Polishing method, slurry, and abrasive grains

Abstract

Provided is a polishing method comprising a polishing step for using a slurry to polish a resin part of a member to be polished, which has the resin part containing a resin material, wherein: the slurry contains abrasive grains having silicon oxide particles and an aluminum component present on the surface of the silicon oxide particles; and the aluminum component includes at least one compound selected from the group consisting of aluminum acetate, aluminum chloride, and derivatives thereof. Also provided is a slurry for polishing a resin part of a member to be polished, which has the resin part containing a resin material, the slurry containing abrasive grains having silicon oxide particles and an aluminum component present on the surface of the silicon oxide particles, wherein the aluminum component includes at least one compound selected from the group consisting of aluminum acetate, aluminum chloride, and derivatives thereof.

Description

Polishing method, slurry and abrasive grains

[0001] This disclosure relates to polishing methods, slurries, abrasive grains, etc.

[0002] In the semiconductor field, with the increasing performance of ultra-large-scale integrated circuits (ULSIs), it is becoming increasingly difficult to achieve both high integration and high speed through miniaturization techniques that are merely extensions of conventional technologies. Therefore, technologies are being developed that allow for both miniaturization of semiconductor elements and high integration in the vertical direction (i.e., technologies for multi-layer wiring).

[0003] One such technique is hybrid bonding using resin materials. In hybrid bonding, the resin portion (the portion containing resin material) on the metal portion (the portion containing metal material: a metal pattern formed by photolithography (copper pattern, tin-silver alloy pattern, etc.)) is removed by polishing (for example, CMP (chemical mechanical polishing)), thereby obtaining an exposed surface where the metal and resin portions are exposed. This exposed surface can then be bonded to the object to be bonded. The resin portion can be obtained, for example, by supplying a curable resin material onto the metal portion and then curing the resin material.

[0004] CMP (Computer Polishing) is typically performed using a device that can supply polishing fluid onto a polishing pad. The surface of the workpiece is polished by supplying polishing fluid between the workpiece and the polishing pad while pressing the workpiece against the polishing pad. Thus, in CMP technology, the polishing fluid is one of the key technologies, and various polishing fluids have been developed to obtain high-performance polishing fluids (see, for example, Patent Document 1 below).

[0005] Japanese Patent Publication No. 2008-288537

[0006] For slurries that can be used as polishing fluids to polish the resin portion of a workpiece, and for abrasive grains used in such slurries, it is sometimes required to achieve a high polishing speed for the resin material. For example, in the above-mentioned hybrid bonding using resin material, it is required to achieve a high polishing speed for the resin material in order to expose the metal portion.

[0007] One aspect of this disclosure aims to provide a polishing method capable of achieving a high polishing speed for resin materials. Another aspect of this disclosure aims to provide a slurry capable of achieving a high polishing speed for resin materials. Another aspect of this disclosure aims to provide abrasive grains capable of achieving a high polishing speed for resin materials.

[0008] This disclosure includes the following aspects: [1] A polishing method comprising a polishing step of polishing a resin portion of a member to be polished having a resin portion containing a resin material using a slurry, wherein the slurry contains abrasive grains having silicon oxide particles and an aluminum component present on the surface of the silicon oxide particles, and the aluminum component includes at least one selected from the group consisting of aluminum acetate, aluminum chloride and derivatives thereof. [2] The polishing method according to [1], wherein the aluminum component includes at least one selected from the group consisting of aluminum acetate and its derivatives. [3] The polishing method according to [1] or [2], wherein the aluminum component includes at least one selected from the group consisting of aluminum chloride and its derivatives. [4] The polishing method according to any one of [1] to [3], wherein the silicon oxide particles include colloidal silica. [5] The polishing method according to any one of [1] to [4], wherein the average particle size of the abrasive grains is 20.0 to 200 nm. [6] The polishing method according to any one of [1] to [5], wherein the atomic ratio Al / Si of aluminum to silicon obtained by X-ray photoelectron spectroscopy measurement on the surface of the abrasive grains is 0.010 to 1.000. [7] The polishing method according to any one of [1] to [6], wherein the resin material comprises polybenzoxazole. [8] The polishing method according to any one of [1] to [7], wherein the resin material comprises polyimide. [9] The polishing method according to any one of [1] to [8], wherein the resin material comprises polyhydroxystyrene.

[10] A slurry for polishing the resin portion of a member to be polished having a resin portion containing a resin material, comprising abrasive grains having silicon oxide particles and an aluminum component present on the surface of the silicon oxide particles, wherein the aluminum component comprises at least one selected from the group consisting of aluminum acetate, aluminum chloride and derivatives thereof.

[11] The slurry according to

[10] , wherein the aluminum component comprises at least one selected from the group consisting of aluminum acetate and derivatives thereof.

[12] The slurry according to

[10] or

[11] , wherein the aluminum component comprises at least one selected from the group consisting of aluminum chloride and its derivatives.

[13] The slurry according to any one of

[10] to

[12] , wherein the silicon dioxide particles comprise colloidal silica.

[14] The slurry according to any one of

[10] to

[13] , wherein the average particle size of the abrasive grains is 20.0 to 200 nm.

[15] The slurry according to any one of

[10] to

[14] , wherein the atomic ratio Al / Si of aluminum and silicon obtained by X-ray photoelectron spectroscopy on the surface of the abrasive grains is 0.010 to 1.000.

[16] The slurry according to any one of

[10] to

[15] , wherein the resin material contains polybenzoxazole.

[17] The slurry according to any one of

[10] to

[16] , wherein the resin material contains polyimide.

[18] The slurry according to any one of

[10] to

[17] , wherein the resin material contains polyhydroxystyrene.

[19] Abrasive grains for polishing the resin portion of a member to be polished having a resin portion containing a resin material, comprising silicon oxide particles and an aluminum component present on the surface of the silicon oxide particles, wherein the aluminum component comprises at least one selected from the group consisting of aluminum acetate, aluminum chloride and derivatives thereof.

[20] The abrasive grain according to

[19] , wherein the aluminum component comprises at least one selected from the group consisting of aluminum acetate and its derivatives.

[21] The abrasive grain according to

[19] or

[20] , wherein the aluminum component comprises at least one selected from the group consisting of aluminum chloride and its derivatives.

[22] The abrasive grain according to any one of

[19] to

[21] , wherein the silicon oxide particles comprise colloidal silica.

[23] The abrasive grain according to any one of

[19] to

[22] , wherein the average particle size is 20.0 to 200 nm.

[24] The abrasive grain according to any one of

[19] to

[23] , wherein the atomic ratio of aluminum to silicon, Al / Si, obtained by X-ray photoelectron spectroscopy on the surface of the abrasive grain is 0.010 to 1.000.

[25] The abrasive grain according to any one of

[19] to

[24] , wherein the resin material comprises polybenzoxazole.

[26] The abrasive grain according to any one of

[19] to

[25] , wherein the resin material comprises polyimide.

[27] The abrasive grain according to any one of

[19] to

[26] , wherein the resin material comprises polyhydroxystyrene.

[0009] According to one aspect of this disclosure, a polishing method capable of achieving a high polishing speed for resin materials can be provided. According to another aspect of this disclosure, a slurry capable of achieving a high polishing speed for resin materials can be provided. According to yet another aspect of this disclosure, abrasive grains capable of achieving a high polishing speed for resin materials can be provided.

[0010] The embodiments of this disclosure will be described in detail below.

[0011] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. "A or greater" in a numerical range means A and the range exceeding A. "A or less" in a numerical range means A and the range less than A. In numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step can be arbitrarily combined with the upper or lower limit of a numerical range in another step. In numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples. "A or B" means that either A or B is included, or both are included. Unless otherwise specified, the materials exemplified in this specification can be used individually or in combination of two or more. The content of each component in a composition means the total amount of multiple substances present in the composition if there are multiple substances corresponding to each component, unless otherwise specified. The term "film" includes not only structures formed on the entire surface when observed as a plan view, but also structures formed on only a part of it. The term "process" includes not only independent processes, but also any process that cannot be clearly distinguished from other processes, as long as its intended function is achieved.

[0012] The polishing method according to this embodiment comprises a polishing step of polishing the resin portion of a workpiece having a resin portion containing a resin material using a slurry (slurry according to this embodiment). In the polishing method according to this embodiment, the slurry contains abrasive grains (abrasive grains according to this embodiment) having silicon oxide particles and an aluminum component present on the surface of the silicon oxide particles, and the aluminum component includes at least one selected from the group consisting of aluminum acetate, aluminum chloride and derivatives thereof.

[0013] The slurry according to this embodiment is for polishing the resin portion of a workpiece having a resin portion containing a resin material. The slurry according to this embodiment contains abrasive grains (abrasive grains according to this embodiment) having silicon oxide particles and an aluminum component present on the surface of the silicon oxide particles, wherein the aluminum component includes at least one selected from the group consisting of aluminum acetate, aluminum chloride and derivatives thereof. The slurry according to this embodiment can be used as a polishing slurry and can be used as a CMP polishing liquid.

[0014] The abrasive grains according to this embodiment are abrasive grains for polishing the resin portion of a workpiece having a resin portion containing a resin material. The abrasive grains according to this embodiment have silicon oxide particles and an aluminum component present on the surface of the silicon oxide particles, wherein the aluminum component includes at least one selected from the group consisting of aluminum acetate, aluminum chloride and derivatives thereof.

[0015] Hereinafter, an aluminum component comprising at least one selected from the group consisting of aluminum acetate, aluminum chloride, and derivatives thereof will be referred to as "aluminum component X," an abrasive grain having silicon oxide particles and aluminum component X present on the surface of the silicon oxide particles will be referred to as "abrasive grain a," and the entirety of the abrasive grains contained in the slurry according to this embodiment will be referred to as "abrasive grain A," with abrasive grain a constituting at least a portion of abrasive grain A.

[0016] According to the polishing method, slurry, and abrasive grains of this embodiment, it is possible to obtain a high polishing speed for resin materials, and when polishing the resin portion of a workpiece having a resin portion containing polybenzoxazole, a high polishing speed for polybenzoxazole can be obtained. According to the polishing method, slurry, and abrasive grains of this embodiment, in the evaluation method described in the [Examples] below, a polishing speed of 100 nm / min or more (preferably 200 nm / min or more, 300 nm / min or more, 350 nm / min or more, 400 nm / min or more, etc.) for polybenzoxazole can be obtained. It is presumed that a high polishing speed for resin materials can be obtained by increasing the frequency of contact between the abrasive grains and the resin portion due to the interaction between the aluminum component X present on the surface of silicon oxide particles and the resin material (for example, the electrostatic attraction between the positively charged aluminum component X and the negatively charged resin material). However, the factors are not limited to the above.

[0017] The polishing method, slurry, and abrasive grains according to this embodiment only need to have the characteristic of being able to obtain a high polishing speed of polybenzoxazole when polishing the resin portion of a workpiece having a resin portion containing polybenzoxazole, and may be used to polish the resin portion of a workpiece having a resin portion containing a resin material other than polybenzoxazole. In this case, the polishing method, slurry, and abrasive grains according to this embodiment may polish polybenzoxazole and the resin material other than polybenzoxazole simultaneously, or polish the resin material other than polybenzoxazole without polishing the polybenzoxazole. That is, the polishing method, slurry, and abrasive grains according to this embodiment are not limited to a polishing method, slurry, and abrasive grains for polishing the resin portion of a workpiece having a resin portion containing polybenzoxazole, but may also be a polishing method, slurry, and abrasive grains for polishing the resin portion of a workpiece having a resin portion containing a resin material other than polybenzoxazole, and in this case the resin portion may contain polybenzoxazole or may not contain polybenzoxazole.

[0018] According to one embodiment of the polishing method, slurry, and abrasive grains of this embodiment, a high polishing speed of polyimide can be obtained when polishing the resin portion of a workpiece having a resin portion containing polyimide. According to the polishing method, slurry, and abrasive grains of this embodiment, in the evaluation method described in the [Examples] below, a polishing speed of 100 nm / min or more (preferably 200 nm / min or more, 250 nm / min or more, 300 nm / min or more, 400 nm / min or more, etc.) can be obtained for polyimide.

[0019] According to one embodiment of the polishing method, slurry, and abrasive grains of this embodiment, a high polishing speed for polyhydroxystyrene can be obtained when polishing the resin portion of a workpiece having a resin portion containing polyhydroxystyrene. According to the polishing method, slurry, and abrasive grains of this embodiment, in the evaluation method described in the [Examples] below, a polishing speed of 100 nm / min or more (preferably 120 nm / min or more, 140 nm / min or more, 180 nm / min or more, 200 nm / min or more, etc.) can be obtained for polyhydroxystyrene.

[0020] The polishing method, slurry, and abrasive grains according to this embodiment may be used to polish a surface where only a resin portion is present, or to polish a surface where a resin portion and a metal portion (e.g., a copper portion) coexist. The polishing method, slurry, and abrasive grains according to this embodiment may be used to remove a resin portion from a metal portion by polishing, or to polish an exposed surface where a metal portion and a resin portion are exposed.

[0021] The abrasive grains according to this embodiment are abrasive grains a having silicon oxide particles (particles containing silicon oxide) and an aluminum component X present on the surface of the silicon oxide particles. The slurry according to this embodiment contains abrasive grains a having silicon oxide particles (particles containing silicon oxide) and an aluminum component X present on the surface of the silicon oxide particles. Silica particles (particles containing silica) can be used as silicon oxide particles. Colloidal silica may be used as silica particles, or particles different from colloidal silica may be used. The silicon oxide particles may include colloidal silica from the viewpoint of easily obtaining a high polishing speed for the resin material or from the viewpoint of easily reducing the surface roughness of the polished surface after polishing.

[0022] The silicon dioxide content in silicon dioxide particles (based on the total mass of silicon dioxide particles), or the silica content in silica particles (based on the total mass of silica particles), may be 50.0% by mass or more, greater than 50.0% by mass, 60.0% by mass or more, 70.0% by mass or more, 80.0% by mass or more, 90.0% by mass or more, 93.0% by mass or more, 95.0% by mass or more, 98.0% by mass or more, 99.0% by mass or more, 99.5% by mass or more, or 99.9% by mass or more, from the viewpoint of easily obtaining a high polishing speed for the resin material or easily reducing the surface roughness of the polished surface after polishing. The silicon dioxide particles may be substantially composed of silicon dioxide (a form in which substantially 100% by mass of silicon dioxide particles is silicon dioxide). The silica particles may be substantially composed of silica (a form in which substantially 100% by mass of silica particles is silica).

[0023] Aluminum component X can be present on at least a portion of the surface of silicon oxide particles. Aluminum compounds can be used as aluminum component X. In aluminum compounds, the aluminum element is aluminum ions (Al ３＋ It may exist on the surface of silicon dioxide particles in the state of ).

[0024] Aluminum component X is aluminum acetate (Al(CH) ３ COO) ３ ), aluminum chloride (AlCl ３It contains at least one aluminum component X1 selected from the group consisting of aluminum acetate and its derivatives, and may include the aluminum component X1 and an aluminum component X2 that does not correspond to the aluminum component X1. The aluminum component X may include at least one selected from the group consisting of aluminum acetate and its derivatives, and may include at least one selected from the group consisting of aluminum chloride and its derivatives. When the aluminum component X contains at least one selected from the group consisting of aluminum acetate and its derivatives, it is easy to obtain a high polishing rate of polybenzoxazole, polyimide, and polyhydroxystyrene. Also, when polishing a metal part, it is preferable to suppress discoloration of the metal part after polishing. When the aluminum component X contains at least one selected from the group consisting of aluminum acetate and its derivatives, discoloration of the metal part (for example, a copper part) after polishing can be suppressed.

[0025] Derivatives of aluminum acetate are compounds containing aluminum ions and acetate ions (salts containing aluminum ions and at least one acetate ion: excluding aluminum acetate (Al(CH ３ COO) ３ ). Examples of derivatives of aluminum acetate include aluminum acetate hydroxides such as aluminum diacetate monohydrate (basic aluminum acetate) and aluminum monoacetate dihydroxide.

[0026] Derivatives of aluminum chloride are compounds containing aluminum ions and chloride ions (salts containing aluminum ions and at least one chloride ion: excluding aluminum chloride (AlCl ３ ). Examples of derivatives of aluminum chloride include hydrates of aluminum chloride, aluminum chloride hydroxide (for example, [Al ２ (OH) ｎ Cl ６－ｎ ｍ (1 ≤ n ≤ 5): polyaluminum chloride), etc.

[0027] ​Examples of aluminum component X2 include aluminum lactate, aluminum laurate, aluminum stearate, aluminum oxalate, aluminum oxide, aluminum hydroxide, aluminum sulfide, aluminum nitride, aluminum fluoride, aluminum bromide, aluminum iodide, aluminum sulfate, sodium aluminum sulfate, potassium aluminum sulfate, aluminum ammonium sulfate, aluminum nitrate, aluminum perchlorate, aluminum aluminate, aluminum silicate, aluminum phosphate, alkoxyaluminum, aluminosilicate, aluminum compounds containing one or more of these conjugate acids, and their hydrates.

[0028] The atomic ratio Al / Si of aluminum and silicon obtained by X-ray photoelectron spectroscopy (XPS) measurement on the surface of abrasive grain a may be within the following ranges. The atomic ratio Al / Si may be 0.010 or higher, 0.030 or higher, 0.050 or higher, 0.080 or higher, 0.100 or higher, 0.110 or higher, 0.120 or higher, 0.124 or higher, 0.125 or higher, 0.130 or higher, 0.140 or higher, 0.150 or higher, or 0.160 or higher, from the viewpoint of easily obtaining a high polishing speed for resin materials (polybenzoxazole, polyimide, polyhydroxystyrene, etc.), from the viewpoint of adjusting the polishing speed of resin materials (polybenzoxazole, polyimide, polyhydroxystyrene, etc.), or from the viewpoint of easily suppressing discoloration of the metal part (e.g., copper part) after polishing. The atomic ratio Al / Si may be 1.000 or less, less than 1.000, 0.900 or less, 0.800 or less, 0.700 or less, 0.600 or less, 0.500 or less, 0.400 or less, 0.300 or less, 0.200 or less, 0.180 or less, 0.170 or less, 0.160 or less, 0.150 or less, 0.140 or less, 0.130 or less, 0.125 or less, 0.124 or less, 0.120 or less, or 0.110 or less, from the viewpoint of easily obtaining a high polishing rate for resin materials (polybenzoxazole, polyimide, polyhydroxystyrene, etc.) or from the viewpoint of adjusting the polishing rate of resin materials (polybenzoxazole, polyimide, polyhydroxystyrene, etc.). From these perspectives, the atomic ratio Al / Si may be 0.010 to 1.000, 0.010 to 0.500, 0.010 to 0.200, 0.010 to 0.150, 0.010 to 0.120, 0.100 to 1.000, 0.100 to 0.500, 0.100 to 0.200, 0.100 to 0.150, 0.100 to 0.120, 0.120 to 1.000, 0.120 to 0.500, 0.120 to 0.200, 0.120 to 0.150, 0.150 to 1.000, 0.150 to 0.500, or 0.150 to 0.200. The atomic ratio Al / Si can be measured by the method described in [Examples] below, and may be the average value of three measurement points. In this embodiment, the atomic ratio Al / Si of abrasive particles a in a slurry, aqueous dispersion of abrasive particles a, etc., can be measured by recovering the abrasive particles a from the liquid.In surface treatment of silicon oxide particles using an aluminum component, the atomic ratio Al / Si can be adjusted by controlling the amount of aluminum component adhering to the surface of the silicon oxide particles. The atomic ratio Al / Si tends to remain the same before and after mixing abrasive grains a with other components to prepare the slurry.

[0029] The atomic ratio of chlorine to silicon (Cl / Si) obtained by X-ray photoelectron spectroscopy (XPS) measurement on the surface of abrasive grain a may be within the following ranges. The atomic ratio of Cl / Si may be 0.001 or higher, 0.003 or higher, 0.005 or higher, 0.008 or higher, 0.010 or higher, 0.015 or higher, 0.018 or higher, 0.019 or higher, 0.020 or higher, 0.022 or higher, 0.024 or higher, 0.025 or higher, 0.028 or higher, 0.030 or higher, 0.035 or higher, or 0.037 or higher, from the viewpoint of easily obtaining a high polishing speed for resin materials (polybenzoxazole, polyimide, polyhydroxystyrene, etc.), from the viewpoint of adjusting the polishing speed of resin materials (polybenzoxazole, polyimide, polyhydroxystyrene, etc.), or from the viewpoint of easily suppressing discoloration of the metal part (e.g., copper part) after polishing. The atomic ratio of Cl / Si may be 0.100 or less, 0.090 or less, 0.080 or less, 0.070 or less, 0.060 or less, 0.050 or less, 0.040 or less, 0.037 or less, 0.035 or less, 0.030 or less, 0.028 or less, 0.025 or less, 0.024 or less, 0.022 or less, 0.020 or less, or 0.019 or less, from the viewpoint of easily obtaining a high polishing rate for resin materials (polybenzoxazole, polyimide, polyhydroxystyrene, etc.) or from the viewpoint of adjusting the polishing rate of resin materials (polybenzoxazole, polyimide, polyhydroxystyrene, etc.). From these viewpoints, the atomic ratio Cl / Si may be 0.001 to 0.100, 0.001 to 0.040, 0.001 to 0.030, 0.001 to 0.020, 0.010 to 0.100, 0.010 to 0.040, 0.010 to 0.030, 0.010 to 0.020, 0.020 to 0.100, 0.020 to 0.040, 0.020 to 0.030, 0.030 to 0.100, or 0.030 to 0.040. The atomic ratio Cl / Si can be measured by the method described in [Examples] below, and may be the average value of three measurement points. In this embodiment, the atomic ratio Cl / Si in abrasive particles a in a slurry, an aqueous dispersion of abrasive particles a, etc., can be measured by recovering the abrasive particles a from the liquid. In surface treatment of silicon dioxide particles using a compound containing chlorine atoms (for example, an aluminum component containing chlorine atoms), the atomic ratio Cl / Si can be adjusted by controlling the amount of chlorine atoms attached to the surface of the silicon dioxide particles.The atomic ratio of Cl / Si tends to remain the same before and after mixing abrasive grains a with other components to prepare the slurry.

[0030] The average particle size of abrasive grain A, or the average particle size of abrasive grain a, may be within the following ranges, from the viewpoint of easily obtaining a high polishing speed for the resin material, or from the viewpoint of easily reducing the surface roughness of the polished surface after polishing. The average particle size may be 10.0 nm or more, 20.0 nm or more, 25.0 nm or more, greater than 25.0 nm, 30.0 nm or more, 40.0 nm or more, 50.0 nm or more, greater than 50.0 nm, 55.0 nm or more, 60.0 nm or more, greater than 60.0 nm, 65.0 nm or more, 70.0 nm or more, greater than 70.0 nm, 75.0 nm or more, 80.0 nm or more, greater than 80.0 nm, 85.0 nm or more, 88.0 nm or more, 89.0 nm or more, 90.0 nm or more, greater than 90.0 nm, 93.0 nm or more, 95.0 nm or more, 96.0 nm or more, 98.0 nm or more, or 99.0 nm or more. The average particle size may be 1000 nm or less, 900 nm or less, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, 300 nm or less, 200 nm or less, 150 nm or less, 120 nm or less, 100 nm or less, 99.0 nm or less, 98.0 nm or less, 96.0 nm or less, 95.0 nm or less, 93.0 nm or less, 90.0 nm or less, 89.0 nm or less, 88.0 nm or less, 85.0 nm or less, 80.0 nm or less, 75.0 nm or less, 70.0 nm or less, or 65.0 nm or less. From these perspectives, the average particle size may be 10.0–1000 nm, 10.0–500 nm, 10.0–200 nm, 10.0–100 nm, 20.0–1000 nm, 20.0–500 nm, 20.0–200 nm, 20.0–100 nm, 30.0–1000 nm, 30.0–500 nm, 30.0–200 nm, 30.0–100 nm, 50.0–1000 nm, 50.0–500 nm, 50.0–200 nm, 50.0–100 nm, 80.0–1000 nm, 80.0–500 nm, 80.0–200 nm, or 80.0–100 nm. The average particle size is the average particle size in the slurry and may be the 50% cumulative diameter (D50) in the mass-based cumulative particle size distribution curve. The average particle size can be measured by the method described in [Examples] below.

[0031] The zeta potential of abrasive grain A, or the zeta potential of abrasive grain a, may be positive in the slurry (the zeta potential may exceed 0 mV) from the viewpoint of easily obtaining a high polishing speed for resin materials. It is presumed that a positive zeta potential allows for suitable polishing of resin materials that tend to carry a negative charge (such as polybenzoxazole, polyimide, and polyhydroxystyrene). The zeta potential can be measured by the method described in the [Examples] below.

[0032] The slurry according to this embodiment may contain abrasive grains other than abrasive grain a. Examples of abrasive grains other than abrasive grain a include silicon oxide particles without aluminum component X on their surface; cerium oxide particles; aluminum oxide particles; silicon nitride particles; zirconium oxide particles; titanium oxide particles; yttrium oxide particles, etc.

[0033] The content of abrasive grains a in abrasive grain A may be 50.0% by mass or more, greater than 50.0% by mass, 60.0% by mass or more, 70.0% by mass or more, 80.0% by mass or more, 90.0% by mass or more, 93.0% by mass or more, 95.0% by mass or more, 98.0% by mass or more, 99.0% by mass or more, 99.5% by mass or more, or 99.9% by mass or more, based on the total mass of abrasive grain A, from the viewpoint of easily obtaining a high polishing speed of the resin material. Abrasive grain A may be substantially composed of abrasive grains a (a mode in which substantially 100% by mass of abrasive grain A is abrasive grains a).

[0034] The content of abrasive grains A or the content of abrasive grains a may be within the following ranges based on the total mass of the slurry, from the perspective of easily obtaining a high polishing rate of the resin material. The content of abrasive grains A or the content of abrasive grains a may be 0.10% by mass or more, 0.30% by mass or more, 0.50% by mass or more, 0.80% by mass or more, 1.00% by mass or more, 1.50% by mass or more, 2.00% by mass or more, 2.50% by mass or more, 3.00% by mass or more, 3.50% by mass or more, 4.00% by mass or more, 4.50% by mass or more, 5.00% by mass or more, 5.50% by mass or more, or 6.00% by mass or more. The content of abrasive grains A or the content of abrasive grains a may be 50.0% by mass or less, 30.0% by mass or less, 20.0% by mass or less, 10.0% by mass or less, 8.00% by mass or less, 6.00% by mass or less, 5.50% by mass or less, 5.00% by mass or less, 4.50% by mass or less, or 4.00% by mass or less. From these perspectives, the content of abrasive grains A or the content of abrasive grains a may be 0.10 - 50.0% by mass, 0.10 - 10.0% by mass, 0.10 - 5.00% by mass, 1.00 - 50.0% by mass, 1.00 - 10.0% by mass, 1.00 - 5.00% by mass, 3.00 - 50.0% by mass, 3.00 - 10.0% by mass, 3.00 - 5.00% by mass, 5.00 - 50.0% by mass, or 5.00 - 10.0% by mass.

[0035] The slurry according to the present embodiment may contain water. The water is not particularly limited, and examples include deionized water, ion-exchanged water, ultrapure water, etc.

[0036] The slurry according to the present embodiment may contain additives (components not corresponding to abrasive grains and water). Examples of such additives include acid components, base components, organic solvents, polymer compounds, metal corrosion inhibitors, oxidizing agents, etc.

[0037] The slurry according to the present embodiment may contain an acid component. The acid component may include an organic acid component and may include an inorganic acid component.

[0038] Organic acid components include organic acids, organic acid esters, and organic acid salts. Examples of organic acids include glycine, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, 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 Examples of organic acid esters include 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, fumaric acid, tartaric acid, citric acid, p-toluenesulfonic acid, p-phenolsulfonic acid, methylsulfonic acid, lactic acid, itaconic acid, quinaldic acid, etc. Examples of organic acid esters include esters of the above organic acids. Examples of organic acid salts include ammonium salts, alkali metal salts, alkaline earth metal salts, halides, etc. Examples of organic acid components include amino acids, amino acid esters, amino acid salts, etc.

[0039] Inorganic acid components include inorganic acids, ammonium salts of inorganic acids, and metal salts of inorganic acids (alkali metal salts, alkaline earth metal salts, etc.). Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, chromic acid, and phosphoric acid. Examples of ammonium salts of inorganic acids include monovalent ammonium salts of inorganic acids such as ammonium nitrate, ammonium chloride, and ammonium bromide; divalent ammonium salts of inorganic acids such as ammonium carbonate, ammonium bicarbonate, ammonium sulfate, and ammonium persulfate; and trivalent ammonium salts of inorganic acids such as ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium borate.

[0040] From the perspective of easily obtaining a high polishing rate for resin materials and metal materials, the acid component may contain an organic acid component, may contain an amino acid component, and may contain at least one selected from the group consisting of amino acids, amino acid esters, and amino acid salts, and may contain at least one selected from the group consisting of glycine, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, esters of these amino acids, and salts of these amino acids.

[0041] As the content of the acid component, the content of the organic acid component, or the content of the amino acid component, the content B1 may be in the following range based on the total mass of the slurry from the perspective of easily obtaining a high polishing rate for resin materials and metal materials. The content of the acid component may be 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, 0.15% by mass or more, 0.20% by mass or more, 0.25% by mass or more, or 0.30% by mass or more. The content of the acid component may be 5.00% by mass or less, 3.00% by mass or less, 2.00% by mass or less, 1.00% by mass or less, 0.80% by mass or less, 0.60% by mass or less, 0.50% by mass or less, 0.40% by mass or less, or 0.30% by mass or less. From these perspectives, the content of the acid component may be 0.01 to 5.00% by mass, 0.01 to 1.00% by mass, 0.01 to 0.50% by mass, 0.10 to 5.00% by mass, 0.10 to 1.00% by mass, 0.10 to 0.50% by mass, 0.20 to 5.00% by mass, 0.20 to 1.00% by mass, or 0.20 to 0.50% by mass. From the same perspective, the content of the compound group or compound included in the acid component (for example, the content of the organic acid component, the amino acid component, etc.) may also be in each of the above ranges.

[0042] From the viewpoint of easily obtaining a high polishing speed for the resin material, the content of the acid component may be within the following ranges per 100 parts by mass of abrasive grain A or abrasive grain a: The content of the acid component may be 0.1 parts by mass or more, 0.5 parts by mass or more, 1.0 parts by mass or more, 1.5 parts by mass or more, 2.0 parts by mass or more, 2.5 parts by mass or more, 3.0 parts by mass or more, 3.5 parts by mass or more, 4.0 parts by mass or more, 4.5 parts by mass or more, 5.0 parts by mass or more, 5.5 parts by mass or more, 6.0 parts by mass or more, 6.5 parts by mass or more, 7.0 parts by mass or more, or 7.5 parts by mass or more. The content of the acid component may be 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 9.5 parts by mass or less, 9.0 parts by mass or less, 8.5 parts by mass or less, 8.0 parts by mass or less, 7.5 parts by mass or less, 7.0 parts by mass or less, 6.5 parts by mass or less, 6.0 parts by mass or less, 5.5 parts by mass or less, or 5.0 parts by mass or less. From these viewpoints, the content of the acid component may be 0.1 to 20 parts by mass, 0.1 to 10 parts by mass, 0.1 to 8.0 parts by mass, 0.1 to 6.0 parts by mass, 1.0 to 20 parts by mass, 1.0 to 10 parts by mass, 1.0 to 8.0 parts by mass, 1.0 to 6.0 parts by mass, 3.0 to 20 parts by mass, 3.0 to 10 parts by mass, 3.0 to 8.0 parts by mass, 3.0 to 6.0 parts by mass, 6.0 to 20 parts by mass, 6.0 to 10 parts by mass, or 6.0 to 8.0 parts by mass. From a similar viewpoint, the group of compounds included in the acid component or the content of the compounds (for example, the content of organic acid components, amino acid components, etc.) may also be within the above ranges.

[0043] The slurry according to this embodiment may contain a basic component, or may not contain a basic component. Examples of basic components include metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; and ammonia.

[0044] The slurry according to this embodiment may contain an organic solvent. Examples of organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, isopropanol (isopropyl alcohol), and 3-methyl-3-methoxybutanol (MMB); carbonate esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; lactones such as butyrolactone and propiolactone; glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, hexylene glycol, and tripropylene glycol; and alkylene glycol monoalkyl ethers. Examples include glycol derivatives such as alkylene glycol dialkyl ethers; ether compounds such as tetrahydrofuran, dioxane, dimethoxyethane, polyethylene oxide, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether; ketone compounds such as acetone and methyl ethyl ketone; phenol compounds such as phenol; amide compounds such as dimethylformamide; sulfolane compounds such as sulfolane; and N-methylpyrrolidone. From the viewpoint of easily obtaining a high polishing speed for the resin material or easily reducing the surface roughness of the polished surface after polishing, the organic solvent may contain an ether compound, a glycol ether, or a propylene glycol monopropyl ether. That is, the slurry according to this embodiment may contain an ether compound, and the ether compound may contain a glycol ether or a propylene glycol monopropyl ether.

[0045] The organic solvent content may be within the following ranges based on the total mass of the slurry, from the viewpoint of easily obtaining a high polishing speed for the resin material or easily reducing the surface roughness of the polished surface after polishing. The organic solvent content may be 0.001% by mass or more, 0.005% by mass or more, 0.010% by mass or more, greater than 0.010% by mass, 0.020% by mass or more, greater than 0.020% by mass, 0.030% by mass or more, 0.050% by mass or more, 0.080% by mass or more, or 0.100% by mass or more. The organic solvent content may be 5.000% by mass or less, 3.000% by mass or less, 1.000% by mass or less, 0.800% by mass or less, 0.600% by mass or less, 0.500% by mass or less, 0.400% by mass or less, 0.300% by mass or less, 0.200% by mass or less, or 0.100% by mass or less. From these viewpoints, the content of the organic solvent may be 0.001 to 5.000% by mass, 0.001 to 1.000% by mass, 0.001 to 0.500% by mass, 0.010 to 5.000% by mass, 0.010 to 1.000% by mass, 0.010 to 0.500% by mass, 0.050 to 5.000% by mass, 0.050 to 1.000% by mass, or 0.050 to 0.500% by mass. From a similar viewpoint, the group of compounds contained in the organic solvent or the content of the compounds (for example, the content of ether compounds, glycol ethers, etc.) may also be within the above ranges.

[0046] The content of the organic solvent may be within the following ranges per 100 parts by mass of abrasive grains A or abrasive grain a, from the viewpoint of easily obtaining a high polishing speed for the resin material or easily reducing the surface roughness of the polished surface after polishing. The content of the organic solvent may be 0.1 parts by mass or more, 0.3 parts by mass or more, 0.5 parts by mass or more, 0.8 parts by mass or more, 1.0 parts by mass or more, 1.2 parts by mass or more, 1.5 parts by mass or more, 1.8 parts by mass or more, 2.0 parts by mass or more, 2.2 parts by mass or more, or 2.5 parts by mass or more. The content of the organic solvent may be 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 9.0 parts by mass or less, 8.0 parts by mass or less, 7.0 parts by mass or less, 6.0 parts by mass or less, 5.0 parts by mass or less, 4.0 parts by mass or less, 3.5 parts by mass or less, 3.0 parts by mass or less, 2.5 parts by mass or less, or 2.0 parts by mass or less. From these viewpoints, the content of the organic solvent may be 0.1 to 20 parts by mass, 0.1 to 10 parts by mass, 0.1 to 5.0 parts by mass, 0.1 to 2.0 parts by mass, 1.0 to 20 parts by mass, 1.0 to 10 parts by mass, 1.0 to 5.0 parts by mass, 1.0 to 2.0 parts by mass, 2.0 to 20 parts by mass, 2.0 to 10 parts by mass, or 2.0 to 5.0 parts by mass. From a similar viewpoint, the group of compounds included in the organic solvent or the content of the compounds (for example, the content of ether compounds, glycol ethers, etc.) may also be within the above ranges.

[0047] The slurry according to this embodiment may contain a polymer compound, or may not contain a polymer compound substantially. Examples of polymer compounds include glycerin polymers such as polyglycerin and polyglycerin derivatives; polycarboxylic acids such as polyacrylic acid and polymaleic acid; acrylic polymers such as polyacrylamide and polydimethylacrylamide; polysaccharides such as carboxymethylcellulose, agar, curdlan, dextrin, cyclodextrin, and pullulan; and vinyl polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrolein.

[0048] The slurry according to this embodiment may contain a nitrogen-containing aromatic ring compound (a compound having an aromatic ring containing nitrogen). The nitrogen-containing aromatic ring compound may be used as a metal corrosion inhibitor. Examples of nitrogen-containing aromatic ring compounds include triazole compounds (compounds having a triazole ring), imidazole compounds (compounds having an imidazole ring), tetrazole compounds (compounds having a tetrazole ring), pyrazole compounds (compounds having a pyrazole ring), and pyrimidine compounds (compounds having a pyrimidine ring). From the viewpoint of easily obtaining a high polishing speed for resin materials or easily obtaining a suitable corrosion inhibitory effect, the nitrogen-containing aromatic ring compound may contain a triazole compound, and may also contain a benzotriazole compound (a compound having a benzotriazole ring).

[0049] Examples of triazole compounds include 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxy-1H-benzotriazole, 4-carboxy-1H-benzotriazole methyl ester (1H-benzotriazole-4-carboxylate methyl), 4-carboxy-1H-benzotriazole butyl ester (1H-benzotriazole-4-carboxylate butyl), 4-carboxy-1H-benzotriazole octyl ester (1H-benzotriazole-4-carboxylate octyl), 5-hexylbenzotriazole, and [1,2,3-benzotriazole]. Triazolyl-1-methyl][1,2,4-triazolyl-1-methyl][2-ethylhexyl]amine, tolyltriazole, naphthotriazole, bis[(1-benzotriazolyl)methyl]phosphonic acid, 3H-1,2,3-triazolo[4,5-b]pyridine-3-ol, 1H-1,2,3-triazolo[4,5-b]pyridine, 1-acetyl-1H-1,2,3-triazolo[4,5-b] Examples include 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, and 2-methylsulfanyl-5,7-diphenyl-4,7-dihydro-[1,2,4]triazolo[1,5-a]pyrimidine. Nitrogen-containing aromatic ring compounds may include benzotriazole from the viewpoint of easily obtaining a high polishing speed for resin materials or easily obtaining a suitable corrosion-preventive effect.

[0050] The nitrogen-containing aromatic ring compound content may be within the following ranges, based on the total mass of the slurry, from the viewpoint of easily obtaining a high polishing speed for the resin material or easily obtaining a suitable corrosion protection effect. The nitrogen-containing aromatic ring compound content may be 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 0.010% by mass or more. The nitrogen-containing aromatic ring compound content may be 1.000% by mass or less, 0.800% by mass or less, 0.500% by mass or less, 0.300% by mass or less, 0.200% by mass or less, 0.100% by mass or less, 0.080% by mass or less, 0.060% by mass or less, 0.050% by mass or less, 0.040% by mass or less, 0.030% by mass or less, 0.020% by mass or less, or 0.010% by mass or less. From these viewpoints, the content of nitrogen-containing aromatic ring compounds may be 0.001 to 1.000% by mass, 0.001 to 0.500% by mass, 0.001 to 0.100% by mass, 0.003 to 1.000% by mass, 0.003 to 0.500% by mass, 0.003 to 0.100% by mass, 0.005 to 1.000% by mass, 0.005 to 0.500% by mass, or 0.005 to 0.100% by mass. From a similar viewpoint, the content of the group of compounds included in nitrogen-containing aromatic ring compounds or the compounds themselves (for example, the content of triazole compounds, benzotriazole compounds, etc.) may also be within the above ranges.

[0051] The content of nitrogen-containing aromatic ring compounds may be within the following ranges per 100 parts by mass of abrasive grains A or abrasive grain a, from the viewpoint of easily obtaining a high polishing speed for resin materials or easily obtaining a suitable corrosion protection effect. The content of nitrogen-containing aromatic ring compounds may be 0.01 parts by mass or more, 0.03 parts by mass or more, 0.05 parts by mass or more, 0.08 parts by mass or more, 0.10 parts by mass or more, 0.12 parts by mass or more, 0.15 parts by mass or more, 0.18 parts by mass or more, 0.20 parts by mass or more, 0.22 parts by mass or more, or 0.25 parts by mass or more. The content of the nitrogen-containing aromatic ring compound is 5.00 parts by mass or less, 3.00 parts by mass or less, 2.00 parts by mass or less, 1.00 parts by mass or less, 0.80 parts by mass or less, 0.70 parts by mass or less, 0. The amount may be 60 parts by mass or less, 0.50 parts by mass or less, 0.40 parts by mass or less, 0.35 parts by mass or less, 0.30 parts by mass or less, 0.25 parts by mass or less, or 0.20 parts by mass or less. From these viewpoints, the content of nitrogen-containing aromatic ring compounds may be 0.01 to 5.00 parts by mass, 0.01 to 1.00 parts by mass, 0.01 to 0.50 parts by mass, 0.01 to 0.20 parts by mass, 0.10 to 5.00 parts by mass, 0.10 to 1.00 parts by mass, 0.10 to 0.50 parts by mass, 0.10 to 0.20 parts by mass, 0.20 to 5.00 parts by mass, 0.20 to 1.00 parts by mass, or 0.20 to 0.50 parts by mass. From a similar viewpoint, the content of the group of compounds included in nitrogen-containing aromatic ring compounds or the compounds themselves (for example, the content of triazole compounds, benzotriazole compounds, etc.) may also be within the above ranges.

[0052] The slurry according to this embodiment may contain an oxidizing agent. The slurry according to this embodiment may be prepared by mixing in an oxidizing agent before or during use. By adjusting the content of the oxidizing agent, the amount of protrusion of the metal part can be adjusted when the metal part protrudes from the resin part after polishing, as described later. Examples of oxidizing agents include hydrogen peroxide, potassium periodate, hypochlorous acid, and ozonated water.

[0053] The content of the oxidizing agent may be within the following ranges, based on the total mass of the slurry, from the viewpoint of easily obtaining a high polishing speed for the resin material or from the viewpoint of easily adjusting the amount of protrusion of the metal part. The content of the oxidizing agent may be 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, 0.20% by mass or more, 0.30% by mass or more, 0.40% by mass or more, or 0.50% by mass or more. The content of the oxidizing agent may be 5.00% by mass or less, 3.00% by mass or less, 1.00% by mass or less, 0.80% by mass or less, 0.60% by mass or less, or 0.50% by mass or less. From these viewpoints, the content of the oxidizing agent may be 0.01 to 5.00% by mass, 0.01 to 3.00% by mass, 0.01 to 1.00% by mass, 0.10 to 5.00% by mass, 0.10 to 3.00% by mass, 0.10 to 1.00% by mass, 0.30 to 5.00% by mass, 0.30 to 3.00% by mass, or 0.30 to 1.00% by mass. From a similar viewpoint, the group of compounds included in the oxidizing agent or the content of the compounds (for example, the content of hydrogen peroxide, etc.) may also be within the above ranges.

[0054] From the viewpoint of easily obtaining a high polishing speed for the resin material or easily adjusting the amount of protrusion of the metal part, the content of the oxidizing agent may be in the following ranges per 100 parts by mass of abrasive grain A or abrasive grain a. The content of the oxidizing agent may be 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, or 12 parts by mass or more. The content of the oxidizing agent may be 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, or 10 parts by mass or less. From these viewpoints, the content of the oxidizing agent may be 1 to 30 parts by mass, 1 to 20 parts by mass, 1 to 10 parts by mass, 5 to 30 parts by mass, 5 to 20 parts by mass, 5 to 10 parts by mass, 10 to 30 parts by mass, or 10 to 20 parts by mass. From a similar viewpoint, the group of compounds included in the oxidizing agent or the content of the compounds (for example, the content of hydrogen peroxide, etc.) may also be in the above ranges.

[0055] The pH (at 25°C) of the slurry according to this embodiment may be within the following range. From the viewpoint of easily obtaining a high polishing speed for the resin material, the pH may be 1.0 or higher, 1.5 or higher, 2.0 or higher, 2.5 or higher, 3.0 or higher, greater than 3.0, 3.5 or higher, 3.8 or higher, 4.0 or higher, greater than 4.0, 4.1 or higher, 4.2 or higher, 4.3 or higher, 4.4 or higher, or 4.5 or higher. The pH may be 13.0 or lower, 12.5 or lower, 12.0 or lower, 11.5 or lower, 11.0 or lower, 10.5 or lower, 10.0 or lower, 9.5 or lower, 9.0 or lower, 8.5 or lower, 8.0 or lower, 7.5 or lower, 7.0 or lower, 6.5 or lower, 6.0 or lower, 5.5 or lower, 5.0 or lower, 4.8 or lower, 4.5 or lower, 4.4 or lower, 4.3 or lower, 4.2 or lower, or 4.1 or lower. From these perspectives, the pH may be 1.0 to 13.0, 1.0 to 9.0, 1.0 to 5.0, 3.0 to 13.0, 3.0 to 9.0, 3.0 to 5.0, 4.0 to 13.0, 4.0 to 9.0, or 4.0 to 5.0. The pH can be measured by the method described in the [Examples] below.

[0056] The slurry according to this embodiment may be stored as a storage liquid with a reduced amount of water compared to that used during polishing. One embodiment of the slurry according to this embodiment may be such a storage liquid. The storage liquid can be used by diluting it with water before or during polishing.

[0057] If the slurry according to this embodiment contains at least one additive in addition to abrasive grains, the slurry may be stored as a one-component slurry containing abrasive grains and additives, or as a multi-component slurry (slurry set) having at least a first liquid and a second liquid. In a multi-component slurry, the components of the slurry may be separated into a first liquid and a second liquid so that at least the first liquid and the second liquid are mixed to form the slurry (slurry for polishing). For example, in a multi-component slurry, the components of the slurry according to this embodiment may be stored separated into at least a first liquid and a second liquid, with the first liquid containing abrasive grains and the second liquid containing at least one additive. The components of the slurry may be stored separated into three or more liquids. Each liquid (first liquid, second liquid, etc.) in a multi-component slurry may be mixed before or during polishing. In a multi-liquid slurry, each liquid (first liquid, second liquid, etc.) may be supplied onto a polishing platen, where they may be mixed. The liquids constituting the multi-liquid slurry (first liquid, second liquid, etc.) may be stored as a storage liquid with less water than used during polishing, and may be used by diluting them with water before or during polishing.

[0058] The slurry and abrasive grains according to this embodiment are for polishing the resin portion of a workpiece having a resin portion containing a resin material. The polishing method according to this embodiment comprises a polishing step of polishing the resin portion of a workpiece having a resin portion containing a resin material using the slurry according to this embodiment. Examples of resin materials include polybenzoxazole (PBO), polybenzoxazole precursors, polyimide (excluding polyimidephenol), phenolic resins (polyhydroxystyrene, novolac resin, polyimidephenol, etc.), epoxy resins, acrylic resins, methacrylic resins, polyesters (unsaturated polyester resins and polyesters that do not fall under unsaturated polyester resins), maleimide resins, polyamideimide, and polyallyl ethers. The resin portion may contain at least one of these as its main component. The resin material may contain polybenzoxazole, polyimide, phenolic resin, and polyhydroxystyrene. The resin portion may be a cured product of a curable resin or may be uncured. The zeta potential of the resin material may be negative (the zeta potential may be less than 0 mV).

[0059] The member to be polished may further have a metal part containing a metallic material. The metallic part may be covered by a resin part and may be exposed on the polished surface together with the resin part. Examples of metallic materials include copper, cobalt, tantalum, aluminum, titanium, tungsten, manganese, tin, silver, and alloys thereof. The metallic material may contain copper and may contain a tin-silver alloy. The polishing step of the polishing method according to this embodiment may be a step of polishing the resin part and the metallic part. The slurry according to this embodiment may be used in the step of polishing the resin part and the metallic part.

[0060] In the above hybrid bonding, by removing the resin portion on the metal portion by polishing, a polished surface (exposed surface) with the metal portion and resin portion exposed can be obtained. Furthermore, by polishing the polished surface (exposed surface) with the metal portion and resin portion exposed, the metal portion can be made to protrude from the resin portion in a direction perpendicular to the polished surface (exposed surface). The polishing step of the polishing method according to this embodiment is a polishing step for polishing the resin portion of a member to be polished having a resin portion and a metal portion covered by the resin portion, and may be a step of polishing the resin portion until the metal portion is exposed, or a step of polishing the resin portion until the metal portion protrudes from the resin portion in a direction perpendicular to the polished surface. The slurry according to this embodiment may be used as a polishing step for polishing the resin portion of a member to be polished having a resin portion and a metal portion covered by the resin portion, and may be used as a step of polishing the resin portion until the metal portion is exposed, or may be used as a step of polishing the resin portion until the metal portion protrudes from the resin portion in a direction perpendicular to the polished surface.

[0061] The shape of the member to be polished is not particularly limited and may be, for example, a film. In the polishing process, it is possible to polish the surface of the member to be polished, to polish the surface where resin material is present, and to polish the surface where both resin material and metal material are present. In the polishing process, it is possible to polish and remove at least a portion of the member to be polished, and to polish and remove at least a portion of the resin material. The member to be polished is not particularly limited and may be a wafer (e.g., a semiconductor wafer) or a chip (e.g., a semiconductor chip). The member to be polished may be a wiring board or a circuit board.

[0062] The method for manufacturing a component according to this embodiment includes a component manufacturing step of obtaining a component using a member to be polished by the polishing method according to this embodiment. The component according to this embodiment is a component obtained by the method for manufacturing a component according to this embodiment. The component according to this embodiment is not particularly limited, but may be an electronic component (e.g., a semiconductor component such as a semiconductor package), a wafer (e.g., a semiconductor wafer), or a chip (e.g., a semiconductor chip). As one embodiment of the method for manufacturing a component according to this embodiment, the method for manufacturing an electronic component according to this embodiment obtains an electronic component using a member to be polished by the polishing method according to this embodiment. As one embodiment of the method for manufacturing a component according to this embodiment, the method for manufacturing a semiconductor component according to this embodiment obtains a semiconductor component (e.g., a semiconductor package) using a member to be polished by the polishing method according to this embodiment. The method for manufacturing a component according to this embodiment may include a polishing step of polishing the member to be polished by the polishing method according to this embodiment before the component manufacturing step.

[0063] As one aspect of the component manufacturing process according to this embodiment, the component manufacturing process may include a piece-forming step in which the member to be polished by the polishing method according to this embodiment is pieced into individual pieces. The piece-forming step may be, for example, a step of dicing a wafer (e.g., a semiconductor wafer) polished by the polishing method according to this embodiment to obtain a chip (e.g., a semiconductor chip). As one aspect of the component manufacturing process according to this embodiment, the electronic component manufacturing process according to this embodiment may include a step of obtaining an electronic component (e.g., a semiconductor component) by piece-forming the member to be polished by the polishing method according to this embodiment. As one aspect of the component manufacturing process according to this embodiment, the semiconductor component manufacturing process according to this embodiment may include a step of obtaining a semiconductor component (e.g., a semiconductor package) by piece-forming the member to be polished by the polishing method according to this embodiment.

[0064] The method for manufacturing a part according to this embodiment may include, as one aspect of the part manufacturing process, a connection step of connecting (for example, electrically connecting) a member to be polished by the polishing method according to this embodiment to another connected body. The connected body connected to the member to be polished by the polishing method according to this embodiment is not particularly limited and may be the member to be polished by the polishing method according to this embodiment, or it may be a connected body different from the member to be polished by the polishing method according to this embodiment. In the connection step, the member to be polished and the connected body may be directly connected (connected in a state where the member to be polished and the connected body are in contact), or they may be connected via another member (such as a conductive member). The connection step can be performed before the individualization step, after the individualization step, or before and after the individualization step.

[0065] The connection step may be a step of connecting the surface of the member to be polished, which has been polished by the polishing method according to this embodiment, to the connected body, or a step of connecting the connecting surface of the member to be polished, which has been polished by the polishing method according to this embodiment, to the connecting surface of the connected body. The connecting surface of the member to be polished may be the surface of the member to be polished, which has been polished by the polishing method according to this embodiment. By the connection step, a connected body comprising the member to be polished and the connected body can be obtained. In the connection step, if the connecting surface of the member to be polished has a metal part, the connected body may be brought into contact with the metal part. In the connection step, if the connecting surface of the member to be polished has a metal part and the connecting surface of the connected body has a metal part, the metal parts may be brought into contact with each other. The metal part may contain copper, or it may contain a tin-silver alloy.

[0066] The device according to this embodiment (for example, an electronic device such as a semiconductor device) comprises a member to be polished by the polishing method according to this embodiment, and at least one selected from the group consisting of the component according to this embodiment.

[0067] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0068] <Preparation of Polishing Slurry> (Example 1) An aqueous dispersion A was prepared containing abrasive particles having silicon dioxide particles (colloidal silica) and aluminum monohydroxydiacetate present on the surface of the silicon dioxide particles. Polishing slurry was prepared by mixing this aqueous dispersion A with glycine, benzotriazole, propylene glycol monopropyl ether, hydrogen peroxide, and ion-exchanged water. The content of each component in the polishing slurry (reference: total amount of polishing slurry) was as follows: abrasive particle content was 4.00% by mass, glycine content was 0.30% by mass, benzotriazole content was 0.01% by mass, propylene glycol monopropyl ether content was 0.10% by mass, and hydrogen peroxide content was 0.50% by mass.

[0069] (Example 2) A water dispersion B was prepared containing abrasive particles having silicon dioxide particles (colloidal silica) and aluminum hydroxide chloride present on the surface of the silicon dioxide particles. A polishing slurry was prepared in the same manner as in Example 1, except that water dispersion B was used instead of water dispersion A.

[0070] (Example 3) An abrasive slurry was prepared in the same manner as in Example 2, except that the amount of aqueous dispersion B used was increased and the abrasive content was changed to 6.00% by mass.

[0071] (Example 4) An aqueous dispersion C was prepared containing abrasive particles having silicon dioxide particles (colloidal silica) and aluminum hydroxide chloride present on the surface of the silicon dioxide particles. A polishing slurry was prepared in the same manner as in Example 1, except that aqueous dispersion C was used instead of aqueous dispersion A.

[0072] (Example 5) An aqueous dispersion D was prepared containing abrasive particles having silicon oxide particles (colloidal silica) and aluminum hydroxide chloride present on the surface of the silicon oxide particles. A polishing slurry was prepared in the same manner as in Example 1, except that aqueous dispersion D was used instead of aqueous dispersion A.

[0073] (Comparative Example 1) A water dispersion E containing silicon oxide particles (colloidal silica) without aluminum components as abrasive grains was prepared. A polishing slurry was prepared in the same manner as in Example 1, except that water dispersion E was used instead of water dispersion A.

[0074] <X-ray photoelectron spectroscopy measurement of abrasive grains> By performing X-ray photoelectron spectroscopy (XPS) measurements, the average value and standard deviation of the atomic ratio Al / Si (atomic ratio of aluminum to silicon) on the surface of abrasive grains in aqueous dispersions A to D were calculated, the average value and standard deviation of the atomic ratio C / Si (atomic ratio of carbon to silicon) on the surface of abrasive grains in aqueous dispersions A and E were calculated, and the average value and standard deviation of the atomic ratio Cl / Si (atomic ratio of chlorine to silicon) on the surface of abrasive grains in aqueous dispersions B to D were calculated.

[0075] For each of the aqueous dispersions A to E, use a container of the same material and rotate at 13,500 min. －１ The mixture was centrifuged, and the supernatant was removed to collect the precipitate. The precipitate was air-dried for 12 hours on filter paper of the same material to obtain dry abrasive grains, which were then stored in a container of the same material. X-ray photoelectron spectroscopy measurements were performed on these abrasive grains on the same platen under the following conditions. Measurements were taken at three different locations on the same sample, and the average and standard deviations of each atomic ratio were calculated. Apparatus: K-Alpha ＋ (Manufactured by ThermoFisher Scientific) X-ray source: Al-Kα rays (50.4W, 12kV) Measurement range: 200μmΦ Pass energy: 50eV (narrow scan) Step size: 0.100eV (narrow scan) Photoelectron extraction angle: 90° Neutralization conditions: Electron gun and Ar ＋ Gun charge correction: C1s C-C 284.8eV

[0076] The atomic ratios at each measurement point were calculated using the following procedure. The "Smart" algorithm, standard on the instrument, was used to correct the background of the spectra obtained from the measurements. This method is a correction technique based on the Shirley method, which removes background signals by considering changes in electron density between peaks. This algorithm is implemented in ThermoFisher Scientific's XPS analysis software and conforms to their technical documentation. The above algorithm was applied to Si2p, Al2p, C1s, and Cl2p narrow spectra to obtain peak areas, and the respective atomic ratios were obtained based on the elemental concentrations (unit: atom%) converted from these peak areas.

[0077] For the abrasive grains in aqueous dispersion A, the average atomic ratio Al / Si was 0.110 with a standard deviation of 0.003, and the average atomic ratio C / Si was 0.299 with a standard deviation of 0.026. For the abrasive grains in aqueous dispersion B, the average atomic ratio Al / Si was 0.124 with a standard deviation of 0.002, and the average atomic ratio Cl / Si was 0.019 with a standard deviation of 0.003. For the abrasive grains in aqueous dispersion C, the average atomic ratio Al / Si was 0.125 with a standard deviation of 0.002, and the average atomic ratio Cl / Si was 0.024 with a standard deviation of 0.003. For the abrasive grains in aqueous dispersion D, the average atomic ratio Al / Si was 0.164 with a standard deviation of 0.002, and the average atomic ratio Cl / Si was 0.037 with a standard deviation of 0.004. For the abrasive particles in aqueous dispersion E, the average atomic ratio C / Si was 0.045, and its standard deviation was 0.008.

[0078] By comparing the atomic ratio C / Si of the abrasive particles in aqueous dispersion A with that of the abrasive particles (unmodified abrasive particles) in aqueous dispersion E, the presence of an organic modification component (aluminum monohydroxydiacetate) on the surface of the silicon oxide particles in aqueous dispersion A can be confirmed. Specifically, the atomic ratio C / Si of the abrasive particles in aqueous dispersion A (average value 0.299) is significantly larger than that of the abrasive particles in aqueous dispersion E (average value 0.045), confirming the presence of an organic modification component (aluminum monohydroxydiacetate) on the surface of the silicon oxide particles in aqueous dispersion A.

[0079] <Measurement of Abrasive Grain Size> The average particle size (D50) of the abrasive grains in the above polishing slurry was measured under the following conditions. The average particle size was 95.9 nm in Example 1, 99.0 nm in Example 2, 88.5 nm in Example 3, 89.6 nm in Example 4, 64.3 nm in Example 5, and 96.5 nm in Comparative Example 1. Measurement temperature: 25°C Measurement device: Wyatt Technology Co., Ltd., product name "Mobius" Measurement method: Approximately 4 mL of polishing slurry was placed in a 1 cm square cell, and the cell was then placed in the measurement device. Measurements were performed under the conditions of laser wavelength 532 nm, measurement temperature 25°C, measurement angle 163.5°, and 100 cumulative measurements. The average particle size was obtained by calculating the D50 value of the particle size distribution from the scattering intensity converted to mass of the measurement results.

[0080] <Zeta Potential Measurement> An appropriate amount of the above-mentioned polishing slurry was placed in a product called "DelsaNano C" manufactured by Beckman Coulter, Inc., and measurements were taken twice at 25°C. The average value of the displayed zeta potential was obtained as the zeta potential. In both the example and comparative example, the zeta potential of the abrasive grains was positive.

[0081] <pH Measurement> The pH of the polishing slurry described above was measured under the following conditions. The pH was 4.5 in Example 1, 4.2 in Example 2, 4.1 in Example 3, 4.5 in Example 4, 4.2 in Example 5, and 4.7 in Comparative Example 1. Measurement temperature: 25°C Measuring device: Horiba, Ltd., product name "Model (F-73)" Measurement method: A pH meter was calibrated at three points using phthalate pH standard solution (pH: 4.01), neutral phosphate pH standard solution (pH: 6.86), and borate pH standard solution (pH: 9.18) as pH standard solutions. After that, the electrode of the pH meter was placed in the polishing slurry, and the pH was measured using the above measuring device after it had stabilized for more than 2 minutes.

[0082] <Evaluation> (Polishing speed of resin material) Three φ300 mm blanket wafers with resin films on their surfaces were prepared: a wafer with a polybenzoxazole film (PBO) on its surface, a wafer with a polyimide film (PI) on its surface, and a wafer with a polyhydroxystyrene film (PHS) on its surface. These wafers were polished using the above polishing slurry under the following polishing conditions. Polishing apparatus: F-REX300X (manufactured by Ebara Corporation) Slurry flow rate: 250 mL / min Polishing pad: Foamed polyurethane resin with closed cells (manufactured by Rohm & Haas Japan Co., Ltd., model number: IC1000) Polishing pressure: 20.7 kPa (3.0 psi) Plate rotation speed: 93 min －１ Head rotation speed: 87 min －１ Polishing time: 60 seconds. Cleaning: After polishing, the wafer was washed with water and then dried using the ROTAGONI drying method.

[0083] Using an optical interference film thickness measuring device (device name: NOVA i500) manufactured by Nova Measuring Instruments, the film thickness of the resin film on the above wafer was measured at 65 points before and after polishing. The 65 film thickness measurements were taken on a straight line including the center of the wafer, with the wafer center as the reference point, at positions of 149 mm, 148 mm, 147 mm, and 145 mm, at 5 mm intervals between 145 mm and -145 mm (140 mm, 135 mm, ..., -135 mm, -140 mm), and at -145 mm, -147 mm, -148 mm, and -149 mm (with the wafer center as the reference point, distances opposite to positive distances are indicated by negative values). The change in film thickness was calculated using the average value of the 65 film thickness measurements. The polishing speed was calculated based on the change in film thickness and the polishing time. The results are shown in Table 1.

[0084] (Observation of the surface condition of the copper plating film) Using the polishing slurry described above, a φ300 mm blanket wafer with a copper plating film on its surface was polished under the same polishing conditions as the resin material, at the same polishing speed.

[0085] Using a light curing unit (manufactured by Senner & Burns Co., Ltd., product name: 185D POWER SUPPLY, voltage: 10.0V), light was shone from an oblique direction onto the center of the polished copper plating surface, and the center of the polished surface was visually observed from the opposite side of the light curing unit. The more discolored the polished surface, the clearer the light was observed. If the polished surface was not discolored and no light was observed, it was evaluated as "A"; if the polished surface was discolored and a slight amount of light was observed, it was evaluated as "B"; if the polished surface was discolored and a sufficient amount of light was observed, it was evaluated as "C"; and if the polished surface was discolored and a clear amount of light was observed, it was evaluated as "D". The results are shown in Table 1.

[0086]

Claims

1. A polishing method comprising a polishing step of polishing a resin portion of a member to be polished, which has a resin portion containing a resin material, using a slurry, wherein the slurry contains abrasive grains having silicon oxide particles and an aluminum component present on the surface of the silicon oxide particles, and the aluminum component includes at least one selected from the group consisting of aluminum acetate, aluminum chloride and derivatives thereof.

2. The polishing method according to claim 1, wherein the aluminum component comprises at least one selected from the group consisting of aluminum acetate and its derivatives.

3. The polishing method according to claim 1, wherein the aluminum component comprises at least one selected from the group consisting of aluminum chloride and its derivatives.

4. The polishing method according to claim 1, wherein the silicon dioxide particles include colloidal silica.

5. The polishing method according to claim 1, wherein the average particle size of the abrasive grains is 20.0 to 200 nm.

6. The polishing method according to claim 1, wherein the atomic ratio of aluminum to silicon, Al / Si, obtained by X-ray photoelectron spectroscopy on the surface of the abrasive grains is 0.010 to 1.

000.

7. The polishing method according to any one of claims 1 to 6, wherein the resin material comprises polybenzoxazole.

8. The polishing method according to any one of claims 1 to 6, wherein the resin material includes polyimide.

9. The polishing method according to any one of claims 1 to 6, wherein the resin material comprises polyhydroxystyrene.

10. A slurry for polishing a resin portion of a member to be polished, the slurry comprising abrasive grains having silicon oxide particles and an aluminum component present on the surface of the silicon oxide particles, wherein the aluminum component comprises at least one selected from the group consisting of aluminum acetate, aluminum chloride and derivatives thereof.

11. The slurry according to claim 10, wherein the aluminum component comprises at least one selected from the group consisting of aluminum acetate and its derivatives.

12. The slurry according to claim 10, wherein the aluminum component comprises at least one selected from the group consisting of aluminum chloride and its derivatives.

13. The slurry according to claim 10, wherein the silicon dioxide particles include colloidal silica.

14. The slurry according to claim 10, wherein the average particle size of the abrasive grains is 20.0 to 200 nm.

15. The slurry according to claim 10, wherein the atomic ratio of aluminum to silicon, Al / Si, obtained by X-ray photoelectron spectroscopy on the surface of the abrasive grains is 0.010 to 1.

000.

16. The slurry according to any one of claims 10 to 15, wherein the resin material comprises polybenzoxazole.

17. The slurry according to any one of claims 10 to 15, wherein the resin material comprises polyimide.

18. The slurry according to any one of claims 10 to 15, wherein the resin material comprises polyhydroxystyrene.

19. Abrasive grains for polishing a resin portion of a member to be polished, which has a resin portion containing a resin material, comprising silicon oxide particles and an aluminum component present on the surface of the silicon oxide particles, wherein the aluminum component includes at least one selected from the group consisting of aluminum acetate, aluminum chloride and derivatives thereof.

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