Silica polishing particles and slurry composition for chemical-mechanical polishing comprising same

Abstract

The present disclosure relates to silica polishing particles capable of suppressing the occurrence of damage to an object to be polished while exhibiting a high polishing rate, and a slurry composition for chemical-mechanical polishing comprising same.

Description

Silica abrasive particles and a chemical-mechanical polishing slurry composition containing the same

[0001] The present disclosure relates to silica abrasive particles and a chemical-mechanical polishing slurry composition containing the same.

[0002] As semiconductor devices become more diverse and highly integrated, finer pattern formation technologies are being used. Consequently, the surface structure of semiconductor devices is becoming more complex, and interlayer flatness in each process is playing a crucial role in improving the precision of photolithography. In the manufacturing of semiconductor devices, the chemical mechanical polishing (CMP) process is utilized as such a planarization technology. For example, it is widely used as a process for interlayer isolation (ILD) to remove excess insulating film deposited for interlayer insulation, as a process for planarizing insulating film for shallow trench isolation (STI) to insulate between chips, and as a process for forming metal conductive films such as wiring, contact plugs, and via contacts.

[0003] In the CMP process, the polishing speed, the flatness of the polished surface, and the degree of scratch occurrence are important and are determined by the CMP process conditions, the type of slurry, and the type of polishing pad. In particular, the slurry composition used in this CMP process contains silica particles for polishing. To improve the performance of the CMP process, polishing silica particle technology incorporating surface modifiers is being developed.

[0004] However, conventional surface-modified silica focuses on polishing performance such as high polishing speed and selectivity, which leads to the problem of defects, such as scratches, being formed on the object to be polished by the abrasive particles.

[0005] Accordingly, there is a need to develop technology for abrasive particles that offer excellent polishing performance while preventing damage, such as scratches, from occurring on the object being polished.

[0006] The present disclosure provides silica polishing particles capable of suppressing damage to a polishing target while having a high polishing speed, and a chemical-mechanical polishing slurry composition containing the same.

[0007] However, the problems that this disclosure aims to solve are not limited to those mentioned above, and other unmentioned problems will be clearly understood by those skilled in the art from the description below.

[0008] One embodiment of the present disclosure is a Si-Si-O3 (Si ) with respect to the Si 2p peak area measured by X-ray photoelectron spectroscopy (XPS). 3+ ) Provides silica abrasive particles having a peak area ratio of 50% or more and 80% or less.

[0009] According to one embodiment of the present disclosure, the silica abrasive particles have a surface area of ​​5 m² 2 / g or more 35 m 2 It may contain micropores of 1 / g or less.

[0010] According to one embodiment of the present disclosure, the content of metal impurities in the total weight of the silica abrasive particles may be 200 ppm or less.

[0011] One embodiment of the present disclosure provides a chemical-mechanical polishing slurry composition comprising the silica polishing particles.

[0012] According to one embodiment of the present disclosure, based on 100 parts by weight of the chemical-mechanical polishing slurry composition, the content of the silica polishing particles may be 1 part by weight or more and 5 parts by weight or less.

[0013] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition further comprises a pH adjuster, and the pH of the chemical-mechanical polishing slurry composition may be 1 or more and 5 or less.

[0014] According to one embodiment of the present disclosure, the content of metal impurities in the total weight of the chemical-mechanical polishing slurry composition may be 200 ppm or less.

[0015] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition may be a silicon oxide polishing composition.

[0016] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition may have a polishing rate of 50 Å / min or more for a silicon oxide film.

[0017] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition may have 220 or fewer scratches having a size of 70 nm or less after polishing a circular silicon oxide film having a diameter of 12 inches.

[0018]

[0019] Silica polishing particles according to one embodiment of the present disclosure can effectively prevent damage, such as scratches, from occurring on the surface of a polishing target.

[0020] In addition, the silica polishing particles according to one embodiment of the present disclosure can easily achieve a high polishing speed for a chemical-mechanical polishing slurry composition with respect to a polishing target.

[0021] In addition, a chemical-mechanical polishing slurry composition according to one embodiment of the present disclosure can effectively suppress damage such as scratches on the surface of a polishing target.

[0022] In addition, a chemical-mechanical polishing slurry composition according to one embodiment of the present disclosure can easily achieve a high polishing speed for a polishing target.

[0023] In addition, by using a chemical-mechanical polishing slurry composition according to one embodiment of the present disclosure, a semiconductor device with better reliability and characteristics can be manufactured.

[0024] The effects of the present disclosure are not limited to those described above, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and the accompanying drawings.

[0025] Figure 1 is a figure showing the Si 2p peaks obtained through XPS for silica before and after modification of Example 3 of the present disclosure.

[0026] Throughout this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0027] Throughout this specification, when a component is described as being located "on" another component, this includes not only cases where a component is in contact with another component, but also cases where another component exists between the two components.

[0028] Throughout the entire specification, the unit "parts by weight" may refer to the ratio of weight between each component.

[0029] Throughout this specification, terms including ordinal numbers, such as “first” and “second,” are used for the purpose of distinguishing one component from another and are not limited by said ordinal numbers. For example, within the scope of the invention, the first component may also be named the second component, and similarly, the second component may be named the first component.

[0030]

[0031] The present specification will be described in more detail below.

[0032] One embodiment of the present disclosure provides silica polishing particles in which the ratio of the Si-Si-O3(Si3+) peak area to the Si 2p peak area measured by X-ray photoelectron spectroscopy (XPS) is 50% or more and 80% or less.

[0033] Silica abrasive particles according to one embodiment of the present disclosure can effectively suppress damage, such as scratches, from occurring on the surface of a polishing target. In addition, the silica abrasive particles can easily achieve a high polishing speed on the polishing target.

[0034] According to one embodiment of the present disclosure, the silica abrasive particles are Si 4+ (Si-O4), Si 3+ (Si-Si-O3), Si 2+ (Si2-Si-O2) and Si + It may include (Si3-Si-O). In this case, Si 3+ (Si-Si-O3) is Si 4+ Compared to (Si-O4), it can correspond to a structure lacking oxygen (O). Si corresponding to the oxygen-deficient structure 3+ As the area ratio calculated through the aforementioned XPS analysis satisfies the above, the silica polishing particles can improve the polishing speed and effectively suppress damage to the polishing target. Meanwhile, Si 2+ (Si2-Si-O2) and Si + (Si3-Si-O) is included in the silica polishing particles in a trace amount and may not affect the physical properties of the silica polishing particles.

[0035] According to one embodiment of the present disclosure, a Si 2p peak can be obtained through XPS measurement of the silica polishing particles. At this time, the Si 2p peak is Si 4+ (Si-O4) peak, Si 3+ (Si-Si-O3) peak, Si 2+(Si2-Si-O2) peak and Si + It may include the (Si3-Si-O) peak. That is, the Si 2p peak area is Si 4+ Peak area, Si 3+ Peak area, Si 2+ Peak area and Si + It can mean the total sum of peak areas.

[0036] Meanwhile, regarding the Si 2p peak area, Si 2+ Peak area and Si + The peak area is Si 4+ Peak area and Si 3+ Having a very small area compared to the peak area, Si relative to the Si 2p peak area 3+ It may not cause a significant difference when calculating the ratio of peak areas.

[0037] That is, the above silica abrasive particles are Si measured through XPS measurement 4+ (Si-O4) peak and Si 3+ Si relative to the total area of ​​the (Si-Si-O3) peak 3+ The ratio of (Si-Si-O3) can be between 50% and 80%. Si 3+ The silica polishing particles having a ratio of (Si-Si-O3) satisfying the aforementioned range can improve the polishing speed and effectively suppress damage to the polishing target.

[0038] According to one embodiment of the present disclosure, the silica abrasive particles may have a ratio of oxygen-deficient structures calculated through Formula 1 below of 50% or more and 80% or less.

[0039] Oxygen-deficient structure ratio (%) = Si 3+ XPS peak area / (Si 4+ XPS peak area + Si 3+ XPS Peak Area) X 100

[0040] Specifically, the oxygen-deficient structure ratio of the silica polishing particles is 50% or more and 78% or less, 50% or more and 76% or less, 51% or more and 76% or less, 51% or more and 75% or less, 55% or more and 69% or less, 57% or more and 67% or less, 59% or more and 65% or less, 60% or more and 63% or less, 50% or more and 65% or less, 51% or more and 62% or less, 53% or more and 61% or less, 55% or more and 59% or less, 55% or more and 80% or less, 57.5% or more and 77.5% or less, 60% or more and 75% or less, 62.5% or more and 72.5% or less, 60% or more and 70% or less, 65% or more and 70% or less, 60% or more and 80% or less, 63% or more and 78% or less, and 65% or more. It may be 76% or less, or 67% or more and 74% or less. The silica polishing particles, in which the ratio of the oxygen-deficient structure calculated through Equation 1 above satisfies the aforementioned range, can improve the polishing speed and effectively suppress damage to the polishing target.

[0041] According to one embodiment of the present disclosure, the silica polishing particles may include micropores and mesopores. The size of the micropores may be greater than 0 nm and less than 2 nm. Additionally, the size of the mesopores may be 2 nm or more and 50 nm or less. In this case, the size of the micropores and mesopores contained in the silica polishing particles may be measured using measuring equipment used in the art. For example, measuring equipment capable of measuring the pore size within a measurement range of 1 Å or more and 10 Å or less may be used.

[0042] According to one embodiment of the present disclosure, the surface area of ​​the micropores of the silica abrasive particles is 5 m 2 / g or more 35 m 2 It may be less than / g. Specifically, the total surface area of ​​the micropores contained in the silica polishing particles is 7.5 m² 2 / g or more 35 m 2 / g or less, 7.5 m 2 / g or more 30 m 2 / g or less, 10 m 2 / g or more 33 m 2 / g or less, 12.5 m 2 / g or more 31.5 m 2 / g or less, 15 m 2 / g or more 35 m 2 / g or less, 15 m 2 / g or more 30 m 2 / g or less, 17.5 m 2 / g or more 28 m 2 / g or less, 20 m 2 / g or more 25 m 2 / g or less, 5 m 2 / g or more 25 m 2 / g or less, 8 m 2 / g or more 24.5 m 2 / g or less, 10.5 m 2 / g or more and 24.5 m2 / g or less, 13 m2 / g or more and 24.5 m2 / g or less, 16.5 m2 / g or more and 24.5 m 2 / g or less, 19 m 2 / g or more 24.5 m 2 / g or less, 20.5 m 2 / g or more 24.5 m 2 / g or less, 20 m 2 / g or more 35 m 2 / g or less, 20 m 2 / g or more 32 m 2 / g or less, 20 m 2 / g or more 30 m 2 / g or less, 20 m 2 / g or more 28 m 2 / g or less, 20 m 2 / g or more 26.5 m 2 / g or less, or 20.5 m 2 / g or more 25 m 2It may be less than / g. When the surface area of ​​the micropores of the silica polishing particles satisfies the aforementioned range, the polishing speed of the silicon oxide film can be improved, and damage to the silicon oxide film during the polishing process can be effectively prevented.

[0043] At this time, the surface area of ​​the micropores contained in the silica polishing particles can be measured using measuring equipment, measuring methods, etc. used in the industry. For example, the surface area of ​​the micropores can be measured using the t-Plot measurement method among BET measurement methods.

[0044] According to one embodiment of the present disclosure, the silica polishing particles may comprise at least one of silica particles surface-treated with plasma and silica particles surface-treated with a surface modifier. Specifically, the silica polishing particles may comprise silica particles surface-treated with a surface modifier. More specifically, the silica polishing particles may be silica particles surface-treated with a surface modifier. The silica polishing particles comprising silica particles surface-treated with a surface modifier can achieve excellent polishing performance on silicon oxide films. Furthermore, the silica particles surface-treated with the surface modifier may be purified. Specific details regarding this will be described later.

[0045] According to one embodiment of the present disclosure, the surface modifier may be any surface modifier used in the art without limitation. Specifically, the surface modifier may include at least an aminosilane-based compound. The above amino silane compounds are aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 4-aminobutyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, aminophenyltrimethoxysilane, 3-aminopropyltrimethoxysilane, aminoundecylethoxysilane, N-(2-aminoethyl)-3-aminopropylmethoxysilane, (3-trimethoxysilylpropyl)diethylenetriamine, butylaminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, (3-(N-ethylamino)isobutyl)trimethoxysilane, (N,N-diethylaminomethyl)triethoxysilane, (N,N-diethyl-3-aminopropyl)trimethoxysilane, It may include at least one of (N,N-dimethyl-3-aminopropyl)trimethoxysilane, bis(methyldiethoxysilylpropyl)amine, bis(methyldimethoxysilylpropyl)-N-methylamine, and bis(3-triethoxysilylpropyl)amine. By using a surface modifier containing the aminosilane compound, silica polishing particles with excellent polishing performance can be effectively provided.

[0046] According to one embodiment of the present disclosure, the content of metal impurities in the total weight of the silica abrasive particles may be 200 ppm or less. Specifically, the content of metal impurities in the total weight of the silica polishing particles is 50 ppm or more and 200 ppm or less, 60 ppm or more and 180 ppm or less, 70 ppm or more and 150 ppm or less, 80 ppm or more and 130 ppm or less, 80 ppm or more and 120 ppm or less, 80 ppm or more and 100 ppm or less, 50 ppm or more and 100 ppm or less, 65 ppm or more and 90 ppm or less, 70 ppm or more and 87.5 ppm or less, 75 ppm or more and 85 ppm or less, 80 ppm or more and 82.5 ppm or less, 75 ppm or more and 200 ppm or less, 75 ppm or more and 175 ppm or less, 75 ppm or more and 145 ppm or less, 75 ppm or more and 135 ppm or less, 75 ppm or more and 130 ppm or less, and 75 ppm or more It may be 120 ppm or less, or 75 ppm or more and 100 ppm or less. When the content of metal impurities contained in the silica polishing particles is within the aforementioned range, the polishing speed of the silicon oxide film can be improved, and damage to the silicon oxide film during the polishing process can be effectively prevented.

[0047] According to one embodiment of the present disclosure, the metal impurity may include at least one of K, Na, Ti, Mg, Li, B, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ag, Cd, Sn, Ta, W, Pt, and Al. Additionally, the silica polishing particles may include at least one metal cation impurity among K, Na, Ti, Mg, Li, B, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ag, Cd, Sn, Ta, W, Pt, and Al. At this time, the content of metal cation impurities in the total weight of the silica polishing particles is 200 ppm or less, 50 ppm or more and 200 ppm or less, 60 ppm or more and 180 ppm or less, 70 ppm or more and 150 ppm or less, 80 ppm or more and 130 ppm or less, 80 ppm or more and 120 ppm or less, 80 ppm or more and 100 ppm or less, 50 ppm or more and 100 ppm or less, 65 ppm or more and 90 ppm or less, 70 ppm or more and 87.5 ppm or less, 75 ppm or more and 85 ppm or less, 80 ppm or more and 82.5 ppm or less, 75 ppm or more and 200 ppm or less, 75 ppm or more and 175 ppm or less, 75 ppm or more and 145 ppm or less, 75 ppm or more and 135 ppm or less, 75 ppm or more and 130 ppm The content may be 75 ppm or more and 120 ppm or less, or 75 ppm or more and 100 ppm or less. When the content of metal cation impurities contained in the silica polishing particles is within the aforementioned range, the polishing speed of the silicon oxide film can be improved, and damage to the silicon oxide film during the polishing process can be effectively prevented.

[0048] According to one embodiment of the present disclosure, the silica polishing particles may include monovalent metal cation impurities and divalent or higher metal cation impurities. The monovalent metal cation impurities may include at least one cation among K, Li, Ag, and Na. Specifically, the monovalent metal cation impurities may include K and Na. The divalent or higher metal cation impurities may include at least one cation among Ti, Mg, B, Ca, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Mo, Cd, Sn, Ta, W, Pt, and Al. Specifically, the divalent or higher metal cation impurities may include Zr, Zn, Ca, Mg, Al, Fe, and Ti. Based on 100% of the total content of metal cation impurities contained in the silica polishing particles, the content of monovalent metal cation impurities may be 90% or more. When the content of monovalent metal cation impurities contained in the above silica polishing particles is within the aforementioned range, the polishing speed of the silicon oxide film can be improved, and damage to the silicon oxide film during the polishing process can be effectively prevented.

[0049]

[0050] One embodiment of the present disclosure provides a chemical-mechanical polishing (CMP) slurry composition comprising the silica polishing particles.

[0051] A chemical-mechanical polishing slurry composition according to one embodiment of the present disclosure can effectively suppress damage, such as scratches, on the surface of a polishing target. In addition, the chemical-mechanical polishing slurry composition can easily achieve a high polishing speed on the polishing target. By using the chemical-mechanical polishing slurry composition, a semiconductor device with superior reliability and characteristics can be manufactured.

[0052] According to one embodiment of the present disclosure, based on 100 parts by weight of the chemical-mechanical polishing slurry composition, the content of the silica polishing particles may be 1 part by weight or more and 5 parts by weight or less. Specifically, the content of the silica polishing particles may be 1.2 parts by weight or more and 4.8 parts by weight or less, 1.4 parts by weight or more and 4.5 parts by weight or less, 1.5 parts by weight or more and 4 parts by weight or less, 1.5 parts by weight or more and 3.5 parts by weight or less, 1.5 parts by weight or more and 3 parts by weight or less, 1.5 parts by weight or more and 2.5 parts by weight or less, 1.5 parts by weight or more and 2 parts by weight or less, 1 part by weight or more and 3 parts by weight or less, 1 part by weight or more and 2.5 parts by weight or less, 1 part by weight or more and 2 parts by weight or less, 1 part by weight or more and 1.8 parts by weight or less, 1 part by weight or more and 1.6 parts by weight or less, 1.5 parts by weight or more and 5 parts by weight or less, 2 parts by weight or more and 5 parts by weight or less, or 3 parts by weight or more and 5 parts by weight or less, based on 100 parts by weight of the chemical-mechanical polishing slurry composition. When the content of the silica polishing particles included in the above CMP slurry composition is within the aforementioned range, the CMP slurry composition can achieve a high polishing speed for the polishing target and can effectively suppress damage to the surface of the polishing target during the polishing process.

[0053] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition may further comprise a pH adjuster. In this case, the pH adjuster may comprise at least one of a basic adjuster and an acid adjuster. For example, the basic adjuster may comprise at least one of imidazole, diethanolamine, monoethanolamine, and triethanolamine. However, the type of basic adjuster is not limited thereto, and any basic adjuster used in the art may be used without limitation. The acid adjuster may comprise at least one of acetic acid, nitric acid, hydrochloric acid, and sulfuric acid. However, the type of acid adjuster is not limited thereto, and any acid adjuster used in the art may be used without limitation.

[0054] According to one embodiment of the present disclosure, the pH of the chemical-mechanical polishing slurry composition may be 1 or more and 5 or less, 1.5 or more and 4.5 or less, 2 or more and 4 or less, 2.5 or more and 3.8 or less, 3 or more and 3.7 or less, 1 or more and 4 or less, 2 or more and 4 or less, 3 or more and 5 or less, 3.5 or more and 5 or less, or 3.6 or more and 4 or less. When the acidity of the CMP slurry composition satisfies the aforementioned ranges, stable dispersion of the silica polishing particles can be induced, and excellent polishing properties for the polishing target can be realized. Meanwhile, in order to adjust the acidity of the CMP slurry composition to a desired range, the content of the pH adjuster may be adjusted.

[0055] According to one embodiment of the present disclosure, the content of metal impurities in the total weight of the chemical-mechanical polishing slurry composition may be 200 ppm or less. In this case, the type of metal impurity included in the CMP slurry composition may be the same as the type of metal impurity contained in the silica polishing particles described above.

[0056] Specifically, the content of metal impurities in the total weight of the CMP slurry composition is 50 ppm or more and 200 ppm or less, 60 ppm or more and 180 ppm or less, 70 ppm or more and 150 ppm or less, 80 ppm or more and 130 ppm or less, 80 ppm or more and 120 ppm or less, 80 ppm or more and 100 ppm or less, 50 ppm or more and 100 ppm or less, 65 ppm or more and 90 ppm or less, 70 ppm or more and 87.5 ppm or less, 75 ppm or more and 85 ppm or less, 80 ppm or more and 82.5 ppm or less, 75 ppm or more and 200 ppm or less, 75 ppm or more and 175 ppm or less, 75 ppm or more and 145 ppm or less, 75 ppm or more and 135 ppm or less, 75 ppm or more and 130 ppm or less, and 75 ppm. It may be between 120 ppm and 75 ppm and 100 ppm. When the content of metal impurities included in the CMP slurry composition is within the aforementioned range, the polishing speed of the silicon oxide film can be improved, and damage to the silicon oxide film during the polishing process can be effectively prevented.

[0057] In addition, the CMP slurry composition may include at least one metal cation impurity among K, Na, Ti, Mg, Li, B, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ag, Cd, Sn, Ta, W, Pt, and Al. At this time, the content of metal cation impurities in the total weight of the CMP slurry composition is 200 ppm or less, 50 ppm or more and 200 ppm or less, 60 ppm or more and 180 ppm or less, 70 ppm or more and 150 ppm or less, 80 ppm or more and 130 ppm or less, 80 ppm or more and 120 ppm or less, 80 ppm or more and 100 ppm or less, 50 ppm or more and 100 ppm or less, 65 ppm or more and 90 ppm or less, 70 ppm or more and 87.5 ppm or less, 75 ppm or more and 85 ppm or less, 80 ppm or more and 82.5 ppm or less, 75 ppm or more and 200 ppm or less, 75 ppm or more and 175 ppm or less, 75 ppm or more and 145 ppm or less, 75 ppm or more and 135 ppm or less, 75 ppm or more It may be 130 ppm or less, 75 ppm or more and 120 ppm or less, or 75 ppm or more and 100 ppm or less. When the content of metal cation impurities included in the CMP slurry composition is within the aforementioned range, the polishing speed of the silicon oxide film can be improved, and damage to the silicon oxide film during the polishing process can be effectively prevented.

[0058] According to one embodiment of the present disclosure, the CMP slurry composition may include monovalent metal cation impurities and divalent or higher metal cation impurities. The monovalent metal cation impurities may include at least one cation among K, Li, Ag, and Na. Specifically, the monovalent metal cation impurities may include K and Na. The divalent or higher metal cation impurities may include at least one cation among Ti, Mg, B, Ca, V, Cr, Mn, Fe, Co, Cu, Zn, Zr, Mo, Cd, Sn, Ta, W, Pt, and Al. Specifically, the divalent or higher metal cation impurities may include Zr, Zn, Ca, Mg, Al, Fe, and Ti. Based on 100% of the total content of metal cation impurities contained in the CMP slurry composition, the content of monovalent metal cation impurities may be 90% or more. When the content of monovalent metal cation impurities contained in the above CMP slurry composition is within the aforementioned range, the polishing speed of the silicon oxide film can be improved, and damage to the silicon oxide film during the polishing process can be effectively prevented.

[0059] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition may be a composition for polishing a silicon oxide film. As described above, the CMP slurry composition can achieve excellent polishing properties for a silicon oxide film by including the silica polishing particles. Specifically, the CMP slurry composition can achieve a high polishing rate for a silicon oxide film. In addition, by using the CMP slurry composition, damage to the silicon oxide film during the polishing process can be effectively suppressed.

[0060] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition may have a polishing rate of 50 Å / min or more for a silicon oxide film. Specifically, the polishing speed of the silicon oxide film of the CMP slurry composition is 50 Å / min or more and 400 Å / min or less, 60 Å / min or more and 380 Å / min or less, 80 Å / min or more and 350 Å / min or less, 100 Å / min or more and 330 Å / min or less, 120 Å / min or more and 330 Å / min or less, 125 Å / min or more and 300 Å / min or less, 140 Å / min or more and 280 Å / min or less, 160 Å / min or more and 260 Å / min or less, 180 Å / min or more and 240 Å / min or less, 50 Å / min or more and 250 Å / min or less, 60 Å / min or more and 230 Å / min or less, 80 Å / min or more and 200 Å / min or less, 100 The polishing speed may be greater than or equal to 400 Å / min, greater than or equal to 375 Å / min, greater than or equal to 125 Å / min, greater than or equal to 350 Å / min, greater than or equal to 300 Å / min, or greater than or equal to 180 Å / min, or greater than or equal to 280 Å / min. The CMP slurry composition, in which the polishing speed of the silicon oxide film satisfies the aforementioned range, can effectively exhibit excellent polishing characteristics for the silicon oxide film.

[0061] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition may have 220 or fewer scratches having a size of 70 nm or less after polishing a circular silicon oxide film having a diameter of 12 inches. Specifically, after polishing a circular silicon oxide film having a diameter of 12 inches using the CMP composition, the number of scratches having a size of 70 nm or less formed on the polished silicon oxide film may be 215 or fewer, 210 or fewer, 200 or fewer, 190 or fewer, 180 or fewer, 160 or fewer, 150 or fewer, or 145 or fewer. In addition, after polishing a circular silicon oxide film having a diameter of 12 inches using the above CMP composition, the number of scratches having a size of 70 nm or less formed on the polished silicon oxide film may be 0, 1 or more, 5 or more, 10 or more, 20 or more, 40 or more, 50 or more, 75 or more, or 100 or more. The above CMP slurry composition, in which the number of scratches formed on the surface of the silicon oxide film after polishing satisfies the aforementioned range, can effectively suppress damage to the silicon oxide film during the polishing process.

[0062] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition may include a solvent. In this case, the solvent may be any solvent used in the art for chemical-mechanical polishing slurry compositions without limitation. For example, the solvent may include at least one of an alcohol-based solvent such as methanol or ethanol and water. However, the type of solvent is not limited thereto.

[0063] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition may further comprise one or more biosides. The biosides are used to prevent microbial contamination and, for example, may include polyhexamethylene guanidine (PHMG) or isothiazolinone compounds. As for the isothiazolinone compounds, one or more selected from the group consisting of methylisothiazolinone (MIT), chloromethylisothiazolinone (CMIT), and 1,2-benzisothiazol-3(2H)-one (benzisothiazolinone, BIT) may be used.

[0064] According to one embodiment of the present disclosure, the content of the bioside may be 0.0001 parts by weight or more and 0.1 parts by weight or less, based on 100 parts by weight of the chemical-mechanical polishing slurry composition. When the content of the bioside included in the CMP slurry composition is within the aforementioned range, excellent sterilization action can be achieved to prevent the occurrence of microorganisms and effectively suppress changes in CMP performance.

[0065] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition may further include a polishing modifier. The polishing modifier may be any one used in the art without limitation. For example, the polishing modifier may include at least one of trimethylamine, triethylamine, tributylamine, tripropylamine, ethylenediamine, hexamethylenediamine, and monoethanolamine. However, the type of polishing modifier is not limited thereto. The content of the polishing modifier may be 0.0001 parts by weight or more and 10 parts by weight or less, based on 100 parts by weight of the chemical-mechanical polishing slurry composition. When the content of the polishing modifier included in the CMP slurry composition is within the aforementioned range, the polishing speed required for the object to be polished can be easily controlled.

[0066] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition may further include an additive. The additive may be any used in the art without limitation. The additive may include an additive that controls the non-uniformity of polishing of the CMP slurry composition, an additive that ensures selectivity of the polishing target, etc. For example, the additive may include at least one of polydextrose, pullulan, dextrin, and hydroxyethyl cellulose, but the type of the additive is not limited thereto.

[0067] According to one embodiment of the present disclosure, the chemical-mechanical polishing slurry composition may further comprise a surfactant. The surfactant may be any surfactant used in the art without limitation. By using a surfactant, the wettability of the CMP slurry composition can be improved. The surfactant may comprise at least one of a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant. For example, the surfactant may comprise a surfactant having an acetylenic diol structure, but the type of surfactant is not limited thereto.

[0068] One embodiment of the present disclosure provides a method for manufacturing silica polishing particles, comprising the steps of: preparing a colloidal silica solution containing silica particles; purifying the silica solution; and adding a surface modifier to the purified silica solution to produce silica polishing particles.

[0069] A method for manufacturing silica polishing particles according to one embodiment of the present disclosure can easily manufacture silica polishing particles that have a high polishing speed with respect to the polishing target and can effectively suppress damage to the polishing target during polishing.

[0070] The method for manufacturing silica polishing particles according to the present embodiment may be the same as the method for manufacturing silica polishing particles according to the aforementioned embodiment. Accordingly, the silica particles, surface modifier, and silica polishing particles in the method for manufacturing silica polishing particles according to the present embodiment may each be identical to the silica particles, surface modifier, and silica polishing particles in the silica polishing particles according to the aforementioned embodiment.

[0071] According to one embodiment of the present disclosure, the step of preparing the silica solution may involve preparing a colloidal silica solution containing silica particles having a particle size of 50 nm or more and 150 nm or less. Specifically, the particle size of the silica particles contained in the silica solution may be 60 nm or more and 135 nm or less, 70 nm or more and 120 nm or less, 80 nm or more and 110 nm or less, 50 nm or more and 110 nm or less, 75 nm or more and 100 nm or less, 75 nm or more and 150 nm or less, 80 nm or more and 130 nm or less, or 85 nm or more and 110 nm or less. By using a silica solution containing silica particles having the aforementioned particle sizes, silica polishing particles capable of achieving a high polishing speed on a polishing target and reducing damage to the polishing target can be easily manufactured. In this case, the particle size of the silica particles may refer to the average particle size of the silica particles contained in the silica solution.

[0072] According to one embodiment of the present disclosure, the silica solution may be purified using a purification method or purification apparatus used in the art, etc., in addition to the step of purifying the silica solution. For example, the purification step may purify the silica solution using methods such as purification using an ion exchange resin; purification using an ion filter; electro-purification such as electrodialysis (ED), electrodeionization (EDI), or capacitive deionization (CDI); purification using a zeolite; or purification through pH adjustment.

[0073] According to one embodiment of the present disclosure, the ionic conductivity of the purified silica solution may be 20 μS / cm or more and 200 μS / cm or less. Specifically, the ionic conductivity of the silica solution purified by the above method is 25 μS / cm or more and 180 μS / cm or less, 27.5 μS / cm or more and 150 μS / cm or less, 30 μS / cm or more and 125 μS / cm or less, 35 μS / cm or more and 100 μS / cm or less, 40 μS / cm or more and 80 μS / cm or less, 20 μS / cm or more and 100 μS / cm or less, 25 μS / cm or more and 80 μS / cm or less, 25 μS / cm or more and 70.5 μS / cm or less, 25 μS / cm or more and 65 μS / cm or less, 25 μS / cm or more and 55 μS / cm or less, 25 μS / cm or more and 45 μS / cm or less, 25 μS / cm or more and 40 μS / cm or less, 25 μS / cm or more and 35 μS / cm or less. It may be 100 μS / cm or more and 200 μS / cm or less, 110 μS / cm or more and 180 μS / cm or less, 120 μS / cm or more and 165 μS / cm or less, or 130 μS / cm or more and 150 μS / cm or less. By controlling the ionic conductivity of the silica solution to the aforementioned range, silica polishing particles capable of achieving a high polishing speed on the polishing target and reducing damage to the polishing target can be easily manufactured.

[0074] According to one embodiment of the present disclosure, the step of manufacturing silica polishing particles may involve adding a surface modifier to the purified silica solution. At this time, the content of the surface modifier added to the silica solution may be 0.001 parts by weight or more and 5 parts by weight or less per 100 parts by weight of silica particles contained in the silica solution. Specifically, the content of the surface modifier added to the silica solution is, with respect to 100 parts by weight of silica particles contained in the silica solution, 0.005 parts by weight or more and 5 parts by weight or less, 0.01 parts by weight or more and 5 parts by weight or less, 0.04 parts by weight or more and 5 parts by weight or less, 0.05 parts by weight or more and 5 parts by weight or less, 0.08 parts by weight or more and 5 parts by weight or less, 0.1 parts by weight or more and 5 parts by weight or less, 0.15 parts by weight or more and 5 parts by weight or less, 0.2 parts by weight or more and 5 parts by weight or less, 0.3 parts by weight or more and 5 parts by weight or less, 0.005 parts by weight or more and 2 parts by weight or less, 0.01 parts by weight or more and 1.8 parts by weight or less, 0.03 parts by weight or more and 1.5 parts by weight or less, 0.04 parts by weight or more and 1.3 parts by weight or less, 0.06 parts by weight or more and 1.1 parts by weight or less, and 0.08 parts by weight or more and 1 The amount may be less than or equal to 0.1 parts by weight or more, 0.85 parts by weight or more, 0.15 parts by weight or more, 0.8 parts by weight or less, 0.25 parts by weight or more, 0.7 parts by weight or less, 0.35 parts by weight or more, 0.5 parts by weight or less, 0.15 parts by weight or more, 0.3 parts by weight or less, 1 part by weight or more, 5 parts by weight or less, 2 parts by weight or more, 4 parts by weight or less, or 2.5 parts by weight or more, 3.5 parts by weight or less. By adjusting the amount of the surface modifier added to the aforementioned range, silica polishing particles capable of achieving a high polishing speed on the polishing target and reducing damage to the polishing target can be easily manufactured.

[0075] According to one embodiment of the present disclosure, the step of manufacturing silica polishing particles may be performed at a temperature of 20°C or higher and 60°C or lower. Specifically, the temperature at which the modification of silica particles is performed may be 25°C or higher and 55°C or lower, 25°C or higher and 50°C or lower, 30°C or higher and 45°C or lower, 35°C or higher and 40°C or lower, 20°C or higher and 40°C or lower, 20°C or higher and 30°C or lower, 40°C or higher and 60°C or lower, or 50°C or higher and 60°C or lower. By controlling the temperature at which the step of manufacturing silica polishing particles is performed to the aforementioned range, the surface of the silica particles can be modified more stably and effectively.

[0076] According to one embodiment of the present disclosure, the particle size of the silica polishing particles may be larger than the particle size of the silica particles before treatment with a surface modifier. Specifically, the ratio of the particle size of the silica particles before treatment with a surface modifier to the particle size of the silica polishing particles may be 1:1.1 to 1:2. When the particle size of the silica polishing particles satisfies the aforementioned conditions, the CMP composition containing the silica polishing particles may have excellent polishing performance with respect to the polishing target and may minimize damage to the surface of the polishing target during the polishing process.

[0077]

[0078] Hereinafter, the present disclosure will be described in detail with reference to examples to specifically explain the present disclosure. However, the embodiments according to the present disclosure may be modified in various different forms, and the scope of the present disclosure is not to be interpreted as being limited to the embodiments described below. The embodiments of this specification are provided to more completely explain the present disclosure to those with average knowledge in the art.

[0079]

[0080] Example 1

[0081] Preparation of colloidal silica solution

[0082] 3.2 g of a silica solution with an average particle size of about 85 nm (silica content 50 wt%; Nalco) was diluted with purified water to prepare 100 g of a colloidal silica solution with a silica content of 1.6 wt%.

[0083]

[0084] Purification of silica solution

[0085] The silica solution was purified using an electro-purification method. The silica solution was purified using a capacitive desalination method with an activated carbon electrode (Siontec).

[0086] Specifically, a silica solution was fed through a pump at a rate of 10 ml / min and circulated for a total of 60 minutes under a voltage of 1V to remove metal ions in the silica solution and to control the ionic conductivity of the solution.

[0087]

[0088] Manufacture of silica abrasive particles

[0089] Aminopropyltriethoxysilane was prepared as a surface modifier. The surface modifier was added to the colloidal silica solution purified above. The surface modifier was added slowly while stirring the silica solution, and stirring was maintained at 25°C for 3 hours. At this time, the amount of surface modifier added was 0.15 parts by weight per 100 parts by weight of silica contained in the silica solution.

[0090]

[0091] Preparation of CMP composition

[0092] Acetic acid or potassium hydroxide was added as a pH adjuster to the modified colloidal silica solution to prepare a CMP composition with a final pH of 3.7. At this time, the content of silica polishing particles was about 1.6 parts by weight based on 100 parts by weight of the CMP composition.

[0093]

[0094] Examples 2 to 11

[0095] For the above Example 1, silica polishing particles and a CMP composition were prepared in the same manner as in Example 1, except that the purification time of the silica solution and the amount of surface modifier added were adjusted as shown in Table 1 below.

[0096] At this time, the CMP compositions prepared in Examples 2 to 11 had a silica polishing particle content of about 1.6 parts by weight based on 100 parts by weight of the CMP composition.

[0097]

[0098] Purification Time (min) Surface Modifier Content (parts by weight) Surface Modification Temperature (°C) Example 1 600.1525 Example 2 900.1525 Example 3 1500.1525 Example 4 2500.1525 Example 5 900.0125 Example 6 900.0425 Example 7 900.0825 Example 8 900.2425 Example 9 900.325 Example 10 100.325 Example 11 900.1550

[0099] In Table 1 above, the content (parts by weight) of the surface modifier is based on 100 parts by weight of silica contained in the silica solution.

[0100]

[0101] Comparative Examples 1 to 3

[0102] For the above Example 1, silica polishing particles and a CMP composition were prepared in the same manner as in Example 1, except that the purification time of the silica solution and the amount of surface modifier added were adjusted as shown in Table 2 below.

[0103] At this time, the CMP compositions prepared in Comparative Examples 1 to 3 had a silica polishing particle content of about 1.6 parts by weight based on 100 parts by weight of the CMP composition.

[0104]

[0105] Purification time (min) Surface modifier content (parts by weight) Surface modification temperature (°C) Comparative Example 100 - Comparative Example 200.1525 Comparative Example 390025

[0106]

[0107] In Table 2 above, the content (parts by weight) of the surface modifier is based on 100 parts by weight of silica contained in the silica solution.

[0108]

[0109] Experimental Example

[0110] pH measurement

[0111] The acidity of the CMP composition was measured using Metrohm 704 (Metrohm).

[0112]

[0113] Ionic conductivity measurement

[0114] The ionic conductivity of the silica solution was measured using a Thermo Scientific Orion Star A212.

[0115]

[0116] Impurity content measurement

[0117] The metal impurity content was analyzed using ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometry), a method capable of analyzing the content of inorganic elements in the sample in ppm units.

[0118] Meanwhile, the content of metal cation impurities was measured by completely dissolving the particles contained in the solution through hydrofluoric acid treatment of the silica solution.

[0119]

[0120] Particle size analysis

[0121] The particle size of the silica particles used was analyzed using DLS (Litesizer 500; Anton Paar).

[0122]

[0123] Measurement of oxygen-deficient structure ratio

[0124] A solution containing silica polishing particles was centrifuged and filtered to obtain silica particles, and the dried powder was used for measurement. The fitted peak area was obtained through deconvolution of the Si 2p peak measured by X-ray photoelectron spectroscopy (XPS), and the ratio of oxygen-deficient structures was calculated using Equation 1 below.

[0125] [Equation 1]

[0126] Oxygen-deficient structure ratio (%) = Si 3+ XPS peak area (A) / (Si 4+ XPS peak area (B) + Si 3+ XPS Peak Area (A) X 100

[0127]

[0128] [XPS Analysis Conditions]

[0129] - Source Gun: Al K Alpha 1486.6 eV

[0130] - Analyser Mode: CAE (constant analyzer energy) Mode

[0131] - Pass Energy : 200.0 ev

[0132] - Energy Step Size: 1000 eV

[0133]

[0134] Specifically, the Si 2p (100.5 eV to 107.5 eV) spectrum of silica polishing particles obtained through XPS analysis was deconvolved and fitted into two different peaks. The two different peaks are, respectively, a peak in the 100.5 eV to 106.5 eV region and a peak in the 101.5 eV to 107.5 eV region. Subsequently, the area (A) of the peak (Si3+) in the 100.5 eV to 106.5 eV region and the area (B) of the peak (Si4+) in the 101.5 eV to 107.5 eV region were measured.

[0135]

[0136] FIG. 1 is a figure showing the Si 2p peaks obtained via XPS for silica before and after modification of Example 3 of the present disclosure. Specifically, FIG. 1(a) shows the Si 2p peaks obtained via XPS for silica before modification with a surface modifier, and FIG. 1(b) shows the Si 2p peaks obtained via XPS for silica after modification with a surface modifier.

[0137] Referring to Fig. 1, through treatment with a surface modifier, Si, which is the oxygen-deficient structure of the silica abrasive particles 3+ It was confirmed that the XPS peak area increased.

[0138]

[0139] Micropore surface area analysis

[0140] A solution containing silica abrasive particles was centrifuged and filtered to obtain silica particles, and the dried powder was used for measurement. The analysis was performed using the t-Plot Micropore Area in the BET method, specifically the amount of N2 adsorbed within a Statistical Thickness (Å) in the range of 0.1 to 1.0 nm.

[0141]

[0142] Grinding speed measurement

[0143] As a target for polishing, a 12-inch diameter and 1 μm thick wafer equipped with a silicon oxide film (PE-TEOS) was used.

[0144] Using AP-300 (CTS) as the polisher, polishing was performed for 60 seconds under the evaluation conditions shown in Table 3 below, and the polishing speed was calculated using Equation 2 below. The wafer thickness was measured using ST-5000 (K-Mac).

[0145]

[0146] RPMPlaten115Head121CMP Composition Flow Rate 200 ml / min Pressure (psi) W 11.25 W 21.10 W 31.00 W 41.00 W 51.00 Pad IC1010

[0147]

[0148] [Equation 2]

[0149] Polishing rate = (Wafer thickness before CMP - Wafer thickness after CMP) / CMP process time (min)

[0150]

[0151] Check the number of scratches

[0152] The number of scratches formed on the silicon oxide film after the above polishing speed measurement was completed was checked. At this time, the size and number of scratches formed on the silicon oxide film were checked using a Litesizer (Anton Paar) device.

[0153]

[0154] Silica solution ionic conductivity (μS / cm) Metal impurity content (ppm) (1)(2)(3)(4)(5) Example 1 67.270.2122.724.598.2 Example 2 33.229.290.38.981.4 Example 3 68.329.387.67.380.3 Example 4 73.731.187.26.780.5 Example 5 33.231.690.38.981.4 Example 6 33.229.990.38.981.4 Example 7 33.229.690.38.981.4 Example 8 33.229.790.38.981.4 Example 933.230.190.38.981.4 Example 10140.2152.2194.263.25130.95 Example 1133.238.590.38.981.4 Comparative Example 1186.7-211.575.9135.6 Comparative Example 2186.7197.3211.575.9135.6 Comparative Example 3119.9125.4177.350.6126.7

[0155]

[0156] In Table 4 above, (1) is the ionic conductivity after purification of the silica solution, and (2) is the ionic conductivity after purifying the silica solution and adding a surface modifier. Also, in Table 4 above, (3) is the content of metal impurities contained in the entire CMP composition, (4) is the content of metal impurities contained in the CMP composition from which silica polishing particles have been removed, and (5) is the content of metal impurities contained in the silica polishing particles. Meanwhile, in Table 4 above, the content of metal impurities may correspond to the content of metal cation impurities.

[0157]

[0158] Silica particles (1)(2)(3) Example 186.5 nm 51.2% 10.8 m 2 / g Example 285.3 nm 68.1 % 24.2 m 2 / g Example 386.7 nm 60.4 % 20.5 m 2 / g Example 488.1 nm 61.3 % 21.1 m 2 / g Example 589.7 nm 57 % 20.88 m 2 / g Example 689.04 nm 59% 25.3 m2 / g Example 785.6 nm 60 % 21.59 m 2 / g Example 890.3 nm69 %22.6 m 2 / g Example 995.4 nm67 %23.1 m 2 / g Example 1098.1 nm 58% 7.8 m 2 / g Example 11109.2 nm76 %31.2 m 2 / g Comparative Example 183.8 nm 47 % 1.1 m 2 / g Comparative Example 285.9 nm 45.9 % 2.3 m 2 / g Comparative Example 382.1 nm 49.6 % 12.4 m 2 / g

[0159]

[0160] In Table 5 above, (1) is the particle size of silica particles contained in the purified silica solution after treatment with a surface modifier, (2) is the ratio of oxygen-deficient structures calculated through the above formula (1) of silica polishing particles after treatment with a surface modifier, and (3) is the surface area of ​​micropores contained in silica polishing particles after treatment with a surface modifier. Meanwhile, in the case of Comparative Example 1, it is not treated with a surface modifier, so (1) of Comparative Example 1 refers to the particle size of silica particles contained in the silica solution not treated with a surface modifier.

[0161]

[0162] Polishing speed (Å / min) 70 nm or less Number of scratches (ea) Example 1 50 18 2 Example 2 12 5 141 Example 3 14 3 143 Example 4 12 0 160 Example 5 6 11 90 Example 69 21 70 Example 7 11 7 155 Example 8 19 31 72 Example 9 25 8 190 Example 10 12 11 98 Example 11 32 42 12 Comparative Example 11 0 242 Comparative Example 29 34 1 Comparative Example 3 15 220

[0163]

[0164] Referring to Tables 4 to 6 above, it was confirmed that the CMP composition containing silica polishing particles prepared in Examples 1 to 11 of the present disclosure achieves a high polishing rate for silicon oxide films, and at the same time, the number of scratches having a size of 70 nm or less corresponds to 200 or less, thereby effectively suppressing damage to the silicon oxide film during polishing.

[0165] Meanwhile, in the case of the CMP composition containing silica polishing particles prepared in Comparative Examples 1 to 3, it was confirmed that the polishing rate for the silicon oxide film was very low and the number of scratches having a size of 70 nm or less exceeded 200, causing a problem where the silicon oxide film was damaged during the polishing process.

[0166] Accordingly, it can be seen that the silica polishing particles according to one embodiment of the present disclosure can achieve a high polishing rate for the silicon oxide film while effectively suppressing damage to the silicon oxide film during the polishing process.

Claims

1. Si-Si-O3 (Si 2p peak area measured by X-ray photoelectron spectroscopy (XPS) 3+ Silica abrasive particles having a peak area ratio of 50% or more and 80% or less.

2. In Paragraph 1, Surface area 5 m² 2 / g or more 35 m 2 Silica abrasive particles containing micropores of 1 / g or less.

3. In Paragraph 1, Silica abrasive particles having a metal impurity content of 200 ppm or less in the total weight of the silica abrasive particles.

4. A chemical-mechanical polishing slurry composition comprising silica polishing particles according to claim 1.

5. In Paragraph 4, A chemical-mechanical polishing slurry composition having a content of 1 part by weight or more and 5 parts by weight or less of the silica polishing particles based on 100 parts by weight of the chemical-mechanical polishing slurry composition.

6. In Paragraph 4, It further contains a pH adjuster, A chemical-mechanical polishing slurry composition having a pH of 1 or more and 5 or less.

7. In Paragraph 4, A chemical-mechanical polishing slurry composition having a metal impurity content of 200 ppm or less in the total weight of the chemical-mechanical polishing slurry composition.

8. In Paragraph 4, The chemical-mechanical polishing slurry composition above is a chemical-mechanical polishing slurry composition that is a composition for polishing silicon oxide films.

9. In Paragraph 4, The above chemical-mechanical polishing slurry composition is, A slurry composition for chemical-mechanical polishing having a polishing rate of 50 Å / min or more for a silicon oxide film.

10. In Paragraph 4, The above chemical-mechanical polishing slurry composition is, A chemical-mechanical polishing slurry composition having 220 or fewer scratches with a size of 70 nm or less after polishing a circular silicon oxide film having a diameter of 12 inches.

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