JP2001348563A - Polishing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polishing material for an insulation film layer of a semiconductor capable of improving a polishing speed in the abrasion of an insulation film layer of a semiconductor by CMP method, at the same time, capable of reducing scratch and dust, and having excellent quality. SOLUTION: The polishing material comprises a slurry liquid prepared by dispersing a compound oxide particles of cerium and zirconium having an average particle size of secondary particles of <=5 μm in an aqueous solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a semiconductor substrate, a wiring substrate, a semiconductor device, a glass material, a hard disk, a photomask, a glass substrate such as a liquid crystal display, an optical lens, a crystal oscillator, a magnetic head, a video deck head,
The present invention relates to an abrasive for an optical fiber connector or the like. More specifically, the present invention relates to a polishing slurry for an insulating film layer of a semiconductor, comprising a slurry liquid in which composite oxide particles of cerium and zirconium are dispersed in an aqueous solution.

[0002]

2. Description of the Related Art In recent years, with the increase in the degree of integration of semiconductor devices, the minimum processing line width accompanying the increase in the number of wiring layers and the miniaturization of wiring patterns has been progressing in the direction of adopting fine line widths on the order of 0.1 μm. I am doing it.

Accordingly, in order to compensate for the lack of depth of focus of an exposure apparatus for drawing a wiring pattern, it is necessary to flatten the device surface in an intermediate step of semiconductor device manufacturing.

[0004] As a method of such flattening, an etch-back method, a reflow method, or a chemical mechanical polishing method (abbreviated as CMP method) is used.
g), etc., a technology to polish the interlayer insulating film such as silica so as to have a uniform thickness has been developed. However, since it is particularly effective for global flattening derived from the density of wiring,
The CMP method has become mainstream.

At present, in the CMP method, a technique using a slurry liquid containing silica particles and a slurry liquid containing cerium oxide particles has been industrially put to practical use.

Among them, the slurry liquid containing silica particles has the highest versatility, but the slurry liquid containing silica particles has
In order for the polishing liquid to have an etching action, it is necessary to make the polishing liquid highly alkaline, and there are problems such as an increase in impurities such as potassium and a reduction in polishing rate, depending on the strong alkaline solution used.

On the other hand, the slurry containing cerium oxide particles has a high polishing rate because of its high reactivity with silica as a material of the insulating film. However, scratches called scratches are generated on the surface of the material to be polished. In addition, there is a problem that cerium oxide particles easily remain on the surface to be polished, generating so-called dust.

[0008]

An object of the present invention is to provide a CM
An object of the present invention is to provide a high-performance semiconductor insulating film layer polishing agent which can improve the polishing rate in polishing a semiconductor insulating film layer by the P method and can reduce scratches and dust.

[0009]

Means for Solving the Problems To solve such problems, the abrasive of the present invention has the following constitution. That is, it is an abrasive made of a slurry liquid in which composite oxide particles of cerium and zirconium whose secondary particles have an average particle diameter of 5 μm or less are dispersed in an aqueous solution.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies and as a result,
Surprisingly, it has been found that the above-mentioned problems can be solved at once by a polishing agent comprising a slurry liquid in which composite oxide particles of cerium and zirconium (hereinafter simply referred to as composite oxide particles) are dispersed in an aqueous solution. Things.

The abrasive according to the present invention is used for polishing an insulating film layer in a semiconductor manufacturing process. In particular, it can be preferably applied to a method called STI (Shallow Trench Isolation) for uniformly polishing the surface of an insulating film by utilizing the difference in polishing rate between a stop film made of silicon nitride or the like and an insulating film made of silica or the like.

In the present invention, the composite oxide particles used for the abrasive are formed by oxidizing cerium oxide or ceric oxide (hereinafter collectively referred to as cerium oxide) and zirconium oxide to form a solid solution. A compound in which cerium and zirconium oxide have reacted to form a compound can be preferably used, but a simple mixture can also be used.

In the present invention, the composite oxide particles forming a solid solution can be obtained, for example, by the following method.

A water-soluble trivalent cerium compound such as cerium nitrate, cerium sulfate and cerium chloride is mixed with a water-soluble zirconium compound such as zirconium oxychloride in an aqueous solution, and the mixture is reacted by adding aqueous ammonia or the like. Then, a water-insoluble compound of cerium and zirconium is formed, and an oxidizing agent such as hydrogen peroxide is further added to perform oxidation treatment.

Next, the solution is filtered and centrifuged to collect a coprecipitate composed of composite oxide particles. Here, in order to increase the purity of the composite oxide particles, it is effective to repeatedly wash the coprecipitate with ultrapure water or the like.

Next, after drying the coprecipitate, the coprecipitate is dried in an oven for 3 hours.
By performing a heat treatment at a temperature of 00 ° C. or higher, powder of composite oxide particles is obtained.

In the present invention, the apparent density of the powder is preferably 1.5 g / cm ³ or less. 1.5g /
If it exceeds cm ³ , scratches may occur on the surface to be polished when used as an abrasive for a semiconductor insulating film layer. Here, the apparent density of the powder can be measured by an ordinary stationary method according to JIS R6126.

In the present invention, the apparent density of the powder is as follows:
At least 0.3 g / cm ³ is often sufficient for achieving the effects of the present invention.

The composite oxide particles have an average primary particle diameter of 10 to 1000 nm, preferably 50 to 5 nm.
It is preferably 00 nm. When it is less than 10 nm, the particles are too fine, and when used as a polishing agent for an insulating film layer of a semiconductor, the polishing performance may be poor.
If it exceeds 0 nm, scratches may occur on the surface to be polished. Here, the “primary particle” refers to a minimum unit of particles constituting a powder or an aggregate that can exist without breaking bonds between molecules.

The average particle diameter of the primary particles is determined by, for example, observing the obtained TEM photograph by a transmission electron microscope (TEM) for each primary particle under magnification, determining the equivalent circle diameter by image processing, and determining the equivalent circle diameter. Can be determined from the 50% diameter (median diameter) in the particle size distribution.

In the present invention, the content of cerium oxide contained in the composite oxide particles is 25 to 99.9% by weight, preferably 30 to 100% by weight based on the total composite oxide particles.
The content is preferably from 95 to 95% by weight, more preferably from 35 to 90% by weight, and still more preferably from 40 to 85% by weight. If the content is less than 25% by weight, scratches may occur on the surface to be polished when used as an abrasive for a semiconductor insulating film layer.

In the present invention, the composite oxide particles are
The content of impurities such as sodium, copper, iron, aluminum, and calcium is preferably less than 1% by weight, and preferably less than 0.5% by weight, based on 100% by weight of the total composite oxide particles. If the content of the impurities is 1% by weight or more, the impurities may remain in the semiconductor to be polished, thereby deteriorating the quality of the semiconductor. The content of the impurity can be measured by ICP emission spectroscopy.

The slurry of the present invention, that is, the slurry containing the composite oxide particles, can be obtained by dispersing the composite oxide particles obtained by the above-described method in an aqueous solution as usual. . The distribution method here is
For example, a method using an ordinary stirrer, a method using a ball mill or the like can be adopted.

For dispersion, it is preferable to add a dispersant. As the dispersant, those containing no metal ions can be preferably used. Specifically, water-soluble organic polymers such as ammonium salts of polyacrylic acid and polyvinyl alcohol; water-soluble anionic surfactants such as ammonium lauryl sulfate; and water-soluble nonionic surfactants such as polyethylene glycol monostearate. Activators and water-soluble amines such as monoethanolamine. If the dispersant is not added, particles may adhere to the surface of the material to be polished to form so-called dust, or the dispersibility of the slurry liquid may decrease. The composite oxide particles need to have an average particle diameter of secondary particles of 5 μm or less, preferably 3 μm or less, and more preferably 2 μm or less. If it exceeds 5 μm, scratches may occur on the surface to be polished when used as an abrasive for a semiconductor insulating film layer. Here, the “secondary particle” refers to a particle unit formed by aggregating the primary particles and larger than the primary particles.

In the present invention, if the secondary particle diameter of the composite oxide particles is 0.01 μm, it is often sufficient to achieve the effects of the present invention.

Here, the secondary particle size of the composite oxide particles is measured by a light scattering type particle size distribution analyzer (MICR, manufactured by Nikkiso Co., Ltd.).
OTRAC, type 7995). Here, the average particle diameter of the secondary particles of the composite oxide particles is 50 based on volume.
% Integrated diameter. In the present invention, the pH of the abrasive made of a slurry liquid in which composite oxide particles are dispersed in an aqueous solution is preferably 3 to 11, and more preferably 5 to 9. p
If H is out of the above range, the degree of acidity or alkalinity is increased, which may make drainage treatment difficult or corrode the production equipment.

[0027]

(Example 1) 2080 g of an aqueous solution of cerous chloride containing 24% by weight of ceric oxide and 2080 g of zirconium oxide so that the mixing ratio of cerium oxide and zirconium oxide becomes 50:50 in terms of weight. Was mixed and stirred with 2500 g of an aqueous solution of zirconium oxychloride having a concentration of 20% by weight to prepare a mixed aqueous solution of cerous chloride and zirconium oxychloride.

Next, 3000 g of aqueous ammonia having a concentration of 7% by weight was added to the aqueous solution and stirred to adjust the pH of the aqueous solution to 7%.
And Furthermore, 77 g of hydrogen peroxide solution was added and stirred,
A coprecipitate of cerium hydroxide and zirconium hydroxide was obtained.

The aqueous solution containing the coprecipitate was heated in an autoclave at 150 ° C. for 24 hours, and filtration and washing were repeated several times, and then dried to obtain a composite oxide powder.

This powder was fired at 1050 ° C. for 2 hours to obtain a powder of composite oxide particles having an apparent density of 0.7 g / cm ³ . The average particle size of the primary particles of the particles constituting the powder is 8
The content of cerium oxide was 49.9% by weight and the content of impurities was 0.2% by weight based on 5 nm and 100% by weight of all the composite oxide particles.

Next, 2700 g of pure water was added to 300 g of the powder of the composite oxide particles, and mixed for 24 hours by a ball mill to obtain a slurry containing the composite oxide particles.

Next, the concentration of the composite oxide particles in the slurry liquid was adjusted to 10% by weight, and an ammonium salt of polyacrylic acid as a dispersant was added to 100% by weight of the composite oxide particles contained in the slurry liquid. A slurry liquid in which composite oxide particles having a concentration of 1% by weight, a secondary particle average particle diameter of 1.2 μm, and a pH of 7.3 were dispersed in an aqueous solution, and the mixture was further diluted with pure water. A polishing agent was obtained.

Using this polishing agent, a silicon oxide film (insulating film layer) on a silicon wafer (size, type: 15 mm ×
(15 mm square) was polished with the following apparatus and conditions.

Polishing device: Wrapping machine (Musashino Electronics Co., Ltd., model number: MA-200) Polishing pad: IC1000 / SUBA400 (Rodel Nitta) Load: 200 g / cm ² Platen rotation speed: 60 rpm Work rotation Number: 60 rpm Polishing time: 5 minutes Abrasive supply amount: 24 cc / min Here, the silicon oxide film after polishing was evaluated by the following apparatus and method.

Measurement of film thickness: Film thickness meter (Lambda Ace, manufactured by Dainippon Screen Co., Ltd.) Observation of scratches and dust: Visual observation was performed with a microscope (manufactured by Keyence Corporation).

The polishing rate was determined by dividing the change in film thickness by the polishing time (5 minutes). From the above, the following results were obtained.

Polishing rate: 141 nm / min. Scratch: not recognized.

Dust: not observed. (Example 2) A polishing agent was adjusted in the same manner as in Example 1 except that the mixing ratio of cerium oxide and zirconium oxide was 80:20 in terms of weight, and a silicon oxide film was formed on a silicon wafer. Was polished and evaluated.

The composite oxide particles had an apparent powder density of 1.2 g / cm ³ and an average primary particle size of 90 n.
m, the content of cerium oxide was 79.8% by weight and the content of impurities was 0.2 with respect to 100% by weight of all composite oxide particles.
% By weight. Further, the prepared abrasive had an average particle diameter of secondary particles of the composite oxide particles of 1.5 μm, a concentration of 1% by weight, and a pH of 7.1. From the above, the following results were obtained.

Polishing rate: 101 nm / min. Scratch: not recognized.

Dust: not observed. (Example 3) A polishing agent was prepared in the same manner as in Example 1 except that the mixing ratio of cerium oxide and zirconium oxide was 99.9: 0.1 in terms of weight, and a silicon wafer was prepared. Then, the silicon oxide film was polished and evaluated.

Here, the composite oxide particles have an apparent powder density of 1.3 g / cm ³ and an average primary particle diameter of 14 g / cm ³ .
The content of cerium oxide was 99.7% by weight and the content of impurities was 0.2% by weight based on 0 nm and 100% by weight of all the composite oxide particles. Further, in the prepared abrasive, the average particle diameter of the secondary particles of the composite oxide particles was 0.8 μm, the concentration was 1% by weight, and the pH was 7.5. From the above, the following results were obtained.

Polishing rate: 130 nm / min. Scratch: not recognized.

Dust: not observed. Comparative Example 1 An abrasive was prepared, and a silicon oxide film was polished on a silicon wafer and evaluated in the same manner as in Example 1 except that cerium oxide powder obtained by pulverizing a natural mineral was used. .

The oxide particles had an apparent powder density of 1.8 g / cm ³ and an average primary particle diameter of 1500.
nm, and the impurity content was 30%. Further, in the prepared abrasive, the average particle diameter of the secondary particles of the composite oxide particles was 12 μm, the concentration was 1% by weight, and the pH was 7.4. From the above, the following results were obtained.

Polishing rate: 76 nm / min. Scratch: Many were observed.

Dust: not observed. (Comparative Example 2) An abrasive was prepared, and a silicon oxide film on a silicon wafer was polished and evaluated in the same manner as in Example 1 except that the firing temperature was 1200 ° C.

The average primary particle diameter of the composite oxide particles was 200 nm, the content of impurities was 0.5%, and the apparent density of the powder was 2.1 g / cm ³ . Further, in the prepared abrasive, the average particle diameter of the secondary particles of the composite oxide particles was 8.8 μm, the concentration was 1% by weight, and the pH was 7.5. From the above, the following results were obtained. Polishing rate: 145 nm / min Scratch: Many were observed. -Dust: not found.

[0049]

According to the present invention, since a slurry in which composite oxide particles of cerium and zirconium having an average secondary particle diameter of 5 μm or less are dispersed in an aqueous solution is used as an abrasive, the CMP method is used. In polishing the semiconductor insulating film layer by the method described above, the polishing rate is significantly improved, and at the same time, the amount of scratches and dust can be significantly reduced as compared with the conventional method.

Claims (9)

[Claims] 1. An abrasive comprising a slurry in which composite oxide particles of cerium and zirconium whose secondary particles have an average particle diameter of 5 μm or less are dispersed in an aqueous solution. 2. The abrasive according to claim 1, wherein said composite oxide particles have an apparent density of powder of 1.5 g / cm ³ or less. 3. The abrasive according to claim 1, which is used for polishing an insulating film layer in a semiconductor manufacturing process. 4. An abrasive according to claim 3, which is used for shallow trench isolation. 5. The abrasive according to claim 1, wherein the primary particles of the composite oxide particles have an average particle size of 10 to 1000 nm. 6. The method according to claim 1, wherein the content of cerium oxide contained in the composite oxide particles is 25 to 99.9% by weight based on 100% by weight of all the composite oxide particles. The abrasive according to the above. 7. The abrasive according to claim 1, wherein the content of impurities contained in the composite oxide particles is less than 1% by weight based on 100% by weight of all the composite oxide particles. . 8. The abrasive according to claim 1, wherein a dispersant is added to said slurry liquid. 9. The abrasive according to claim 1, wherein the pH is 3 to 11.