 0.3% by mass. Below, it may be 0.2 mass % or less, or 0.15 mass % or less. From these points of view, the content of ammonia may be 0.01 to 5% by mass.

The content of ammonia may be within the following range with respect to 100 parts by mass of abrasive grains, from the viewpoint of easily improving the polishing rate of copper. The content of ammonia may be 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 12 parts by mass or more, or 15 parts by mass or more. Ammonia content is 200 parts by mass or less, 150 parts by mass or less, 100 parts by mass or less, 80 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less or 15 parts by mass or less. From these points of view, the content of ammonia may be 1 to 200 parts by mass.

The content of ammonia may be within the following range with respect to 100 parts by mass of the ammonium salt, from the viewpoint of easily improving the polishing rate of copper. The content of ammonia is 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, or 35 parts by mass or more good. The content of ammonia is 200 parts by mass or less, 150 parts by mass or less, 100 parts by mass or less, 80 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, or 36 parts by mass or less good. From these points of view, the content of ammonia may be 1 to 200 parts by mass.

The polishing liquid according to this embodiment may contain an ether compound having a hydroxy group (hereinafter sometimes referred to as "ether compound A"). An ether compound having a hydroxy group is a compound having at least one hydroxy group and at least one ether group. The “ether group” in the ether compound A does not include the “—O—” structure in a hydroxy group (hydroxyl group), carboxyl group, carboxylic acid group, ester group, sulfo group and phosphoric acid group. Hydroxy groups do not include OH groups contained in carboxy groups, ester groups, sulfo groups and phosphate groups. The ether compound A may contain a compound having an ether group that bonds carbon atoms together from the viewpoint of easily improving the polishing rate of copper.

The ether compound A may contain a compound having the number of hydroxy groups within the following range from the viewpoint of easily improving the polishing rate of copper. The number of hydroxy groups is 1 or more, and 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 hydroxy 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 points of view, the number of hydroxy groups may be from 1 to 20. The ether compound A may contain a compound having one hydroxy group and a compound having two or more hydroxy groups, from the viewpoint of easily improving the polishing rate of copper.

The ether compound A may contain a compound having the number of ether groups within the following range from the viewpoint of easily improving the polishing rate of copper. The number of ether groups is 1 or more, and 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 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 points of view, the number of ether groups may be from 1 to 20. The ether compound A may contain a compound having one ether group and a compound having two or more ether groups, from the viewpoint of facilitating an improvement in the polishing rate of copper.

The ether compound A may contain an alkoxy alcohol from the viewpoint of easily improving the polishing rate of copper. Alkoxy alcohols include 2-methoxyethanol, 2-ethoxyethanol, 2-(2-methoxy)ethoxyethanol, 2-(2-butoxyethoxy)ethanol, 2-propoxyethanol, 2-butoxyethanol, 3-methoxy-3 -methyl-1-butanol, 2-(methoxymethoxy)ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-isopentyloxyethanol, 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 contain a compound having an alkoxy group having 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 2 to 3 carbon atoms from the viewpoint of easily improving the polishing rate of copper. The alkoxy alcohol may contain 3-methoxy-3-methyl-1-butanol from the viewpoint of easily improving the polishing rate of copper.

The ether compound A may contain a polyether, and may contain an alkoxy alcohol and a polyether, from the viewpoint of easily improving the polishing rate of copper. Polyethers include polyglycerin, polysaccharides, polyalkylene glycol, polyoxypropylene polyglyceryl ether, polyoxyethylene polyglyceryl ether, 1,4-di(2-hydroxyethoxy)benzene, 2,2-bis(4-polyoxy ethyleneoxyphenyl)propane, 2,2-bis(4-polyoxypropyleneoxyphenyl)propane, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, polyoxyalkylene monophenyl ether, propylene glycol monophenyl ether, polyoxypropylene monomethyl Phenyl ether, polyethylene glycol monomethyl ether, pentaerythritol polyoxyethylene ether, ethylene glycol monoallyl ether, polyoxyethylene monoallyl ether, alkyl glucoside and the like. As polyethers, compounds other than alkoxy alcohols may be used. The polyether may contain polyglycerin from the viewpoint of easily improving the polishing rate of copper.

The ether compound A may contain polyglycerin having an average degree of polymerization of glycerin in the following range from the viewpoint of easily improving 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 points of view, the average degree of polymerization may be 3-100.

The ether compound A may contain polyglycerin with a hydroxyl value in the range below from the viewpoint of easily improving the polishing rate of copper. The hydroxyl value may be 100 or higher, 200 or higher, 300 or higher, 400 or higher, 500 or higher, 600 or higher, 700 or higher, 800 or higher, 850 or higher, or 870 or higher. 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 points of view, the hydroxyl value may range from 100 to 2,000.

The ether compound A may contain a compound having one hydroxy group and one ether group from the viewpoint of easily improving the polishing rate of copper. The ether compound A may contain a compound having an ether group that bonds an alkyl group having a hydroxy group as a substituent and an unsubstituted alkyl group, from the viewpoint of easily improving the polishing rate of copper. , one hydroxy group and one ether group.

The ether compound A may contain compounds having the following molecular weights from the viewpoint of easily improving the polishing rate of copper. The molecular weight may be 50 or greater, 80 or greater, 100 or greater, 110 or greater, 115 or greater, 118 or greater, 120 or greater, 150 or greater, 200 or greater, 200 or greater, 300 or greater, 500 or greater, 700 or greater, or 750 or greater. . The molecular weight may be 3000 or less, 2000 or less, 1500 or less, 1200 or less, 1000 or less, 800 or less, 750 or less, 700 or less, 500 or less, 300 or less, 200 or less, less than 200, 150 or less, or 120 or less. . From these points of view, the molecular weight may be 50-3000. Ether compounds A may include, for example, alkoxy alcohols with a molecular weight of less than 200.

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

The content of alkoxy alcohol is as follows based on the total mass of ether compounds (total mass of ether compounds contained in the polishing liquid) or the total mass of ether compounds A (total mass of ether compounds A contained in the polishing liquid). may be in the range of The content of the alkoxy alcohol is 5% by mass or more, 8% by mass or more, 10% by mass or more, 12% by mass or more, 15% by mass or more, 18% by mass or more, or 20% by mass, from the viewpoint of easily improving the copper polishing rate. % or more, 23 mass % or more, or 24 mass % or more. The content of the alkoxy alcohol is 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, from the viewpoint of easily improving the copper polishing rate. % or less, 60 mass % or less, 55 mass % or less, 50 mass % or less, 45 mass % or less, 40 mass % or less, 35 mass % or less, 30 mass % or less, or 25 mass % or less. The content of alkoxy alcohol may be 24% by mass or less. From these points of view, the content of alkoxy alcohol may be 5 to 95% by mass.

The content D as the content of polyether or the content of polyglycerin is the total mass of ether compounds (total mass of ether compounds contained in the polishing liquid) or the total mass of ether compounds A (the total mass of ether compounds contained in the polishing liquid). The total mass of compound A) may be in the following ranges. The content D is 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, or 35% by mass or more from the viewpoint of easily improving the polishing rate of copper. , 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, or 75% by mass or more. The content D may be 76% by mass or more. The content D is 95% by mass or less, 92% by mass or less, 90% by mass or less, 88% by mass or less, 85% by mass or less, 82% by mass or less, 80% by mass or less from the viewpoint of easily improving the polishing rate of copper. , 77% by mass or less, or 76% by mass or less. From these points of view, the content D may be 5 to 95% by mass.

The content of the ether compound A may be within the following range based on the total mass of the polishing liquid. The content of the ether compound A is 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.8% by mass or more, and 1% by mass from the viewpoint of easily improving the copper polishing rate. Above, more than 1% by mass, 1.1% by mass or more, 1.2% by mass or more, 1.3% by mass or more, 1.31% by mass or more, 1.32% by mass or more, or 1.33% by mass or more can be The content of the ether compound A is 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, and 1.8% by mass or less from the viewpoint of easily improving the copper polishing rate. , 1.7% by mass or less, 1.6% by mass or less, 1.5% by mass or less, 1.4% by mass or less, 1.35% by mass or less, or 1.33% by mass or less. The content of the ether compound A may be 1.32% by mass or less, or 1.31% by mass or less. From these viewpoints, the content of the ether compound A may be 0.1 to 10% by mass, 0.5 to 5% by mass, or 1 to 3% by mass.

The content of alkoxy alcohol may be within the following range based on the total mass of the polishing liquid. The content of the alkoxy alcohol is 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.08% by mass or more, and 0.1% by mass, from the viewpoint of easily improving the copper polishing rate. % or more, 0.15 mass % or more, 0.2 mass % or more, 0.25 mass % or more, 0.3 mass % or more, 0.31 mass % or more, or 0.33 mass % or more . The content of the alkoxy alcohol is 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, and 0.65% by mass, from the viewpoint of easily improving the copper polishing rate. % by mass or less, 0.6% by mass or less, 0.55% by mass or less, 0.5% by mass or less, 0.45% by mass or less, 0.4% by mass or less, 0.35% by mass or less, or 0. It may be 33% by mass or less. The content of alkoxy alcohol may be 0.31% by mass or less. From these points of view, the content of alkoxy alcohol may be 0.01 to 5% by mass, 0.1 to 1% by mass, or 0.2 to 0.8% by mass.

The content E as the content of polyether or the content of polyglycerin may be in the following range based on the total mass of the polishing liquid, from the viewpoint of easily improving the copper polishing rate. Content E is 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, 0.6% by mass or more, 0.8 % by mass or more, 0.9% by mass or more, or 1% by mass or more. Content E is 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. From these points of view, the content E may be 0.01 to 10% by mass, 0.1 to 5% by mass, or 0.5 to 3% by mass.

The content of the ether compound A may be within the following range with respect to 100 parts by mass of the abrasive grains. The content of the ether compound A is 10 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, 80 parts by mass or more, 100 parts by mass or more, more than 100 parts by mass, 110 parts by mass or more, from the viewpoint of easily improving the polishing rate of copper. It may be at least 120 parts by mass, at least 130 parts by mass, at least 131 parts by mass, at least 132 parts by mass, or at least 133 parts by mass. The content of the ether compound A is 1000 parts by mass or less, 800 parts by mass or less, 500 parts by mass or less, 300 parts by mass or less, 200 parts by mass or less, 180 parts by mass or less, 170 parts by mass or less, from the viewpoint of easily improving the copper polishing rate. It may be 160 parts by mass or less, 150 parts by mass or less, 140 parts by mass or less, 135 parts by mass or less, or 133 parts by mass or less. The content of the ether compound A may be 132 parts by mass or less, or 131 parts by mass or less. From these points of view, the content of the ether compound A may be 10 to 1000 parts by mass.

The content of alkoxy alcohol may be within the following range with respect to 100 parts by mass of abrasive grains. The content of the alkoxy alcohol is 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, 15 parts by mass or more, or 20 parts by mass from the viewpoint of easily improving the copper polishing rate. parts or more, 25 parts by mass or more, 30 parts by mass or more, 31 parts by mass or more, or 33 parts by mass or more. The content of the alkoxy alcohol is 500 parts by mass or less, 300 parts by mass or less, 100 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less from the viewpoint of easily improving the polishing rate of copper. parts or less, 55 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less, or 33 parts by mass or less. The content of alkoxy alcohol may be 31 parts by mass or less. From these points of view, the content of alkoxy alcohol may be 1 to 500 parts by mass.

The content F as the content of polyether or the content of polyglycerin may be in the following range with respect to 100 parts by mass of abrasive grains, from the viewpoint of easily improving the polishing rate of copper. The content F is 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. or more. The content F is 1000 parts by mass or less, 800 parts by mass or less, 700 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, 200 parts by mass or less, 150 parts by mass or less, Alternatively, it may be 100 parts by mass or less. From these points of view, the content F may be 1 to 1000 parts by mass.

The content of the ether compound A may be within the following range with respect to 100 parts by mass of the ammonium salt. The content of the ether compound A is 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, from the viewpoint of easily improving the copper polishing rate. It may be at least 120 parts by mass, at least 130 parts by mass, at least 140 parts by mass, at least 150 parts by mass, or at least 155 parts by mass. The content of the ether compound A may be 160 parts by mass or more, 180 parts by mass or more, 200 parts by mass or more, 250 parts by mass or more, 300 parts by mass or more, or 315 parts by mass or more. The content of the ether compound A is 1000 parts by mass or less, 800 parts by mass or less, 700 parts by mass or less, 600 parts by mass or less, 500 parts by mass or less, 400 parts by mass or less, 350 parts by mass or less, from the viewpoint of easily improving the polishing rate of copper. It may be no more than 320 parts by mass, no more than 315 parts by mass, no more than 300 parts by mass, no more than 250 parts by mass, no more than 200 parts by mass, no more than 180 parts by mass, or no more than 160 parts by mass. The content of the ether compound A is 155 parts by mass or less, 150 parts by mass or less, 140 parts by mass or less, 130 parts by mass or less, 120 parts by mass or less, 110 parts by mass or less, 100 parts by mass or less, or 80 parts by mass or less. It's okay. From these points of view, the content of the ether compound A may be 10 to 1000 parts by mass.

The content of the alkoxy alcohol may be within the following range with respect to 100 parts by mass of the ammonium salt. The content of the alkoxy alcohol is 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, or 30 parts by mass from the viewpoint of easily improving the copper polishing rate. parts or more, 35 parts by mass or more, or 38 parts by mass or more. The content of the alkoxy alcohol is 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, 55 parts by mass or more, 60 parts by mass or more, 65 parts by mass or more, 70 parts by mass or more, or 75 parts by mass or more. you can The content of the alkoxy alcohol is 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 or less, 75 parts by mass or less, or 70 parts by mass from the viewpoint of easily improving the copper polishing rate. parts or less, 65 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, or 40 parts by mass or less. The content of the alkoxy alcohol may be 38 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 points of view, the content of the alkoxy alcohol may be 1 to 200 parts by mass.

The content G as the content of polyether or the content of polyglycerin may be in the following range with respect to 100 parts by mass of the ammonium salt. The content G is 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 or more from the viewpoint of easily improving the polishing rate of copper. , 110 parts by mass or more, or 115 parts by mass or more. The content G may be 120 parts by mass or more, 150 parts by mass or more, 180 parts by mass or more, 200 parts by mass or more, or 230 parts by mass or more. The content G is 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, or 250 parts by mass or less from the viewpoint of easily improving the polishing rate of copper. , 230 parts by mass or less, 200 parts by mass or less, 180 parts by mass or less, 150 parts by mass or less, or 120 parts by mass or less. The content G may be 115 parts by mass or less, 110 parts by mass or less, 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, or 60 parts by mass or less. From these viewpoints, the content G may be 10 to 1000 parts by mass.

The content of the alkoxy alcohol may be within the following range with respect to 100 parts by mass of polyether or 100 parts by mass of polyglycerin. The content of the alkoxy alcohol is 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, 15 parts by mass or more, or 20 parts by mass from the viewpoint of easily improving the copper polishing rate. parts or more, 25 parts by mass or more, 30 parts by mass or more, 31 parts by mass or more, or 33 parts by mass or more. The content of the alkoxy alcohol is 200 parts by mass or less, 150 parts by mass or less, 120 parts by mass or less, 100 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass from the viewpoint of easily improving the copper polishing rate. parts or less, 50 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less, or 33 parts by mass or less. The content of alkoxy alcohol may be 31 parts by mass or less. From these points of view, the content of the alkoxy alcohol may be 1 to 200 parts by mass.

The polishing liquid according to this embodiment may contain acid components (excluding compounds corresponding to ammonium salts). It is presumed that the acid component forms a complex with copper, the acid component dissolves copper, and the like, so that the polishing rate of copper is likely to be improved. The polishing liquid according to the present embodiment may contain an organic acid component or an inorganic acid component as the acid component.

Organic acid components include organic acids (excluding amino acids), organic acid esters, organic acid salts, amino acids, and the like. 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-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, 3-methylphthalic acid, 4-methylphthalic acid, 3-aminophthalic acid acid, 4-aminophthalic acid, 3-nitrophthalic acid, 4-nitrophthalic 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, methylsulfonic acid, lactic acid, itaconic acid, maleic acid, quinaldic acid, adipic acid, pimelic acid and the like. Examples of organic acid esters include esters of the above-described organic acids. Examples of organic acid salts include alkali metal salts, alkaline earth metal salts and halides of the above organic acids. Amino acids include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, and the like. 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 is selected from the group consisting of malic acid and glycine, from the viewpoint of further improving the polishing rate of copper. At least one kind may be included.

Examples of inorganic acid components include inorganic acids and chromic acid. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid and the like.

The content of organic acids different from amino acids may be within the following ranges based on the total mass of the polishing liquid. The content of organic acids different from amino acids is 0.001% by mass or more, 0.003% by mass or more, 0.005% by mass or more, 0.008% by mass or more, from the viewpoint of easily improving the polishing rate of copper. Alternatively, it may be 0.01% by mass or more. The content of organic acids different from amino acids is 1% by mass or less, 0.5% by mass or less, 0.1% by mass or less, 0.08% by mass or less, 0.08% by mass or less, from the viewpoint of easily improving the polishing rate of copper. 05% by mass or less, 0.03% by mass or less, 0.02% by mass or less, or 0.01% by mass or less. From these points of view, the content of organic acids different from amino acids may be 0.001 to 1% by mass.

The content H as the content of the acid component or the content of the organic acid component may be within the following ranges based on the total mass of the polishing liquid. The content H is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, and 0.3% by mass or more from the viewpoint of easily improving the polishing rate of copper. , 0.4% by mass or more, or 0.41% by mass or more. The content H is 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, and 0.5% by mass, from the viewpoint of easily improving the polishing rate of copper. % by mass or less, 0.45 mass % or less, or 0.41 mass % or less. The content H may be 0.4% by mass or less. From these points of view, the content H may be 0.01 to 2% by mass.

The polishing liquid according to the present embodiment may contain an anticorrosive agent (anticorrosive agent for metal) as a compound having an anticorrosive action on metal. By forming a protective film on the metal, the anticorrosive suppresses the etching of the metal and tends to reduce the roughness of the surface to be polished.

The anticorrosive agent may contain at least one selected from the group consisting of triazole compounds, pyridine compounds, pyrazole compounds, pyrimidine compounds, imidazole compounds, guanidine compounds, thiazole compounds, tetrazole compounds, triazine compounds and hexamethylenetetramine. A "compound" is a general term for compounds having the skeleton thereof, and for example, a "triazole compound" means a compound having a triazole skeleton. The anticorrosion agent may contain a triazole compound from the viewpoint of easily obtaining a suitable anticorrosion action.

Triazole compounds include 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, benzotriazole, 1-hydroxybenzotriazole, and 1-dihydroxypropylbenzotriazole. , 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxy-1H-benzotriazole, 4-carboxy-1H-benzotriazole methyl ester (methyl 1H-benzotriazole-4-carboxylate), 4 -Carboxy-1H-benzotriazole butyl ester (1H-benzotriazole-4-carboxylate butyl), 4-carboxy-1H-benzotriazole octyl ester (1H-benzotriazole-4-carboxylate octyl), 5-hexylbenzotriazole , [1,2,3-benzotriazolyl-1-methyl][1,2,4-triazolyl-1-methyl][2-ethylhexyl]amine, tolyltriazole, naphthotriazole, bis[(1-benzotriazole solyl)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. A compound having a triazole skeleton and other skeletons in one molecule is classified as a triazole compound. The polishing liquid according to the present embodiment may contain a triazole compound having a hydroxy group, and may contain 1-hydroxybenzotriazole, from the viewpoint of easily obtaining a suitable anticorrosion action.

The content of the anticorrosive agent may be within the following range based on the total mass of the polishing liquid, from the viewpoint of easily obtaining a suitable anticorrosive action. The content of the anticorrosive agent is 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, or , 0.025% by mass or more. The content of the anticorrosive agent is 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, and 0.04% by mass. % by mass or less, 0.03% by mass or less, or 0.025% by mass or less. From these points of view, the content of the anticorrosive agent may be 0.001 to 1% by mass.

The polishing liquid according to this embodiment may contain a basic hydroxide. By using a basic hydroxide, the polishing rate of copper tends to be improved. Basic hydroxides include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides; tetramethylammonium hydroxide (TMAH) and the like.

The content of the basic hydroxide may be within the following range based on the total mass of the polishing liquid, from the viewpoint of easily improving the polishing rate of copper. The content of basic hydroxide is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.15% by mass or more, 0.2% by mass or more, 0.25% by mass Above, it may be 0.3% by mass or more, 0.35% by mass or more, 0.4% by mass or more, 0.45% by mass or more, or 0.48% by mass or more. The content of the basic hydroxide is 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 0.5% by mass or less, or 0.48% by mass or less. The basic hydroxide content may be 0.45% by mass or less, 0.4% by mass or less, 0.35% by mass or less, 0.3% by mass or less, or 0.25% by mass or less . From these points of view, the basic hydroxide content may be 0.01 to 5% by mass.

The polishing liquid according to this embodiment does not have to contain peroxide. As the peroxide, including the above-mentioned ammonium salts, ammonium persulfate, potassium persulfate, hydrogen peroxide, ferric nitrate, cerium diammonium nitrate, iron sulfate, ozone, hypochlorous acid, hypochlorous acid salts, potassium periodate, peracetic acid and the like. The polishing liquid according to this embodiment does not have to contain hydrogen peroxide. Peroxide content or hydrogen peroxide content is 0.1% by mass or less, less than 0.1% by mass, 0.01% by mass or less, or 0.001% by mass, based on the total mass of the polishing liquid. less than or substantially 0% by mass.

(pH)
The pH of the polishing liquid according to the present embodiment is 9.00 or more from the viewpoint of improving the polishing rate of copper. The pH of the polishing liquid according to the present embodiment may be within the following range from the viewpoint of adjusting the polishing rate while improving the polishing rate of copper. The pH of the polishing liquid is 9.10 or higher, 9.15 or higher, 9.20 or higher, 9.25 or higher, 9.30 or higher, 9.35 or higher, 9.40 or higher, 9.45 or higher, 9.50 or higher. , 9.55 or more, 9.60 or more, 9.65 or more, 9.70 or more, 9.75 or more, 9.80 or more, 9.85 or more, 9.90 or more, 9.95 or more, 10.00 or more , 10.05 or greater, or 10.10 or greater. The pH of the polishing liquid is 13.00 or less, 12.50 or less, 12.00 or less, 11.50 or less, 11.00 or less, 10.50 or less, 10.10 or less, 10.05 or less, 10.00 or less. , 9.95 or less, 9.90 or less, 9.85 or less, 9.80 or less, 9.75 or less, 9.70 or less, 9.65 or less, 9.60 or less, 9.55 or less, 9.50 or less , 9.45 or less, 9.40 or less, 9.35 or less, 9.30 or less, 9.25 or less, 9.20 or less, or 9.15 or less. From these points of view, the pH of the polishing liquid may be 9.00-13.00, 9.00-12.00, or 9.00-11.00. The pH of the polishing liquid can be adjusted with the aforementioned ammonium salt, ammonia, acid component, basic hydroxide, and the like.

The pH of the polishing liquid according to this embodiment can be measured with a pH meter (for example, model number: PHL-40 manufactured by Toa DKK Co., Ltd.). For example, after two-point calibration of a pH meter using a phthalate pH buffer (pH: 4.01) and a neutral phosphate pH buffer (pH: 6.86) as standard buffers, The electrode is placed in the polishing solution and the value is measured after the electrode has stabilized for two minutes or longer. At this time, the temperature of both the standard buffer solution and the polishing solution is set to 25°C.

(Preservation mode)
The polishing liquid according to the present embodiment may be stored as a polishing liquid storage liquid with the amount of water reduced compared to when it is used. The polishing liquid storage liquid is a storage liquid for obtaining the polishing liquid, and the polishing liquid can be obtained by diluting the polishing liquid storage liquid with water before or during use. The dilution ratio is, for example, 1.5 times or more.

The polishing liquid according to the present embodiment may be stored as a one-component polishing liquid containing at least abrasive grains and an ammonium salt, and may be a multi-component polishing liquid having a slurry (first liquid) and an additive liquid (second liquid). It may be stored as a formula polishing liquid. In the multi-liquid 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. Components other than the abrasive grains, the ammonium salt, and water may be contained in the additive liquid of the slurry and the additive liquid. The components of the polishing liquid may be divided into three or more liquids and stored. In the multi-liquid polishing liquid, the polishing liquid may be prepared by mixing the slurry and the additive liquid immediately before or during polishing. The slurry and the additive liquid in the multi-liquid polishing liquid may be separately supplied onto the polishing platen, and the slurry and the additive liquid may be mixed on the polishing platen to prepare the polishing liquid.

<Polishing method>
The polishing method according to this embodiment includes a polishing step of polishing a member to be polished containing copper using the polishing liquid according to this embodiment. In the polishing step, the surface to be polished of the member to be polished can be polished, and the surface to be polished on which copper is present can be polished. The member to be polished may contain resin and metal (eg, copper). In the polishing step, the surface to be polished on which resin and metal are present can be polished.

<Manufacturing method etc.>
The component manufacturing method according to the present embodiment includes a singulation step of singulating the member to be polished (substrate) that has been polished by the polishing method according to the present embodiment. The singulation step may be, for example, a step of obtaining chips (eg, semiconductor chips) by dicing a wafer (eg, semiconductor wafer) polished by the polishing method according to the present embodiment. As one aspect of the method for manufacturing a component according to the present embodiment, the method for manufacturing a semiconductor component according to the present embodiment comprises dividing the member to be polished by the polishing method according to the present embodiment into individual semiconductor components ( For example, a step of obtaining a semiconductor chip). The component manufacturing method according to the present embodiment may include a polishing step of polishing the member to be polished by the polishing method according to the present embodiment before the singulation step. The component according to this embodiment is a component obtained by the method for manufacturing a component according to this embodiment, and may be a semiconductor component, a chip (for example, a semiconductor chip), or the like.

The method for manufacturing a joined body according to this embodiment includes the bonding surface of a member to be polished polished by the polishing method according to this embodiment, or the bonding surface of a component obtained by the method for manufacturing a component according to this embodiment ( For example, a bonding step of bonding a bonding surface of a semiconductor component obtained by the method for manufacturing a semiconductor component according to the present embodiment and a bonding surface of an object to be bonded. The joint surface of the member to be polished or the joint surface of the part may be the surface to be polished by the polishing method according to the present embodiment. The object to be bonded to the member or part to be polished may be a member to be polished polished by the polishing method according to the present embodiment, or a part obtained by the method for manufacturing a part according to the present embodiment. The object to be joined may be different from these members and parts to be polished. In the bonding step, when the bonding surface of the member or component to be polished has a metal portion and the bonding surface of the object to be bonded has a metal portion, the metal portions may be brought into contact with each other. The metal portion may contain copper. A joined body according to the present embodiment is a joined body obtained by the method for manufacturing a joined body according to the present embodiment.

An electronic device according to the present embodiment includes at least one selected from the group consisting of a member to be polished by the polishing method according to the present embodiment, the component according to the present embodiment, and the joined body according to the present embodiment. .

The present disclosure will be specifically described below based on examples, but the present disclosure is not limited to these.

<Preparation of Polishing Liquid>
A polishing liquid having the composition shown in Table 1 was obtained by mixing each component shown in Table 1 and distilled water. Table 1 shows the content (unit: % by mass) of each component based on the total mass of the polishing liquid, and the balance is distilled water. Cerium oxide particles (manufactured by Showa Denko Materials Co., Ltd., trade name: HS-8005) or colloidal silica (manufactured by Fuso Chemical Industry Co., Ltd., trade name: PL-3) were used as abrasive grains. Table 1 shows the content of silica particles, which is a solid content, as the content of colloidal silica. "MMB" means 3-methoxy-3-methyl-1-butanol and "HBTA" means 1-hydroxybenzotriazole. As polyglycerin, trade name "PGL750" (glycerin decamer, weight average molecular weight: 750, hydroxyl value: 870 to 910) manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. was used.

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

<pH of Polishing Liquid>
The pH of the polishing liquid was measured using a pH meter (manufactured by Toa DKK Co., Ltd., model number: PHL-40). After two-point calibration of the pH meter using phthalate pH buffer (pH: 4.01) and neutral phosphate pH buffer (pH: 6.86) as standard buffers, the electrode of the pH meter was It was placed in the polishing liquid and after two minutes or more had passed, the value was measured. Table 1 shows the results.

<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 polishing apparatus (manufactured by APPLIED MATERIALS, trade name: Reflexion LK), the substrate was attached to a substrate attachment holder to which a suction pad was attached. A holder was placed on a surface plate to which a porous urethane resin pad was attached so that the surface to be polished faced the pad. The substrate was pressed against the pad with a polishing load of 4 psi while supplying the aforementioned polishing liquid onto the pad at a supply rate of 350 mL/min. At this time, the surface plate was rotated at 147 min ⁻¹ and the holder at 153 min ⁻¹ for 1 minute for polishing. The polished substrate was thoroughly washed with pure water and then dried. A change in film thickness of the film to be polished before and after polishing was measured using an optical interference type film thickness measuring device to determine the copper polishing rate (Cu-RR). The average value of the amount of change in thickness was measured at a total of 5 points at 4 points in the central part of the substrate and in the peripheral part of the substrate (4 points at equal intervals from each other centering on the central part of the substrate). Table 1 shows the results.

In each example, it is superior to Comparative Example 1 that does not use abrasive grains containing cerium oxide, Comparative Examples 2 and 3 that do not use an ammonium salt, and Comparative Example 4 that does not have a pH of 9.00 or more. It is confirmed that the polishing rate of

Claims (16)

containing abrasive grains containing cerium oxide and an ammonium salt,
A polishing liquid having a pH of 9.00 or higher. The polishing liquid according to claim 1, wherein the ammonium salt contains ammonium carbonate. The polishing liquid according to claim 2, wherein the ammonium salt further contains ammonium persulfate. The polishing liquid according to any one of claims 1 to 3, wherein the ammonium salt content is 0.3 to 2% by mass. The polishing liquid according to any one of claims 1 to 4, which further contains ammonia. The polishing liquid according to any one of claims 1 to 5, further containing an ether compound having a hydroxy group. The polishing liquid according to claim 6, wherein the ether compound contains an alkoxy alcohol. The polishing liquid according to claim 7, wherein the alkoxy alcohol contains 3-methoxy-3-methyl-1-butanol. The polishing liquid according to claim 7 or 8, wherein the content of the alkoxy alcohol is 0.2 to 0.8 mass% based on the total mass of the polishing liquid. The polishing liquid according to any one of claims 7 to 9, wherein the ether compound further contains polyether. The polishing liquid according to claim 10, wherein the polyether contains polyglycerin. The polishing liquid according to claim 10 or 11, wherein the polyether content is 0.5 to 3% by mass based on the total mass of the polishing liquid. The polishing liquid according to any one of claims 1 to 12, which has a pH of 9.00 to 11.00. A polishing method comprising polishing a member to be polished containing copper using the polishing liquid according to any one of claims 1 to 13. A method for manufacturing a semiconductor component, wherein the semiconductor component is obtained by singulating the member to be polished that has been polished by the polishing method according to claim 14. The joint surface of a member to be polished polished by the polishing method according to claim 14, or the joint surface of a semiconductor component obtained by the semiconductor component manufacturing method according to claim 15 and the joint surface of the object to be joined. A method for manufacturing a joined body, which joins