KR101396250B1 - Cerium basedpolishing particle, slurry comprising the same and the manufacturing method thereof - Google Patents
Cerium basedpolishing particle, slurry comprising the same and the manufacturing method thereof Download PDFInfo
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Abstract
The present invention relates to a cerium oxide abrasive, a slurry containing the cerium oxide abrasive, and a method for producing the same. The present invention relates to a method for preparing a cerium oxide abrasive grains by mixing a basic metal compound with an organic solvent, And at the same time, the particle size distribution and dispersion of the cerium-based abrasive grains can be reduced during the production of the slurry. It is also possible to quickly obtain abrasive grains that do not contain large grains or fine powders. By using the above-mentioned cerium abrasive grains, it is possible to reduce the occurrence of scratches while maintaining an appropriate polishing rate, Lt; RTI ID = 0.0 > slurry.
Description
TECHNICAL FIELD The present invention relates to a cerium-based abrasive particle, a slurry containing the same, and a method for producing the same.
Generally, chemical mechanical polishing (CMP) is used to polish a semiconductor thin film, which includes a metal oxide abrasive for mechanical polishing, a dispersant and an additive for chemical reaction with a semiconductor substrate to be polished A polishing slurry prepared by dispersing and mixing in deionized water is used. This polishing slurry has good dispersibility, has an excellent polishing rate, and is required to generate few defects such as scratches on the surface of a semiconductor substrate after polishing.
The cerium oxide slurry has a property of selectively polishing silicon oxide as compared with silicon nitride, and is suitable for a shallow trench isolation (STI) process. Due to its non-Prestonian behavior, Is also useful as an interlevel dielectric (ILD) process, which is required as a high-planar slurry.
In recent years, wirings in the semiconductor process have become finer and the intervals between the chips have been reduced. Therefore, the chemical mechanical polishing slurry has been required to have a characteristic of reducing the frequency and the size of scratches.
Therefore, in order to reduce the incidence of scratches directly affecting the semiconductor yield, scratches are reduced when the shape of the abrasive particles present in the polishing slurry is rounded to a rounded shape than when the shape of the abrasive particles is square, . Further, by controlling the strength of the abrasive grains, the occurrence frequency of scratches can be reduced.
It is an object of the present invention to improve the particle size distribution of metal oxide abrasive grains and to control the shape of the particles through the metal oxide abrasive grains and to suppress the generation of large particles or fine powders And to provide a method for improving particle size distribution and dispersion.
Another object of the present invention is to provide a cerium-based abrasive grain, a slurry including the cerium-based abrasive grain, and a method for producing the same, which can improve the polishing rate and reduce defects and scratches during CMP polishing using a slurry having improved particle size distribution.
However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.
A process for producing a cerium-based abrasive grain according to the first aspect of the present invention comprises: mixing a metal salt, a basic substance and an organic solvent to prepare a mixture.
According to one aspect of the present invention, the metal salt may include at least one selected from the group consisting of cerium carbonate, cerium nitrate, cerium acetate, cerium sulfate, cerium ammonium nitrate, and salts thereof, no.
According to one aspect of the present invention, the basic substance is selected from the group consisting of KNO 3 , CH 3 COOK, K 2 SO 4 , KCl, KOH, KF, NaOH, NaF, Na 2 O, CH 3 COONa, Na 2 SO 4 , C 5 H 5 N, NaOCl, K 2 C 2 O 4, propylamine, butylamine, diethylamine, dipropylamine, dibutylamine, triethylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, 2 1-propanol, 1-amino-2-propanol, 1-dimethylamino-2-propanol, 3-dimethylamino- Diethylamino-1-ethanol, 2-ethylamino-1-ethanol, 1- (dimethylamino) 2-propanol, N-methyldiethanolamine , N-propyldiethanolamine, N-isopropyldiethanolamine, N- (2-methylpropyl) diethanolamine, N-butyldiethanolamine, Nt- butylethanolamine, N-cydecylhexyldiethanolamine, 2- (dimethylamino) ethanol, 2-di Aminoethanol, 2-aminoethyl-2-pentanol, 2- [bis (2-hydroxyethyl (2-hydroxyethyl) amino] -2-propanol, N, N-bis (2-hydroxypropyl) ethanolamine, 2-amino- -Methyl-1-propanol, tris (hydroxymethyl) aminomethane, and triisopropanolamine, but the present invention is not limited thereto.
According to an aspect of the present invention, there is provided a method for producing a metal oxide, which comprises calcining the mixture to obtain a metal oxide, but is not limited thereto.
According to one aspect of the present invention, the calcination may be performed at 300 to 1000 ° C, but is not limited thereto.
The cerium-based abrasive particles according to the second aspect of the present invention have a peak area ratio defined by the peak area of the (111) face with respect to the peak area of the (200) face of the XRD pattern by X-ray diffraction analysis is 0.5 to 4.5.
According to one aspect of the present invention, the cerium-based abrasive grains may be prepared according to the first aspect, but the present invention is not limited thereto.
According to one aspect of the present invention, the cerium-based abrasive particles may have a spherical shape, but are not limited thereto.
In the abrasive grain according to the third aspect of the present invention, the peak intensity of the (200) plane of the XRD pattern by X-ray diffraction analysis is larger than the peak intensity of the (220) plane.
According to one aspect of the present invention, the cerium-based abrasive grains may be prepared according to the first aspect, but the present invention is not limited thereto.
The method for producing a slurry according to the fourth aspect of the present invention comprises dispersing the abrasive particles produced according to the first aspect in an aqueous solvent.
According to one aspect of the present invention, the method may further include adding a dispersant to the slurry, but the present invention is not limited thereto.
According to one aspect of the present invention, the dispersing agent is at least one selected from the group consisting of polyvinyl alcohol (PVA), ethylene glycol (EG), glycerin, polyethylene glycol (PEG), polypropylene glycol (PPG) and polyvinylpyrrolidone At least one non-ionic polymer selected from the group consisting of: At least one anionic polymer selected from the group consisting of polyacrylic acid, ammonium polyacrylate and polyacrylic maleic acid; Or a combination thereof, but is not limited thereto.
The method for producing slurry particles according to the fifth aspect of the present invention includes the step of drying and pulverizing the slurry prepared according to the fourth aspect.
A slurry particle according to a sixth aspect of the present invention is a slurry particle prepared by drying and pulverizing a slurry containing cerium-based abrasive particles, which comprises mixing a metal salt, a basic substance and an organic solvent to prepare a mixture, The peak area ratio defined by the peak area of the (111) plane with respect to the peak area of the (200) plane of the XRD pattern by X-ray diffraction analysis is 3.2 to 3.8.
According to one aspect of the present invention, the slurry particles may be prepared according to the fifth aspect, but are not limited thereto.
The slurry particle according to the seventh aspect of the present invention is a slurry particle prepared by drying and pulverizing a slurry containing cerium abrasive grains, wherein the peak intensity of the (200) plane of the XRD pattern by X-ray diffraction analysis is 220) plane, but the present invention is not limited thereto.
According to one aspect of the present invention, the slurry particles may be prepared according to the fifth aspect, but are not limited thereto.
The cerium-based abrasive particles, the slurry including the cerium-based abrasive particles, and the method of manufacturing the same according to the present invention minimize the agglomeration between the cerium oxide particles to maintain the nature of the fine powder, reduce particle size distribution and dispersion, and reduce defects and scratches during CMP polishing Therefore, productivity improvement can be expected when manufacturing semiconductor devices. In addition, the process configuration is very simple, the equipment necessary for production is already widely used in industry, is relatively inexpensive, and it is very easy to enlarge.
1 is an XRD pattern of cerium oxide abrasive grains according to Example 1 of the present invention.
2 is an electron micrograph of a cerium oxide abrasive particle according to Example 3 of the present invention.
3 is an XRD pattern of cerium oxide abrasive grains according to Comparative Example 1 of the present invention.
4 is an XRD pattern of the cerium oxide slurry particle according to Example 4 of the present invention.
5 is a graph showing a dispersion stability of a cerium oxide slurry particle according to Example 5 of the present invention measured by a Blue wave meter.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. Also, terminologies used herein are terms used to properly represent preferred embodiments of the present invention, which may vary depending on the user, intent of the operator, or custom in the field to which the present invention belongs. Therefore, the definitions of these terms should be based on the contents throughout this specification. Like reference symbols in the drawings denote like elements.
Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.
Hereinafter, the method for producing cerium-based abrasive grains of the present invention and the cerium-based abrasive grains will be described in detail with reference to examples and drawings. However, the present invention is not limited to these embodiments and drawings.
A process for producing a cerium-based abrasive grain according to the first aspect of the present invention comprises: mixing a metal salt, a basic substance and an organic solvent to prepare a mixture.
According to one aspect of the present invention, the metal salt may include at least one selected from the group consisting of, for example, cerium carbonate, cerium nitrate, cerium acetate, cerium sulfate, cerium ammonium nitrate, and salts thereof.
According to one aspect of the present invention, the basic substance is selected from the group consisting of KNO 3 , CH 3 COOK, K 2 SO 4 , KCl, KOH, KF, NaOH, NaF, Na 2 O, CH 3 COONa, Na 2 SO 4 , C 5 H 5 N, NaOCl, K 2 C 2 O 4, propylamine, butylamine, diethylamine, dipropylamine, dibutylamine, triethylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, 2 1-propanol, 1-amino-2-propanol, 1-dimethylamino-2-propanol, 3-dimethylamino- Diethylamino-1-ethanol, 2-ethylamino-1-ethanol, 1- (dimethylamino) 2-propanol, N-methyldiethanolamine , N-propyldiethanolamine, N-isopropyldiethanolamine, N- (2-methylpropyl) diethanolamine, N-butyldiethanolamine, Nt- butylethanolamine, N-cydecylhexyldiethanolamine, 2- (dimethylamino) ethanol, 2-di Aminoethanol, 2-aminoethyl-2-pentanol, 2- [bis (2-hydroxyethyl (2-hydroxyethyl) amino] -2-propanol, N, N-bis (2-hydroxypropyl) ethanolamine, 2-amino- -Methyl-1-propanol, tris (hydroxymethyl) aminomethane, and triisopropanolamine.
The basic material may be formed by cutting off the surface of the abrasive grains to make the angular shape into a spherical shape.
The acid dissociation constant pKa of the basic substance may be smaller than the acid dissociation constant pKa of the carbonic acid, and the acid dissociation constant pKa of the basic substance may be 7 or more.
The metal salt may If the cerium carbonate, the basic substance KNO 3, wherein the cerium carbonate with a mixing ratio of the KNO 3 may be a KNO 3 0.1 to 2 mol per 1 mol of cerium carbonate.
According to one aspect of the present invention, the organic solvent is at least one selected from the group consisting of ethylene glycol (EG), polyethylene glycol (PEG), methyl alcohol, isopropyl alcohol, methoxy ethanol, acetone, glycerin, toluene, methyl ethyl ketone, Hexane, butyl lactate, and butyl carbitol acetate.
By adding the organic solvent, the peak arrangement of the abrasive grains is changed from the normal to the inverse order. In the present invention means that the peak intensity of the (200) plane is smaller than the peak intensity of the (220) plane in the XRD diffraction pattern obtained when the XRD diffraction pattern is measured using the standard sample 644b. In the present invention means that the peak intensity of the (200) plane is larger than the peak intensity of the (220) plane in the XRD diffraction pattern obtained when the XRD diffraction pattern is measured using the standard sample 644b. This is because the organic solvent changes the peak arrangement by blocking the external oxygen due to the effect of coating the abrasive particles.
Further, the addition of the organic solvent has an effect of coating the abrasive particles and improving the dispersibility.
After the metal salt is mixed with water, a basic substance and an organic solvent, heat treatment may be performed in a liquid state to obtain a mixture. The heat treatment may be performed at a temperature of room temperature or higher for about 1 to about 5 hours, and the mixture obtained after the heat treatment may be filtered using a nut. In addition, the filtration process for removing the remaining reaction liquid can be performed by carrying out a washing process.
The cake-like mixture can be dried using a spray dryer or a drying oven. The spray drying has an advantage that the subsequent pulverization process is facilitated by controlling the size of the secondary particles, and oven drying has an advantage of drying a large amount in a short time. The drying temperature may be, for example, from about 60 to about 100 캜, preferably from about 60 to about 80 캜. When the drying temperature is less than about 60 ° C, there is a problem that the drying time becomes long. When the drying temperature is more than about 100 ° C, cerium carbonate changes to black.
According to an aspect of the present invention, there is provided a method for producing a metal oxide, comprising calcining the mixture to obtain a metal oxide.
The powder dried using the spray dryer or the drying oven may be calcined in a crucible made of alumina or platinum, or may be continuously produced using a rotary kiln.
According to one aspect of the present invention, the calcination may be performed at, for example, about 300 to about 1000 < 0 > C. The calcination can be maintained at a desired temperature, for example, for about 0.1 to about 10 hours, while maintaining an oxidizing atmosphere in which air is sufficiently supplied. In some cases, the calcination process may be performed by adjusting the partial pressure of oxygen. Preferably, the calcination process can be carried out at a temperature of from about 600 to about 900 DEG C for about 1 hour. Cerium carbonate may be formed of cerium oxide through the calcination process.
The median value of the cerium oxide particle size can be, for example, from about 1 to about 2000 nm.
Then, the metal oxide is pulverized.
According to one aspect of the present invention, the pulverization may use a dry grinding dispersion method and a wet grinding dispersion method. Examples of the dry grinding dispersion include a Zetmill, a disk mill, a beads mill, and the like. Examples of the wet grinding dispersion include a ball mill, (Attritionmill), Dyno mill, Vertical mill and the like. Generally, the dry grinding dispersion is carried out before wet grinding dispersion which can grind evenly coarse particles and evenly distribute the particle size distribution finely and accurately.
The cerium-based abrasive particles according to the second aspect of the present invention have a peak area ratio defined by the peak area of the (111) face with respect to the peak area of the (200) face of the XRD pattern by X-ray diffraction analysis is 0.5 to 4.5.
According to one aspect of the present invention, the cerium-based abrasive grains may be prepared according to the first aspect, but the present invention is not limited thereto.
According to one aspect of the present invention, the cerium-based abrasive particles may have a spherical shape, but are not limited thereto.
In the XRD pattern of the cerium-based abrasive grains, the peak of the (111) plane is a peak having a 2? Value of 27 to 30, the peak of the (200) plane is a peak of 32 to 34.5, Lt; RTI ID = 0.0 > 46 < / RTI > The peak area means the integral area occupied by each peak. Peak intensity refers to the peak intensity of each peak appearing after XRD measurement.
In the present invention, the "peak area ratio" is a value calculated by taking the peak area of the (200) plane as the denominator and the peak area of the (111) plane as the numerator. When the peak area ratio calculated from the XRD pattern of the calcined cerium oxide is less than 0.5, the strength of the particles is too weak to lower the polishing rate during polishing after the production of the slurry, and when the peak area ratio exceeds 4.5, the strength of the particles becomes strong, There is a possibility of scratching. The peak area ratio can be controlled by controlling the partial pressure of oxygen during the calcination or by adding a process capable of blocking contact with oxygen during the calcination process and subjecting it to a calcination process.
The peak area of the (111) plane and the peak area ratio of the (200) plane of the cerium oxide particles are related to the strength of the particles and defects and scratches during CMP polishing after slurry preparation. The cerium oxide particles calcined in the oxygen atmosphere generally have a peak area ratio of the (111) plane and a peak area ratio of the (200) plane in the range of approximately 3.0 to 4.5, and the peak area ratio of the cerium oxide particles calcined in the oxygen- To 3.0. Generally, when oxygen deficiency occurs, the peak area ratio becomes small, and the non-stoichiometric structure due to the oxygen deficiency of cerium oxide is generated, so that the strength of the cerium oxide particles is weakened.
In the abrasive grain according to the third aspect of the present invention, the peak intensity of the (200) plane of the XRD pattern by X-ray diffraction analysis is larger than the peak intensity of the (220) plane.
According to one aspect of the present invention, the cerium-based abrasive grains may be prepared according to the first aspect, but the present invention is not limited thereto.
When the peak intensity of the (200) plane of the XRD pattern by X-ray diffraction analysis is larger than the peak intensity of the (220) plane, the cerium-based abrasive particles exhibit inverse order.
The method for producing a slurry according to the fourth aspect of the present invention includes dispersing the cerium-based abrasive particles produced according to the first aspect in an aqueous solvent.
According to one aspect of the present invention, the method may further include adding a dispersant to the slurry.
According to one aspect of the present invention, the dispersing agent is at least one selected from the group consisting of polyvinyl alcohol (PVA), ethylene glycol (EG), glycerin, polyethylene glycol (PEG), polypropylene glycol (PPG) and polyvinylpyrrolidone At least one non-ionic polymer selected from the group consisting of: At least one anionic polymer selected from the group consisting of polyacrylic acid, ammonium polyacrylate and polyacrylic maleic acid; Or a combination thereof.
The dispersant blend ratio may be from about 0.1 wt.% To about 10.0 wt.% Based on abrasive particles, and preferably from about 0.2 wt.% To about 3.0 wt.% Based on abrasive particles.
The method for producing slurry particles according to the fifth aspect of the present invention includes the step of drying and pulverizing the slurry prepared according to the fourth aspect.
The slurry particles comprising the cerium-based abrasive particles according to the sixth aspect of the present invention are prepared by mixing a metal salt, a basic substance and an organic solvent to prepare a mixture, and then slurry particles prepared by drying and crushing a cerium- , The peak area ratio defined by the peak area of the (111) face with respect to the peak area of the (200) face of the XRD pattern by X-ray diffraction analysis is 3.2 to 3.8.
According to one aspect of the present invention, the slurry particles may be prepared according to the fifth aspect, but are not limited thereto.
The reason why the peak area ratio of the slurry particles after slurry preparation is constantly from about 3.2 to about 3.8 is that the powder in which the grain growth has occurred in the (111) direction and the (200) direction after the calcination is crushed through the cleavage face of the cerium- And the number of particles in the (111) direction and the number of the particles in the (200) direction become constant.
The slurry particle comprising the cerium-based abrasive particles according to the seventh aspect of the present invention is a slurry particle prepared by drying and pulverizing a slurry, wherein the peak intensity of the (200) plane of the XRD pattern by X- 220) plane.
According to one aspect of the present invention, the cerium oxide slurry particles may be prepared according to the fifth aspect, but the present invention is not limited thereto.
When the peak intensity of the (200) plane of the XRD pattern by the X-ray diffraction method is smaller than the peak intensity of the (220) plane, the slurry particles exhibit normal-gravity.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
[Example]
The particle size after the preparation of the slurry was measured using a Malvern Zeta-Sizer (manufactured by Malvern Instrument), and the dispersion stability was measured using a measuring instrument called Blue Wave of Malbunsa. The dispersion stability was confirmed by repeated measurement of the same sample three times to obtain stable peaks.
(Preparation of cerium oxide abrasive grains)
Example 1
15 g of cerium carbonate as a basic substance, 15 g of KNO 3 as a basic substance, 250 g of polyethylene glycol as an organic solvent and 1250 g of water were placed in a glass beaker, stirred and rotated at 300 RPM for 3 hours at a temperature of 60 ° C . The mixture was dried at a temperature of 60 ° C for 12 hours and placed in an alumina vessel. The mixture was heated in a box-type electric furnace at 735 ° C for 1 hour under atmospheric pressure To obtain a yellowish white powder. This powder was analyzed by X-ray
2 is an XRD pattern of cerium oxide abrasive grains according to Example 1 of the present invention.
The size of primary particles was measured to be 27 nm as a half value width of the main peak of the (111) plane. The peak area of the (111) plane and the peak area ratio of the (200) plane were 1.5.
1 is an XRD pattern of cerium oxide abrasive grains according to Example 1 of the present invention. The peak intensity of the (200) plane and the peak intensity of the (220) plane were compared to show inverse order. The shape of the particles was observed with an electron microscope and found to be circular.
Example 2
15 g of cerium carbonate as a basic substance, 15 g of KNO 3 as a basic substance, 250 g of polyethylene glycol as an organic solvent and 1250 g of water were placed in a glass beaker, stirred and rotated at 300 RPM for 3 hours at a temperature of 60 ° C . The mixture was dried at a temperature of 60 ° C for 12 hours and placed in an alumina vessel. The mixture was heated in a box-type electric furnace at 790 ° C for 1 hour under atmospheric pressure To obtain a yellowish white powder. This powder was analyzed by X-ray
The size of the primary particles was measured to be 60 nm as a half-value width of the main peak of the (111) plane. The peak area of the (111) plane and the peak area ratio of the (200) plane were 1.3.
The peak intensity of the (200) plane and the peak intensity of the (220) plane were compared to show inverse order. The shape of the particles was observed with an electron microscope and found to be circular.
Example 3
15 g of cerium carbonate as a basic substance, 15 g of KNO 3 as a basic substance, 250 g of polyethylene glycol as an organic solvent and 1250 g of water were placed in a glass beaker, stirred and rotated at 300 RPM for 3 hours at a temperature of 60 ° C . The mixture was dried at a temperature of 60 ° C for 12 hours and placed in an alumina vessel. The mixture was heated in a box-type electric furnace at 835 ° C for 1 hour under atmospheric pressure To obtain a yellowish white powder. This powder was analyzed by X-ray
The size of the primary particles was measured to be 65 nm as a half-width of the main peak of the (111) plane. The peak area of the (111) plane and the peak area ratio of the (200) plane were 1.6.
The peak intensity of the (200) plane and the peak intensity of the (220) plane were compared to show inverse order. 2 is an electron micrograph of a cerium oxide abrasive particle according to Example 3 of the present invention. The shape of the particles was observed with an electron microscope and found to be circular.
Comparative Example 1
1500 g of cerium carbonate, which is a metal salt substance, was placed in an alumina container and heated in a box-type electric furnace at 835 DEG C for 1 hour under atmospheric pressure to obtain a yellowish white powder. This powder was analyzed by X-ray
The size of the primary particles was calculated as the half width of the main peak of the (111) plane, and the size of the primary particles measured was 43 nm. The peak area of the (111) plane and the peak area ratio of the (200) plane were 3.8.
3 is an XRD pattern of cerium oxide abrasive grains according to Comparative Example 1 of the present invention. (200) plane and the peak intensity of the (220) plane were compared with each other. The morphology of the particles was observed with a scanning electron microscope and was found to have an irregular shape.
(Preparation of cerium oxide slurry particles)
Example 4
Using the cerium oxide abrasive grains obtained in Example 1, an ammonium polyacrylate aqueous solution was mixed at 2.5 wt% based on the abrasive grains, stirred for 60 minutes, and pulverized using a vertical mill with 0.1 mm zirconia beads. The final particle size of the slurry was measured using a Malvern Zeta-Sizer (manufactured by Malvern Instrument), and the final particle size of the slurry was 125 nm. The XRD pattern of the cerium oxide slurry particles according to Example 4 of the present invention was obtained by drying and pulverizing the prepared slurry and measuring the size of the primary particles at a half width of the main peak of the (111) plane as a result of XRD analysis. As a result, nm. The peak area of the (111) plane and the peak area ratio of the (200) plane were 3.5.
4 is an XRD pattern of the cerium oxide slurry particle according to Example 4 of the present invention.
(200) plane and the peak intensity of the (220) plane were compared with each other.
Example 5
The same procedure as in Example 4 was repeated except that the cerium oxide abrasive grains prepared in Example 2 were used to prepare a cerium oxide slurry. The final particle size of the slurry was 128 nm. The XRD pattern of the cerium oxide slurry particles according to Example 5 of the present invention was obtained by drying and pulverizing the prepared slurry and measuring the size of the primary particles at a half width of the main peak of the (111) plane as a result of XRD analysis. As a result, nm. The peak area of the (111) plane and the peak area ratio of the (200) plane were 3.5.
(200) plane and the peak intensity of the (220) plane were compared with each other.
5 is a graph showing the dispersion stability of the cerium oxide slurry particles according to Example 5 of the present invention measured with a blue wave. It can be seen that the cerium oxide slurry particles of Example 5 are excellent in dispersion stability.
Example 6
The same procedure as in Example 4 was repeated except that the cerium oxide abrasive grains prepared in Example 3 were used to prepare a cerium oxide slurry. The final particle size of the slurry was 130 nm. The XRD pattern of the cerium oxide slurry particles according to Example 6 of the present invention was obtained by drying and pulverizing the prepared slurry and measuring the size of the primary particles at a half-width of the main peak of the (111) plane as a result of XRD analysis. As a result, nm. The peak area ratio was 3.5.
(200) plane and the peak intensity of the (220) plane were compared with each other.
Comparative Example 2
The same procedure as in Example 4 was repeated except that the cerium oxide abrasive grains prepared in Comparative Example 1 were used to prepare a cerium oxide slurry. The final particle size of the slurry was 125 nm. The prepared slurry was dried and pulverized and subjected to XRD analysis. As a result, the primary particle size was measured to be 24 nm at a half-width of the main peak of the (111) plane. The peak area ratio was 3.5.
(200) plane and the peak intensity of the (220) plane were compared with each other.
[CMP evaluation]
Experiments were carried out by mixing 5 wt% of slurry and ultrapure water in weight ratio and additive weight ratio of 1: 3: 3. In order to examine the polishing rate and defect count of the slurry itself, the CWM evaluation was carried out by mixing 5 wt% of the ceria slurry dispersion and the weight ratio of ultrapure water at a ratio of 1:10.
Additives were prepared by mixing 9800 g of ultrapure water, 290 g of polyacrylic acid (PAA) and 50 g of polyethylene glycol having a molecular weight of 4000, and then adding an appropriate additive to
The CMP equipment was K UNTEX 231 equipment, and the process conditions were as follows.
1. Grinder: UNIPLA 231 (Doosan Mechatech)
2. Pad: K-7 (Rohm & Hass)
3. Polishing time: 60 s (blanket wafer)
4. Platen RPM: 24
5. Head RPM (Head RPM): 60
6. Flow rate: 200 ml / min
7. Wafers used: 8 inch SiO 2 Blanket wafers (PE-TEOS, Poly)
8. Pressure: 5.0 psi
The polishing rate was reduced to the initial wafer thickness and the wafer thickness was measured with an Atlas machine (Nano Metrics) to calculate the polishing removal rate (Å / min).
Defect analysis was performed by SC-1 after the CMP process and defects were measured using AIT-XP equipment.
CMP results are shown in Table 1 below.
(Å / min)
(Å / min)
(ea)
(Å / min)
(ea)
As shown in Table 1, it was confirmed that the slurry according to the present invention exhibited excellent polishing rate as the number of defects was significantly lowered when the metal salt was pretreated with a basic substance and an organic solvent.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined by the equivalents of the claims, as well as the claims.
Claims (18)
Mixing a metal salt, a basic substance and an organic solvent to prepare a mixture;
Lt; / RTI >
Wherein the cerium-based abrasive particles have a peak area ratio of 0.5 to 4.5, which is defined as a peak area of the (111) face with respect to the peak area of the (200) face of the XRD pattern by X-ray diffraction analysis .
Wherein the metal salt comprises at least one selected from the group consisting of cerium carbonate, cerium nitrate, cerium acetate, cerium sulfate, cerium ammonium nitrate, and salts thereof.
The basic material is selected from the group consisting of KNO 3 , CH 3 COOK, K 2 SO 4 , KCl, KOH, KF, NaOH, NaF, Na 2 O, CH 3 COONa, Na 2 SO 4 , C 5 H 5 N, NaOCl, K 2 C 2 O 4 , propylamine, butylamine, diethylamine, dipropylamine, dibutylamine , triethylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, 2-dimethylamino- 1-propanol, 2-amino-1-propanol, 2-dimethylamino-1-propanol, 2- Diethylamino-1-ethanol, 2-ethylamino-1-ethanol, 1- (dimethylamino) 2-propanol, N-methyldiethanolamine, N-propyldiethanolamine , N-isopropyldiethanolamine, N- (2-methylpropyl) diethanolamine, N-butyldiethanolamine, Nt-butylethanolamine, N-cydecylhexyldiethanolamine, 2- , 2-diethylaminoethanol, 2-dipropyl Amino-2-pentanol, 2- [bis (2-hydroxyethyl) amino] -2-methyl-2-methylaminoethanol, 2- (2-hydroxyethyl) amino] -2-propanol, N, N-bis (2-hydroxypropyl) ethanolamine, 2- Tris (hydroxymethyl) aminomethane, and tris (isopropanolamine). ≪ / RTI >
And calcining the mixture to obtain a metal oxide. ≪ RTI ID = 0.0 > 18. < / RTI >
Wherein the calcination is performed at 300 to 1000 ° C.
Mixing a metal salt, a basic substance and an organic solvent to prepare a mixture;
Lt; / RTI >
Wherein the cerium-based abrasive grains have a peak intensity of the (200) plane of the XRD pattern by X-ray diffraction analysis is larger than a peak intensity of the (220) plane.
Wherein said cerium-based abrasive particles are produced according to any one of claims 1 to 6.
Wherein the cerium-based abrasive grains have a spherical shape.
Wherein said cerium-based abrasive particles are produced according to any one of claims 1 to 6.
And adding a dispersant to the slurry.
Preferably,
At least one nonionic polymer selected from the group consisting of polyvinyl alcohol (PVA), ethylene glycol (EG), glycerin, polyethylene glycol (PEG), polypropylene glycol (PPG) and polyvinylpyrrolidone (PVP) ;
At least one anionic polymer selected from the group consisting of polyacrylic acid, ammonium polyacrylate and polyacrylic maleic acid; or
Combinations thereof;
≪ / RTI >
As a slurry particle, which is prepared by drying and pulverizing a cerium-based slurry,
Wherein the peak area ratio defined by the peak area of the (111) face with respect to the peak area of the (200) face of the XRD pattern by X-ray diffraction analysis is 3.2 to 3.8.
Wherein the peak intensity of the (200) plane of the XRD pattern by X-ray diffraction analysis is smaller than the peak intensity of the (220) plane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9982165B2 (en) | 2015-11-20 | 2018-05-29 | Samsung Display Co., Ltd. | Polishing slurry for silicon, method of polishing polysilicon and method of manufacturing a thin film transistor substrate |
| US11203703B2 (en) | 2018-03-20 | 2021-12-21 | Samsung Display Co., Ltd. | Polishing slurry and method of polishing substrate by using the polishing slurry |
| CN116119616A (en) * | 2023-02-14 | 2023-05-16 | 重庆大学 | Application and preparation of oxygen carrier in chemical looping circulation synthesis gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060011094A (en) * | 2004-07-29 | 2006-02-03 | 주식회사 엘지화학 | Cerium oxide powder and process for producing the same |
| KR20080045326A (en) * | 2006-11-20 | 2008-05-23 | 주식회사 엘지화학 | Methodd for preparing cerium oxide powder using organic solvent and cmp slurry comprising the same |
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2012
- 2012-12-31 KR KR1020120158207A patent/KR101396250B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060011094A (en) * | 2004-07-29 | 2006-02-03 | 주식회사 엘지화학 | Cerium oxide powder and process for producing the same |
| KR20080045326A (en) * | 2006-11-20 | 2008-05-23 | 주식회사 엘지화학 | Methodd for preparing cerium oxide powder using organic solvent and cmp slurry comprising the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9982165B2 (en) | 2015-11-20 | 2018-05-29 | Samsung Display Co., Ltd. | Polishing slurry for silicon, method of polishing polysilicon and method of manufacturing a thin film transistor substrate |
| US11203703B2 (en) | 2018-03-20 | 2021-12-21 | Samsung Display Co., Ltd. | Polishing slurry and method of polishing substrate by using the polishing slurry |
| CN116119616A (en) * | 2023-02-14 | 2023-05-16 | 重庆大学 | Application and preparation of oxygen carrier in chemical looping circulation synthesis gas |
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