JP2003277732A - Abrasive particles and abrasives - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polishing particles having a core-shell structure which does not cause a problem due to an alkali metal. SOLUTION: The polishing particles have an average particle diameter (D) of 5 to 5.
Have a core-shell structure in the range of 300 nm, the thickness of the shell portion (S _T) is composed of silica-based composite oxide composed mainly of silica in the range of 1 to 50 nm. It is desirable to have an ion exchange point of 0.1 to 3 meq per gram of the shell part.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to abrasive particles having a core / shell structure and an abrasive material containing the abrasive particles.

[0002]

2. Description of the Related Art Conventionally, in the manufacture of a substrate with a semiconductor integrated circuit, when a circuit is formed of a metal such as copper on a silicon wafer, irregularities or steps are generated. The metal part of the circuit is preferentially removed so as to eliminate the step. Further, when aluminum wiring is formed on a silicon wafer and an oxide film such as SiO ₂ is provided as an insulating film on the silicon wiring, unevenness is generated by the wiring. Therefore, this oxide film is polished and flattened. . Chemical mechanical polishing (CMP) is well known as such a polishing method. In this method, a substrate having irregularities is pressed against a rotating polishing pad, and the substrate itself is also immersed in an abrasive slurry while rotating, so that the polishing particles contained in the slurry have irregularities due to weighting. It is pressed against the substrate, and as a result, the convex metal portion of the substrate is removed and planarized. Further, similar polishing is performed for the purpose of flattening the surface of the oxide film formed on the substrate, or for flattening the unevenness of the insulating film (oxide film) formed on the circuit. .

At this time, the polishing particles have an average particle size of 2 such as fumed alumina or fumed silica.
Spherical particles with a size of about 00 nm are used. As the polishing material, an oxidizing agent such as hydrogen peroxide for increasing the polishing rate of the metal, or benzotriazole (for suppressing the corrosion or the oxidation of the metal) depending on the type of the material to be polished is used together with such polishing particles. BTA), a chemical-based abrasive such as an acid, and a water-based abrasive slurry containing a pH adjuster are used. In polishing such a substrate, the surface after polishing is required to be flat without any steps or irregularities, and smooth without any micro scratches, and it is also necessary that the polishing rate be high. Furthermore, semiconductor materials are
Although high integration is progressing along with miniaturization and high performance of electronic products, for example, if impurities or the like remain in the transistor isolation layer, the performance may not be exhibited or a defect may occur. In particular, if Na among the alkali metals adheres to the polished semiconductor substrate or oxide film, Na has high diffusivity and is trapped by defects in the oxide film, resulting in insulation failure or short circuit even if a circuit is formed on the semiconductor substrate. In some cases, the dielectric constant was lowered. For this reason, the above-mentioned problems may occur when the use conditions and use are extended.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and polishing particles having a core-shell structure which does not cause the above-mentioned problems due to the alkali metal, and polishing containing the polishing particles. The purpose is to provide wood. Further, the present invention intends to make it possible to adjust the polishing rate, polishing accuracy, and polishing characteristics of the polishing particles and the polishing agent by providing the shell portion or changing the components, composition, thickness, and ratio of the shell portion. To do.

[0005]

Abrasive particles of the present invention SUMMARY OF THE INVENTION have a core-shell structure with an average particle diameter (D) is in the range of 5 to 300 nm, the thickness of the shell portion (S _T) is 1~50nm range It is characterized in that it is composed of the complex oxide in. The composite oxide is preferably a silica-based composite oxide containing silica as a main component. The polishing particles of the present invention have an average particle diameter (D) in the range of 5 to 300 nm,
It has a core-shell structure in which the thickness (S _T ) of the shell part is in the range of 1 to 50 nm, and 0.1 g per 1 g of the shell part.
It is characterized by having an ion exchange point of 3 meq. The core portion is made of SiO ₂ , Al ₂ O ₃ , ZrO.
It is preferable to be composed of one or more kinds of oxides selected from ₂ , SnO ₂ , ZnO, CeO ₂ , TiO ₂ , and MnO. The abrasive of the present invention comprises the above-mentioned abrasive particles.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. Abrasive Particles The abrasive particles according to the present invention are abrasive particles having a core-shell structure and have an average particle diameter (D) of 5 to 300 n.
m, preferably 10 to 200 nm. If the average particle size of the polishing particles is less than 5 nm, the stability of the polishing particle dispersion or the abrasive tends to be insufficient, and the particle size is too small to obtain a sufficient polishing rate. There is. If the average particle diameter of the polishing particles exceeds 300 nm, scratches may remain depending on the type of the substrate or the insulating film, and sufficient smoothness may not be obtained. Therefore, it is desirable to select the average particle size of the polishing particles in consideration of the required polishing rate, polishing accuracy and the like.

The shell portion of the polishing particles has a complex oxide, particularly SiO ₂ , Al ₂ O ₃ , ZrO ₂ , SnO ₂ and Zn.
It is preferably composed of two or more kinds of oxides selected from O, CeO ₂ , TiO ₂ , and MnO. As a result of the shell portion being composed of such a complex oxide, even when the shell portion has an ion exchange point and the core portion contains a large amount of alkali (particularly Na), a large amount of Na is contained in addition to the polishing particles. Even if it contains, it is trapped as Na ions in the shell,
It is less likely that Na ions will adhere to and remain on the polishing substrate. Therefore, even if a circuit is formed on the semiconductor substrate, it does not cause insulation failure or the circuit is short-circuited for a long period of time, and can be preferably used for manufacturing a semiconductor material or the like with a small decrease in dielectric constant. In addition, the above-mentioned SiO ₂ , Al
₂ O ₃ , ZrO ₂ , SnO ₂ , ZnO, CeO ₂ , Ti
It is also possible to adjust the polishing characteristics (polishing rate, smoothness of polishing surface, dishing) of the polishing particles composed of only O ₂ and MnO.

The composition of the composite oxide is such that the main component is 50 to 95.
It is preferable that the content of the components other than the main component (second component) is 5 to 50% by weight. Within this range, many ion exchange points are formed, and Na can be effectively trapped. The main component of the composite oxide is preferably silica. When the main component is silica, many ion exchange points are formed and it is easy to form a shell portion that is in close contact with the core particles. The concentration at the ion exchange point is 0.1 to 3 meq, especially 0.5 to 5 g, per 1 g of the shell part.
It is preferably in the range of 3 meq. If the concentration at the ion exchange point is less than 0.1 meq, Na may not be sufficiently trapped. On the other hand, it is difficult to form a shell portion exceeding 3 meq, and even if it can be formed, it cannot serve as abrasive particles.

The thickness (S _T ) of the shell portion of the polishing particles is 1
It is in the range of -50 nm, preferably 1-20 nm. When the thickness (S _T ) of the shell portion is less than 1 nm, it is difficult to obtain the effect of providing the shell portion. That is, when there are many alkali metals in the core part or when there is an alkali other than the polishing particles, this alkali is trapped in the shell part to prevent the alkali from remaining on the polishing substrate, or by providing the shell part. Alternatively, it is difficult to obtain the effect of adjusting the polishing characteristics by changing the components of the shell portion. On the other hand, when the thickness (S _T ) of the shell portion exceeds 50 nm, the effects of suppressing the diffusion of the alkali metal outside the particles and adjusting the polishing rate are not further improved, and the particle diameter of the core portion is However, there is no difference from making abrasive particles substantially consisting of a shell portion, and the economical efficiency may be reduced. Such shell thickness (S _T ) and average particle diameter (D) of the polishing particles
The ratio of the (S _T) / (D) is generally preferably in the range of 1 / 2-1 / 20.

Further, the content of Na in the shell portion is not particularly limited as long as it can trap alkali, and varies depending on the proportion of the shell portion in the particles and the kind and the composite proportion of the complex oxide in the shell portion. 5000p as Na
pm or less, preferably 1000 ppm or less, particularly preferably 100 ppm or less. Na content is 5000p
When it exceeds pm, the strength and amount of trapping Na decrease, Na remains on the polished substrate, and this Na may cause insulation failure of the circuit formed on the semiconductor substrate or short-circuit the circuit. The dielectric constant of a film provided for insulation (insulating film) may decrease, the impedance of the metal wiring may increase, and the response speed may be delayed and power consumption may increase. In addition, Na ions move (diffuse), and the above-mentioned problem may occur when the use conditions and use are extended for a long period of time.

Core Particles The core portion of the polishing particles has SiO ₂ , Al ₂ O ₃ and Zr.
O ₂ , SnO ₂ , ZnO, CeO ₂ , TiO ₂ , MnO
It is preferable to use one kind or two or more kinds of oxides selected from the following, which can be appropriately selected and used depending on the kind of the substrate to be polished, the required polishing rate, the polishing accuracy and the like. In addition, in the present invention, the Na content of the core portion does not need to be 100 ppm or less. This is because the shell portion has the ability to trap alkali ions. The core portion is preferably spherical particles, and the average particle diameter of the core particles is preferably in the range of 4 to 250 nm.

The polishing particles of the present invention can be used by dispersing them in water and / or an organic solvent. As the organic solvent, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol are preferable, and water-soluble organic solvents such as ethers, esters and ketones can be used. At this time, the concentration of the polishing particle dispersion is preferably in the range of approximately 5 to 50% by weight as a solid content. If the concentration of the dispersion liquid is less than 5% by weight, the concentration of the polishing particles in the abrasive obtained by blending may be too low, and a sufficient polishing rate may not be obtained. If it exceeds 5% by weight, the stability of the dispersion tends to decrease, and a dried product may be formed and adhered in the step of supplying the dispersion for polishing treatment, causing scratches. There is.

Manufacturing Method of Polishing Particles Next, a manufacturing method of the above-mentioned polishing particles will be described. First, the dispersion liquid of the core particles described above is prepared. At this time, the concentration of the core particle dispersion liquid is 0.005 as an oxide.
It is preferably in the range of ˜20% by weight, more preferably 0.01 to 10% by weight. When the concentration of the core particles is less than 0.005% by weight, the productivity is low, and when the concentration of the core particles exceeds 20% by weight, the density of the shell portion depends on the addition rate of the shell portion forming component described later. It tends to be low and inferior in polishing ability, and the resulting polishing particles may aggregate. In the core particle dispersion liquid, SiO ₂ , Al ₂ O ₃ , ZrO
₂ , two or more aqueous solutions of compounds capable of forming two or more complex oxides selected from SnO ₂ , ZnO, CeO ₂ , TiO ₂ and MnO are added simultaneously, alternately or continuously or intermittently. However, it is preferable to add them at the same time. In addition, it is preferable that the addition speed is such that it is added over a period of time within the range in which new particles other than fine gel and core particles are not generated.

As the compound capable of forming the complex oxide, alkali metal silicate, sodium aluminate, sodium aluminosilicate, aluminum chloride, zirconium nitrate, stannous chloride, stannic chloride, zinc chloride, cerium nitrate, In addition to cerium ammonium nitrate, titanium tetrachloride, manganese sulfate, etc., an acidic silicic acid solution obtained by dealkalizing an alkali metal silicate can be preferably used as a silica source. The mixing ratio of each component at this time is such that the composition of the obtained shell is in the range of 50 to 95% by weight as the main component of the oxide and 5 to 50% by weight of the components other than the main component. The mixing ratio capable of increasing the ion exchange point for trapping Na is generally in the range of 60 to 80% by weight of the main component oxide. Furthermore, if necessary, an acid or a base is added to the oxide precursor (hydroxide, complex hydroxide).
The pH of the dispersion liquid can be adjusted in order to control the precipitation rate and complexation of the above on the core particle surface.

Examples of the acidic silicic acid solution as the silica source include (1) the acidic silicic acid solution obtained by dealkalizing an aqueous solution of an alkali metal silicate with an ion exchange resin or the like,
(2) An acidic silicic acid solution obtained by hydrolyzing an organosilicon compound with an acid such as hydrochloric acid, nitric acid or sulfuric acid, (3) an aqueous solution obtained by adding an organosilicon compound to an aqueous solution of an alkali metal hydroxide and / or an aqueous solution of an organic base. A conventionally known acidic silicic acid solution obtained by dealkalizing or deorganizing base with an ion exchange resin or the like can be used. As the alkali of the alkali metal silicate aqueous solution or alkali metal hydroxide aqueous solution, an alkali other than Na is particularly preferable, and in this case, since Na is not substantially present in the obtained acidic silicic acid solution,
It is possible to obtain polishing particles that do not substantially contain Na in the shell portion.

As the above-mentioned organic silicon compound, an organic silicon compound represented by the following chemical formula and a mixture thereof can be used. However, in the formula, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group, R ² represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 2 to 2 carbon atoms. 5 represents an acyl group, and n is an integer of 0 or 1. R ¹ _n Si (OR ² ) _{4-n In the} above chemical formula, since the organosilicon compound with n = 0 does not wait for a hydrocarbon group directly bonded to silicon, the resulting shell has a high density and was used for polishing. In this case, a high polishing rate can be obtained. Specifically, tetraethoxysilane (T
Examples thereof include tetrafunctional organosilicon compounds such as EOS), tetramethoxysilane (TMOS), tetrapropoxysilane (TPOS), and tetrabutoxysilane (TBOS).

As the alkali metal hydroxide aqueous solution, Li
OH, NaOH, KOH, RbOH, CsOH and a mixture thereof can be used, but an aqueous KOH solution is usually preferably used. Further, as the organic base aqueous solution, quaternary ammonium hydroxide is preferable,
Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and the like are preferable.

The amount of the organosilicon compound added to the aqueous alkali metal hydroxide solution and / or the aqueous organic base solution is in the range of 1 to 10% by weight, and further 2 to 7% by weight in terms of the concentration in the aqueous solution calculated as SiO _2. Is preferred. When the added amount is less than 1% by weight calculated as SiO ₂ , hydrolysis with time causes oligomerization of silicic acid, etc., and the ratio of silicic acid monomer in the acidic silicic acid solution obtained by decationization in the subsequent step is high. A low silicic acid solution with a high proportion of silicic acid oligomer may be obtained. The shell of the composite oxide obtained by using such an acidic silicic acid solution has a low density, and when used for polishing, the polishing rate may decrease. If the addition amount exceeds 10% by weight in terms of SiO ₂ , the viscosity of the obtained aqueous solution of alkali metal silicate and / or aqueous solution of organic base silicic acid is high, and alkali cations and / or alkali cations due to an ion exchange resin or the like are obtained in the subsequent step. The removal of organic cations becomes difficult, and the resulting acidic silicic acid solution may have low stability and gel. The concentration of such an acidic silicic acid solution is in the range of 1 to 10% by weight, and further 2 to 7% by weight in terms of SiO ₂ . The pH of the silicic acid solution is preferably in the range of 1-3.5, and more preferably 2-3. In particular, when the pH of the silicic acid solution is in the range of 2 to 3, there are few residual cations in the acidic silicic acid solution and the stability is excellent.

The temperature of the core particle dispersion liquid is 50 to 200.
While maintaining the temperature at 60 ° C., preferably 60 to 150 ° C., an aqueous solution of a compound capable of forming the complex oxide is continuously or intermittently added thereto to form a shell. The addition rate of each component varies depending on the average particle size of the core particles and the concentration in the dispersion liquid, and can be changed approximately in proportion to the total external surface area of the core particles. That is, if the total external surface area is high, it can be added quickly, and if the total external surface area is low, the addition rate of each component is too fast, and a fine gel or new particles other than the core particles are generated or obtained. Abrasive particles may aggregate.

The addition of each component can be performed once or repeatedly until a shell having a desired thickness is formed. After adding each component to the core particle dispersion liquid, if necessary, in a temperature range of 70 to 150 ° C. for 0.5 to 5
It can be aged for 5 hours. By performing such aging, the density of the shell portion of the obtained particles can be increased and a dense shell portion can be formed. Further, if necessary, ions can be removed using an ultrafiltration membrane or the like, or further concentrated or diluted to a desired concentration to obtain a dispersion liquid of polishing particles. Further, it is also possible to obtain a dispersion liquid of polishing particles in which an aqueous solvent is replaced with an organic solvent described later by an ultrafiltration membrane method, a distillation method or the like.

Abrasive Material The abrasive material of the present invention comprises the above-mentioned abrasive particles. In addition to using the above-mentioned polishing particles as the polishing particles, it may be in the form of a dispersion liquid in which the polishing particles are dispersed, if necessary. Water is generally used as the dispersion medium, but if necessary, methyl alcohol, ethyl alcohol, or an organic solvent may be used as the organic solvent.
Alcohols such as isopropyl alcohol can be used, and in addition, water-soluble organic solvents such as ethers, esters, and ketones can be used. The concentration of the polishing particles in the abrasive is preferably 5 to 50% by weight, more preferably 5 to 30% by weight. The concentration of polishing particles is 5
When the content is less than 50% by weight, the concentration may be too low depending on the type of the base material or the insulating film and the polishing rate may be slow, resulting in a problem of productivity. If the concentration of the polishing particles exceeds 50% by weight, the polishing agent The stability becomes insufficient, the polishing rate and the polishing efficiency are not further improved, and the dried product may be generated and adhered in the step of supplying the dispersion liquid for the polishing treatment, which may cause scratches (scratches). It may be a cause.

Depending on the type of substrate to be polished, conventionally known hydrogen peroxide, peracetic acid, urea peroxide, etc., and a mixture thereof may be added to the abrasive material of the present invention. You can When such a hydrogen peroxide or the like is added and used, the polishing accuracy can be effectively improved when the substrate to be polished is a metal. Furthermore, an organic acid such as phthalic acid or citric acid or an organic acid salt thereof can be added and used as a complexing agent. Further, benzotriazole (BTA) or the like can be used to suppress oxidation. Furthermore, an acid or a base may be used to adjust the pH of the abrasive, or a surfactant or the like may be added to enhance the dispersibility and stability of the abrasive.

[0023]

The polishing particles of the present invention have a core-shell structure, and even if the core contains a large amount of alkali metal, the alkali metal can be trapped by ion exchange in the shell. Therefore, it is possible to obtain an abrasive free from the above-mentioned various problems caused by the contained alkali metal. Further, in the present invention, by providing the shell portion or by changing the components, composition and thickness of the shell portion, the polishing speed and polishing accuracy of the polishing particles composed of the core particles alone (smoothness of polishing surface and degree of scratch). It also makes it possible to adjust polishing characteristics such as dishing.

[0024]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Preparation of Polishing Particle (A) Dispersion Silica sol (manufactured by Catalysts & Chemicals Industry Co., Ltd .: SI-50, average particle diameter 25 nm, SiO ₂ concentration 48 wt%, Na content 0.37) SiO ₂ concentration of 5% by weight obtained by diluting
100 g of the core particle dispersion liquid of is heated to 83 ° C.
The pH of the dispersion was adjusted to 10.5 with a KOH aqueous solution of wt%. Then, 1530 g of sodium silicate aqueous solution (SiO ₂ concentration: 1.5% by weight, Na ₂ O concentration: 0.5% by weight)
And an aqueous solution of sodium aluminate (Al ₂ O ₃ concentration of 0.
5% by weight, Na ₂ O concentration 0.386% by weight) 1300 g
And were added simultaneously for 17 hours to form a shell, and after aging for 1 hour, washed with an ultrafiltration membrane until the pH of the dispersion became 7 while adding hydrochloric acid, and then concentrated while heating, A silica / alumina-coated silica particle dispersion having a SiO ₂ · Al ₂ O ₃ concentration of 20% by weight was prepared. Then, the silica / alumina-coated silica particle dispersion is ion-exchanged with an ion-exchange resin to obtain a SiO ₂ · Al ₂ O ₃ concentration of 20% by weight.
A dispersion of abrasive particles (A) was prepared. The average particle size of the obtained polishing particles (A) was measured, and N in the particles was measured.
a was analyzed. The Na content of the shell part was calculated from the Na content of the core particles and the obtained silica particles. Table 1 shows the components and properties of the core part and the compositions and properties of the shell part.

Preparation of Abrasive Material (A) Abrasive particles (A) having a SiO ₂ concentration of 20% by weight obtained above.
An aqueous NH ₄ OH solution having a concentration of 15% by weight was added to the dispersion to adjust the pH of the dispersion to 10.5 to prepare an abrasive (A). Polishing Using a silicon wafer (for polishing test: 30 mm □) having a thermal oxide film formed as a substrate to be polished, it is set in a polishing apparatus (Nano Factor Co., Ltd .: NF300), substrate load is 0.12 MPa, and table rotation speed is 30 rpm. Then, the abrasive (A) was supplied at a rate of 1 ml / sec for 30 seconds for polishing. The thickness before and after polishing was calculated to calculate the polishing rate, and the smoothness of the substrate before and after polishing was evaluated. The results are shown in Table 2.
The smoothness is evaluated by observing the surface after polishing with an optical microscope,
The evaluation was performed according to the following evaluation criteria. ◯: Almost no scratches and streaks before polishing, and the surface is smooth. Δ: The number of scratches and streaks before polishing is reduced to less than half, and the surface is smooth. X: Scratches and streaks before polishing are slightly reduced, but the surface is rough.

Example 2 Preparation of Abrasive Particle (B) Dispersion Liquid and Abrasive Material (B) In Example 1, an aqueous solution of sodium aluminate (Al
₂ O ₃ concentration 0.5 wt%, Na ₂ O concentration 0.386 wt%) instead of 1300 g, aqueous sodium aluminate (Al ₂ O ₃ concentration 0.2 wt%, Na ₂ O concentration 0.1
55% by weight) Si was similarly used except that 1500 g was used.
A dispersion liquid of polishing particles (B) having an O ₂ · Al ₂ O ₃ concentration of 20% by weight was prepared. An abrasive (B) was prepared in the same manner as in Example 1 except that the abrasive particle (B) dispersion was used, and a polishing test was conducted.

Example 3 Preparation of Abrasive Particle (C) Dispersion and Abrasive (C) In Example 1, an aqueous solution of sodium aluminate (Al
₂ O ₃ concentration 0.5 wt%, except for using concentration of Na ₂ O 0.386 wt%) ₂ concentration of 0.5 wt% ammonium zirconyl carbonate solution (ZrO instead of 1300 g) 1300 g In the same manner, SiO ₂ A dispersion of abrasive particles (C) having a ZrO ₂ concentration of 20% by weight was prepared. An abrasive (C) was prepared and a polishing test was conducted in the same manner as in Example 1 except that the polishing particle (C) dispersion was used.

Example 4 Preparation of Abrasive Particle (D) Dispersion Liquid and Abrasive Material (D) Silica sol (manufactured by Catalysts & Chemicals Industry Co., Ltd .: Cataloid SI-45P, average particle size ) was used to prepare a core particle dispersion liquid. 45n
m, SiO ₂ concentration 40% by weight, Na content 0.30% by weight) in the same manner as in Example 1 except that SiO ₂
A dispersion of polishing particles (D) having an Al ₂ O ₃ concentration of 20% by weight was prepared. An abrasive (D) was prepared and a polishing test was conducted in the same manner as in Example 1 except that the abrasive particle (D) dispersion was used.

Example 5 Preparation of Abrasive Particle (E) Dispersion Liquid and Abrasive Material (E) Ethyl Orthosilicate (manufactured by Tama Chemical Co., Ltd .: Na content 0.01)
(ppm) is dissolved in KOH and potassium silicate aqueous solution (Si
O ₂ concentration 21% by weight, SiO ₂ / K ₂ O molar ratio = 3.
5) was obtained. Then, diluted water glass (SiO ₂ concentration 5% by weight) obtained by diluting this was dealkalized with an ion exchange resin to prepare 850 g of an acidic silicic acid solution (pH 2.2, SiO ₂ concentration 3% by weight). Silica sol (Catalyst Kasei Kogyo KK: Cataloid SI-45P, average particle size 45n)
m, SiO ₂ concentration 40% by weight, Na content 0.30% by weight) to obtain 500 g of a core particle dispersion liquid having a SiO ₂ concentration of 5% by weight, which was heated to 83 ° C. to obtain KO having a concentration of 20% by weight.
The pH of the dispersion was adjusted to 10.5 with an H aqueous solution. Then, 850 g of the acidic silicic acid solution obtained above and an aqueous solution of sodium silicate (SiO ₂ concentration 1.5% by weight, Na ₂ O concentration 0.5)
% By weight), and an aqueous solution of sodium aluminate (Al ₂ O ₃ concentration of 0.5% by weight, Na ₂ O concentration of 0.38).
(6% by weight) and 6800 g are added simultaneously in 34 hours to form a shell, which is then aged for 1 hour and then washed with an ultrafiltration membrane until the pH of the dispersion reaches 10, and the alcohol is distilled off while heating. It was removed and concentrated to prepare a silica / alumina-coated silica particle dispersion having a SiO ₂ · Al ₂ O ₃ concentration of 20% by weight. Then, the silica / alumina-coated silica particle dispersion is ion-exchanged with an ion-exchange resin to form SiO ₂
An abrasive particle (E) dispersion having an Al ₂ O ₃ concentration of 20% by weight was prepared. An abrasive (E) was prepared and a polishing test was performed in the same manner as in Example 1 except that the abrasive particle (E) dispersion was used.

[Embodiment 6]Preparation of abrasive particle (F) dispersion and abrasive (F) As the core particle dispersion liquid, titania sol sol (catalyst chemical conversion
Industry Co., Ltd .: Neo Sunveil PW-1010, average particle
Diameter 10 nm, TiO₂Concentration 10% by weight, Na content 0.
Was used in the same manner as in Example 1 except that
iO₂・ SiO ₂・ Al₂O₃Silica with a concentration of 20% by weight
-Abrasive particles (F) consisting of alumina-coated titania particles
A dispersion was prepared. After using the abrasive particle (F) dispersion
Otherwise, the abrasive (F) was prepared in the same manner as in Example 1, and the polishing was performed.
The test was conducted.

[Embodiment 7]Preparation of abrasive particle (G) dispersion and abrasive (G) Zirconium isopropylate (Matsumoto Trading Co., Ltd.)
Product: Organix ZA-50, ZrO₂Concentration 37.
7% by weight) diluted with ethyl alcohol to prepare ZrO ₂concentration
3 wt% zirconium isopropylate solution 5000
g was prepared. 1% by weight NaOH aqueous solution 2
00 g was added over 5 hours and aged for 1 hour. Ultrafiltration membrane
Wash until the pH of the zirconia particle dispersion becomes 9 at
Then, the alcohol is distilled off while heating and concentrated to obtain ZrO.
₂A zirconia particle dispersion liquid having a concentration of 20% by weight was prepared.
The above zirconia particle dispersion liquid was added to ZrO.₂Rarely 5% by weight
Example except that this was used as the core particle dispersion liquid
ZrO as in 1₂・ SiO₂・ Al₂O ₃Concentration 2
A 0% by weight polishing particle (G) dispersion was prepared. For polishing
In the same manner as in Example 1 except that the particle (G) dispersion was used.
An abrasive (G) was prepared and a polishing test was conducted.

Example 8 Preparation of Abrasive Particle (H) Dispersion and Abrasive (H) Diethoxyzinc (Diethoxyzinc manufactured by KANTO Co., Ltd.,
ZnO concentration 52% by weight) was diluted with ethyl alcohol to prepare 5000 g of diethoxyzinc solution having ZnO concentration 3% by weight. 150 wt% of 1 wt% NaOH aqueous solution
g was added over 4 hours and aged for 1 hour. The zinc oxide particle dispersion was washed with an ultrafiltration membrane until the pH became 9, and the alcohol was distilled off while heating to concentrate the ZnO concentration to 20.
A wt% zinc oxide particle dispersion was prepared. Z was prepared in the same manner as in Example 1 except that the zinc oxide particle dispersion was diluted to a ZnO concentration of 5% by weight and used as the core particle dispersion.
A dispersion liquid for polishing particles (H) having a concentration of 20% by weight of nO.SiO ₂ .Al ₂ O ₃ was prepared. An abrasive (H) was prepared and a polishing test was conducted in the same manner as in Example 1 except that the abrasive particle (H) dispersion was used.

Comparative Example 1 Preparation of Abrasive Material (I) Silica sol (manufactured by Catalysts & Chemicals Industry Co., Ltd .: SI-50, average particle diameter 25 nm, SiO ₂ concentration 48% by weight, Na content 0.37% by weight) Was diluted to a SiO ₂ concentration of 20% by weight, and an aqueous NH ₄ OH solution having a concentration of 15% by weight was added to adjust the pH of the dispersion to 10.5 to prepare an abrasive (I). A polishing test was conducted in the same manner as 1.

Comparative Example 2 Preparation of Abrasive Material (J) Silica sol (Catalyst Chemical Industry Co., Ltd .: Cataloid SI-
45P, average particle diameter 45 nm, SiO ₂ concentration 40% by weight, Na content 0.30% by weight) to a SiO ₂ concentration of 20% by weight, and NH ₄ OH with a concentration of 15% by weight.
An aqueous solution was added to adjust the pH of the dispersion liquid to 10.5 to prepare an abrasive (J), and a polishing test was conducted in the same manner as in Example 1.

Comparative Example 3 Preparation of Abrasive (K) Titania sol sol (manufactured by Catalysts & Chemicals Industry Co., Ltd .: Neo Sunveer PW-1010, average particle size 10 nm, TiO ₂ concentration 10% by weight, Na content 0.01). % By weight)
The pH of the dispersion was adjusted to 1 by adding an aqueous solution of NH ₄ OH (wt%).
An abrasive (K) was prepared by adjusting the amount to 0.5, and a polishing test was conducted in the same manner as in Example 1.

Comparative Example 4 Preparation of Abrasive Material (L) To the zirconia particle dispersion liquid having a ZrO ₂ concentration of 20 wt% prepared in Example 7, an aqueous NH ₄ OH solution having a concentration of 15 wt% was added to adjust the pH of the dispersion liquid. Adjusted to 10.5 and abrasive (L)
Was prepared and a polishing test was conducted in the same manner as in Example 1.

Comparative Example 5 Preparation of Abrasive Material (M) To the zinc oxide particle dispersion liquid having a ZnO concentration of 20 wt% prepared in Example 8, an aqueous NH ₄ OH solution having a concentration of 15 wt% was added, and the pH of the dispersion liquid was adjusted. Was adjusted to 10.5 to prepare an abrasive (M), and a polishing test was conducted in the same manner as in Example 1.

[0039]

TABLE 1 Core unit shell portion particulate component average Na-containing core assembly formed thick Na including average grain size Yuryou ratio main component (wt%) Yuryou particle diameter (nm) (ppm) (wt %) subcomponent (wt%) (nm) (ppm) (nm) Example 1 SiO ₂ 25 3700 14.5 SiO ₂ 77.9 10 2300 45 Al ₂ O ₃ 22.1 Example 2 SiO ₂ 25 3700 16.1 SiO ₂ 88.2 9.5 1500 44 Al ₂ O ₃ 11.8 Example 3 SiO ₂ 25 3700 14.5 SiO ₂ 77.9 10 750 45 ZrO ₂ 22.1 Example 4 SiO ₂ 45 3000 14.5 SiO ₂ 77.9 17.5 2400 80 Al ₂ O ₃ 22.1 Example 5 SiO ₂ 45 3000 17.3 SiO ₂ 77.9 16.5 800 78 Al ₂ O ₃ 22.1 Example 6 TiO ₂ 10 100 14.5 SiO ₂ 77.9 7.5 1250 25 Al ₂ O ₃ 22.1 Example 7 ZrO ₂ 10 200 14.5 SiO ₂ 77.9 7.0 1100 24 Al ₂ O ₃ 22.1 Example 8 ZnO 10 150 14.5 SiO ₂ 77.9 10 1300 30 Al ₂ O ₃ 22.1 Comparative Example 1 SiO ₂ 25 3700 100 − − − − 25 − − Comparative Example 2 SiO ₂ 45 3000 100 − − − − 45 − − Comparative Example 3 TiO ₂ 10 100 100 − − − − 10 − − Comparative Example 4 ZrO ₂ 10 200 100 − − − − 10 − − Comparative Example 5 ZnO 10 150 100 − − − − 10

− −

[Table 2]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshiro Komatsu             13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu, Fukuoka             Kasei Industry Co., Ltd. Wakamatsu factory F term (reference) 3C058 AA07 CA01 CB02 DA02 DA12                 3C063 AA01 AB01 BB01 BB03 BB14                       CC01 EE10 EE26 FF23

Claims (5)

[Claims] 1. A core-shell structure having an average particle diameter (D) in the range of 5 to 300 nm and a thickness (S) of the shell portion.
Abrasive particles, characterized in that _T ) is composed of a composite oxide having a range of 1 to 50 nm. 2. The polishing particle according to claim 1, wherein the composite oxide is a silica-based composite oxide containing silica as a main component. 3. A core-shell structure having an average particle diameter (D) in the range of 5 to 300 nm and a shell portion thickness (S _T ) in the range of 1 to 50 nm. Abrasive particles having an ion exchange point of 0.1 to 3 meq. 4. The core portion is made of SiO ₂ , Al ₂ O ₃ , Z
rO ₂ , SnO ₂ , ZnO, CeO ₂ , TiO ₂ , Mn
The polishing particle according to any one of claims 1 to 3, comprising one kind or two or more kinds of oxides selected from O. 5. An abrasive containing the abrasive particles according to claim 1. Description: