JPH10106992A - Cerium oxide abrasive agent and polishing method of substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To evenly polish the surface of an SiO2 insulating film or the like by a method where cerium compound hydrate is burned at a specific temperature as air and/or oxygen gas is introduced at a specific temperature and linear velocity, and the cerium oxide particle obtained by burning is dispersed into dispersion medium for the formation of slurry. SOLUTION: Cerium compound hydrate is burned at temperatures of 400-900 deg.C as air and/or oxygen gas is introduced at a linear velocity of 1cm/min or above, keeping an atmosphere around cerium oxide particle uniform, so as to obtain homogeneous cerium oxide particle. The obtained cerium oxide powder is dispersed into a dispersion composition (medium) composed of water and dispersing agent, as required, so as to obtain slurry. An SiO2 insulating layer is polished with cerium oxide abrasive agent (slurry), then its rough surface is made flat throughout all the surface of the semiconductor substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention provides a cerium oxide abrasive and a method for polishing a substrate.

[0002]

2. Description of the Related Art Conventionally, in the manufacturing process of a semiconductor device,
Colloidal silica-based polishing agents are generally studied as chemical mechanical polishing agents for planarizing an inorganic insulating film layer such as a SiO ₂ insulating film formed by a method such as plasma-CVD or low-pressure-CVD. Colloidal silica-based abrasives are produced by growing silica particles by a method such as thermal decomposition of silicic acid tetrachloride and adjusting the pH with an alkali solution containing no alkali metal such as ammonia. However, such a polishing agent does not have a sufficient polishing rate for the inorganic insulating film, and there is a technical problem of a low polishing rate for practical use.

On the other hand, cerium oxide abrasives have been used for polishing the glass surface for photomasks. Cerium oxide particles have lower hardness than silica particles and alumina particles,
Therefore, it is useful for finish mirror polishing because the polishing surface is hardly damaged. Also, cerium oxide has chemically active properties as known as strong oxidizing agents.
Taking advantage of this advantage, application to a chemical mechanical polishing agent for an insulating film is useful. However, if the cerium oxide abrasive for polishing the glass surface for a photomask is applied as it is to the polishing of the inorganic insulating film, the surface of the insulating film will have polishing scratches that can be visually observed.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cerium oxide abrasive which can polish a surface to be polished such as a SiO ₂ insulating film and the like, and a method for polishing a substrate.

[0005]

The cerium oxide abrasive of the present invention is characterized in that a cerium compound hydrate is heated at 400 ° C. to 900 ° C.
A slurry containing cerium oxide particles obtained by introducing air and / or oxygen gas having a linear velocity of 1 cm / min or more and firing the same and dispersing the particles in a medium is described below.

The method of polishing a substrate according to the present invention is characterized in that a predetermined substrate is polished with the above-mentioned cerium oxide abrasive.

When the cerium compound hydrate was subjected to thermal analysis, the water of crystallization sublimated at 100 ° C. and an oxidation reaction occurred at 300 ° C. Therefore, the atmosphere in the vicinity of the particles during the elimination of the water of crystallization or the oxidation reaction tends to change depending on the way of filling the powder. For example, in the filled central portion, water vapor or carbon dioxide gas released by desorption or oxidation reaction of crystallization water hardly escapes to the outside. On the other hand, it is easy to come off on the outside of the filling. Therefore, the present invention provides cerium carbonate hydrate at 400 ° C. or more and 900 ° C.
By introducing and sintering a sufficient amount of air and / or oxygen gas at a temperature of not more than 1 ° C. and a linear velocity of 1 cm / min or more, the atmosphere around the particles is made uniform to produce uniform cerium oxide particles. It has been found that the use of cerium oxide particles having a uniform particle diameter can improve the flatness after polishing.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Generally, cerium oxide is a carbonate,
It is obtained by calcining cerium compounds such as sulfates and oxalates. Si formed by a TEOS-CVD method or the like
The O ₂ insulating film can be polished at a high speed as the primary particle diameter is large and the crystal distortion is small, that is, as the crystallinity is good. Therefore, the cerium oxide particles used in the present invention are produced without increasing crystallinity. Further, since it is used for polishing semiconductor chips, the content of alkali metals and halogens is 1 ppm.
It is preferable to suppress it to the following.

In the present invention, a firing method can be used as a method for producing cerium oxide particles. Since the oxidation temperature of the cerium compound is 300 ° C., the firing temperature is 600
Perform at or above ° C.

[0010] The cerium oxide slurry in the present invention comprises:
It is obtained by dispersing an aqueous solution containing cerium oxide particles produced by the above method or a composition comprising cerium oxide particles recovered from this aqueous solution, water and, if necessary, a dispersant. Here, there is no limitation on the concentration of the cerium oxide particles, but the concentration of the cerium oxide particles is set at 0.
A range of 5 to 10% by weight is preferred. As the dispersant, those containing no metal ions include acrylic acid polymers and their ammonium salts, methacrylic acid polymers and their ammonium salts, water-soluble organic polymers such as polyvinyl alcohol, ammonium lauryl sulfate, and polyoxyethylene. Water-soluble anionic surfactants such as ammonium lauryl ether sulfate, polyoxyethylene lauryl ether, water-soluble nonionic surfactants such as polyethylene glycol monostearate, monoethanolamine,
And water-soluble amines such as diethanolamine. The addition amount of these dispersants is preferably in the range of 0.01 part by weight to 5 parts by weight based on 100 parts by weight of the cerium oxide particles in view of the dispersibility and anti-settling properties of the particles in the slurry, and enhances the dispersing effect For this purpose, it is preferable that the particles are simultaneously placed in the disperser during the dispersion treatment.

As a method for dispersing these cerium oxide particles in water, a homogenizer, an ultrasonic disperser, a ball mill, or the like can be used in addition to the usual dispersion treatment using a stirrer. In particular, in order to disperse cerium oxide particles as fine particles of 1 μm or less, it is preferable to use a wet disperser such as a ball mill, a vibrating ball mill, a planetary ball mill, and a medium stirring mill. When it is desired to increase the alkalinity of the slurry, an alkaline substance not containing metal ions, such as aqueous ammonia, can be added during or after the dispersion treatment.

In the cerium oxide abrasive of the present invention, the above slurry may be used as it is, but N, N-diethylethanolamine, N, N-dimethylethanolamine,
Additives such as aminoethylethanolamine can be added to make an abrasive.

As a method for forming an inorganic insulating film using the cerium oxide abrasive of the present invention, there are a constant pressure CVD method, a plasma CVD method and the like. SiO ₂ by constant pressure CVD
In forming the insulating film, monosilane: SiH _{4 is} used as a Si source, and oxygen: O ₂ is used as an oxygen source. This is obtained by performing the SiH ₄ —O ₂ -based oxidation reaction at a low temperature of about 400 ° C. or less. When doping phosphorus: P for planarizing the surface by high temperature reflow, SiH ₄ —O ₂ —PH ₃
It is preferable to use a system reaction gas. The plasma CVD method has an advantage that a chemical reaction requiring a high temperature can be performed at a low temperature under normal thermal equilibrium. The plasma generation method includes two types, a capacitive coupling type and an inductive coupling type. As a reaction gas, a SiH ₄ —N ₂ O-based gas using SiH ₄ as a Si source and N ₂ O as an oxygen source, and tetraethoxysilane (TEO)
S) as a Si source using a TEOS-O ₂ based gas (TEOS
-Plasma CVD method). Substrate temperature is 250
The reaction pressure is preferably in the range of 67 to 400 Pa. As described above, the elements such as phosphorus and boron may be doped in the SiO ₂ insulating film of the present invention.

A semiconductor substrate at a stage where circuit elements and wiring patterns are formed,
A substrate in which a SiO ₂ insulating film layer is formed on a semiconductor substrate such as a semiconductor substrate at a stage where circuit elements are formed can be used.
By polishing the SiO ₂ insulating film layer formed on such a semiconductor substrate with the cerium oxide polishing agent,
The unevenness on the surface of the iO ₂ insulating film layer is eliminated, and a smooth surface is formed over the entire surface of the semiconductor substrate. Here, as a polishing apparatus, a holder for holding a semiconductor substrate and a polishing cloth (pad) are used.
A general polishing apparatus having a surface plate on which is attached (a motor or the like whose rotation speed can be changed) is attached can be used.
As a polishing cloth, general nonwoven fabric, foamed polyurethane,
A porous fluororesin or the like can be used, and there is no particular limitation. Further, it is preferable that the polishing cloth is subjected to a groove processing for storing the slurry. Although there is no limitation on the polishing conditions, the rotational speed of the platen 100rpm or lower rotational preferably so that no semiconductor protrude, pressure applied to the semiconductor substrate is a 1 kg / cm ² or less as scratches is not generated after polishing preferable. During polishing, the slurry is continuously supplied to the polishing cloth by a pump or the like. Although the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with the slurry.

After the polishing is completed, the semiconductor substrate is preferably washed well in running water, and then dried using a spin drier or the like to remove water droplets adhering to the semiconductor substrate. On this way, the SiO ₂ insulating film layer which is flattened, forming an aluminum wiring of the second layer, after forming the SiO ₂ insulating film again by the above method on the inter-wiring and the wiring, the cerium oxide By polishing using an abrasive, unevenness on the surface of the insulating film is eliminated, and a smooth surface is formed over the entire surface of the semiconductor substrate. By repeating this process a predetermined number of times, a semiconductor having a desired number of layers is manufactured.

The cerium oxide abrasive of the present invention can be used not only for an SiO ₂ insulating film formed on a semiconductor substrate but also for a SiO ₂ insulating film formed on a wiring board having predetermined wiring, glass,
Inorganic insulating films such as silicon nitride, optical glass such as photomasks, lenses, and prisms; inorganic conductive films such as ITO; End face, scintillation
Used for polishing optical single crystals such as lasers, solid laser single crystals, LED sapphire substrates for blue lasers, semiconductor single crystals such as SiC, GaP, GaAs, glass substrates for magnetic disks, magnetic heads, etc. Is done. Thus the predetermined substrate in the present invention, a semiconductor substrate which SiO ₂ insulating film is formed, SiO ₂ wiring board on which an insulating film is formed, glass,
Inorganic insulating films such as silicon nitride, optical glass such as photomasks, lenses, and prisms; inorganic conductive films such as ITO; End face, scintillation
Optical single crystal such as laser, solid laser single crystal, blue laser LED sapphire substrate, semiconductor single crystal such as SiC, GaP, GaAs, magnetic disk glass substrate, magnetic head, etc.

[0017]

【Example】

(Preparation of Cerium Oxide Particles) Cerium carbonate hydrate (9
(9.9%) 600 g was placed in a container made of platinum, and the linear velocity was 1 c.
By baking in air at 800 ° C. for 2 hours while flowing air at m / min or more, a yellow-white powder was obtained. When this powder was identified by an X-ray diffraction method, it was confirmed that the powder was cerium oxide. Further, observation with a transmission electron microscope confirmed that the primary particle diameter was 200 nm and the particle diameters were uniform.

(Preparation of cerium oxide slurry) 80 g of the above cerium oxide powder was dispersed in 800 g of deionized water, and 8 g of ammonium polyacrylate was added thereto. 5
The resulting mixture was subjected to a dispersion treatment at 2300 rpm for 30 minutes using a mold to obtain a milky white cerium oxide slurry. The pH of each of the slurries was 9.2. When the particle size distribution of the slurry was examined (Master Sizer
), The average particle size was 210 nm smaller, and the half-value width was both 100 nm, indicating a relatively narrow distribution. From this, it was confirmed that the primary particles were monodispersed.

(Polishing of Insulating Film Layer) An SiO ₂ insulating film formed by a TEOS-plasma CVD method was formed on a holder to which a suction pad for attaching a substrate to be held was attached.
The i-wafer was set, and the holder was placed with the insulating film surface down on a surface plate on which a polishing pad made of a porous urethane resin was attached, and a weight was further placed so that the processing load was 160 g / cm ² . . While the cerium oxide slurry (solid content: 2.5 wt%) was dropped at a rate of 35 cc / min on the platen, the platen was rotated at 30 rpm for 3 minutes to polish the insulating film. After polishing, the wafer is removed from the holder, washed well with running water, and then further cleaned with an ultrasonic cleaner.
Washed for minutes. After the cleaning, water droplets were removed from the wafer with a spin dryer, and the wafer was dried with a dryer at 120 ° C. for 10 minutes.
As a result of measuring a change in film thickness before and after polishing using an optical interference type film thickness measuring apparatus, an insulating film having a thickness of 900 nm was removed by the polishing. After polishing each slurry, it was found that the thickness was uniform over the entire surface of the wafer. In addition, no scratch was observed on the surface of the insulating film visually.

Comparative Example 600 g of cerium carbonate hydrate (99.9%) was heated to 800 ° C.
For 2 hours. The firing was performed in air, and no air gas was intentionally flowed. When this powder was subjected to phase identification by an X-ray diffraction method, it was confirmed that the powder was cerium oxide. According to transmission electron microscopy, 90% of the particles had a primary particle diameter of 200 nm by number.
It was found that spherical fine particles of about nm were also present at the same time. A slurry was prepared under the same conditions as in the example. When the particle size distribution of the slurry was examined (Master Sizer
The average particle diameter was 270 nm, respectively, slightly larger than that of the example, and the half-value width was both 300 nm, indicating that the distribution was broader than that of the example. When the SiO ₂ insulating film produced by the TEOS-CVD method was polished under the same conditions as in the example, no damage was visually observed.
By polishing for 3 minutes, the insulating film was 640 nm, and the insulating film was not removed as compared with the example.

[0021]

The polishing agent of the present invention makes it possible to polish a surface to be polished, such as an SiO ₂ insulating film, evenly.

Claims (7)

[Claims] 1. A cerium compound hydrate having a temperature of not less than 400 ° C.
A cerium oxide abrasive containing a slurry in which cerium oxide particles obtained by introducing air and / or oxygen gas at a temperature of 00 ° C. or less and a linear velocity of 1 cm / min or more and firing are dispersed in a medium. 2. The cerium oxide abrasive according to claim 1, wherein the slurry contains a dispersant. 3. The cerium oxide abrasive according to claim 1, wherein the medium is water. 4. The dispersant is at least one selected from a water-soluble organic polymer, a water-soluble anionic surfactant, a water-soluble nonionic surfactant and a water-soluble amine.
The cerium oxide abrasive as described. 5. The cerium oxide abrasive according to claim 1, wherein the slurry has a pH of 7 or more and 10 or less. 6. A method for polishing a substrate, comprising polishing a predetermined substrate with the cerium oxide abrasive according to any one of claims 1 to 5. 7. The method according to claim 6, wherein the predetermined substrate is a substrate on which an SiO ₂ insulating film is formed.