Cerium oxide particles, chemical mechanical polishing slurry composition containing the same, and method for manufacturing semiconductor device

Abstract

To provide cerium oxide particles for chemical mechanical polishing and slurry compositions for chemical mechanical polishing containing the same, and a method for manufacturing the slurry composition for chemical mechanical polishing.SOLUTION: The surface of cerium oxide particles is characterized by the presence of Ce3+ and Ce4+, when using the cerium oxide particles in the present example, the high oxide film removal rate and oxide film polishing selectivity ratio can be demonstrated even in the low content range despite the fine particle size by increasing the ratio of Ce3+ on the cerium oxide surface.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to cerium oxide particles for chemical mechanical polishing and a chemical mechanical polishing polishing substrate containing the same. The present invention relates to a slurry composition and a method for manufacturing a semiconductor device, and more particularly to a method for manufacturing a semiconductor device using conventional cerium oxide particles. Unlike the conventional method, the surface of cerium oxide is formed by synthesis. 3+ By increasing the ratio of A chemical mechanical polishing slurry that has a high oxide film removal rate at low content despite its small particle size The present invention relates to a lithium composition and a method for manufacturing a semiconductor device using the same. [Background technology]

[0002] As semiconductor elements become more diverse and highly integrated, finer pattern formation technology is being used. This has led to more complex surface structures on semiconductor devices, and photolithography has become increasingly common. To improve the accuracy of photolithography, the interlayer flatness in each process is This is a very important factor in the manufacture of semiconductor devices. Chemical mechanical polishing (CMP) is a chemical mechanical polishing technology. For example, an insulating film formed in excess for interlayer insulation is used. As a process for removing the insulating film, the interlayer insulating film (ID) Shallow trench isolation provides isolation between the conductor and the chip. Shallow trench isolation (STI) insulating film and metal conductors such as wiring, contact plugs, and via contacts. It is also widely used as a process for forming conductive films.

[0003] In the CMP process, the polishing speed, the flatness of the polished surface, and the degree of scratch generation are important. It is determined by the conditions of the CMP process, the type of slurry, the type of polishing pad, etc. High-purity cerium oxide particles are used in cerium slurries. In the manufacturing process, there is a demand to achieve even finer wiring, and Grinding scratches are a problem.

[0004] Conventional cerium oxide slurries use particles ranging in size from 30 nm to 200 nm. Even if minute polishing scratches occur during polishing, they are smaller than the conventional wiring width. This was not a problem in the past, but it is now becoming a problem as we continue to achieve high levels of wiring miniaturization. To address this issue, attempts have been made to reduce the average particle size of cerium oxide particles. However, in the case of existing particles, reducing the average particle size reduces the mechanical action, so the polishing There was a problem with the speed decreasing.

[0005] In this way, by controlling the average particle size of cerium oxide particles, the polishing speed and polishing scratches can be reduced. Even if you try to control it, it is very difficult to achieve the target level of polishing scratches while maintaining the polishing speed. It's nice.

[0006] In addition, conventional chemical mechanical polishing slurry compositions contain cerium oxide particles. 3+ vs Ce 4+ The ratio of the particles is optimized, and the average particle size is also optimized. Therefore, the Ce on the cerium oxide surface 3+ Increasing the ratio of The polishing scraper containing cerium oxide particles exhibits a high oxide film removal rate despite its small particle size. The reality is that research into rallies is needed. Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been devised to solve the above problems, and one embodiment of the present invention is Cerium oxide particles for chemical-mechanical polishing are provided.

[0008] Another embodiment of the present invention provides a slurry composition for chemical mechanical polishing.

[0009] Furthermore, another embodiment of the present invention is a method for polishing a substrate using the chemical mechanical polishing slurry composition. A method for manufacturing a semiconductor device is provided, comprising the step of polishing.

[0010] Yet another embodiment of the present invention provides a semiconductor device.

[0011] Yet another embodiment of the present invention is a method for producing cerium oxide particles for chemical mechanical polishing. Provide the law.

[0012] However, the technical problems that the present invention aims to achieve are not limited to the above-mentioned technical problems. The other technical problems not mentioned above will be apparent from the following description, which are common in the technical field to which the present invention pertains. This will be clearly understood by anyone with ordinary knowledge. [Means for solving the problem]

[0013] As a technical means for achieving the above-mentioned technical object, one aspect of the present invention is a chemical mechanism Cerium oxide particles for mechanical polishing, the content of the cerium oxide particles being 1.0 wt.% In an aqueous dispersion prepared as above, the light transmittance for light with a wavelength of 500 nm is 50% or more. The present invention provides cerium oxide particles for chemical mechanical polishing, characterized in that:

[0014] In an aqueous dispersion in which the content of the cerium oxide particles was adjusted to 1.0 wt %, The film may be characterized by having an average light transmittance of 50% or more for light of 0 to 800 nm.

[0015] When the cerium oxide particles are contained in a chemical mechanical polishing slurry, the chemical mechanical polishing The polishing slurry may be characterized as being transparent.

[0016] The cerium oxide particles are monodispersed when contained in a chemical mechanical polishing slurry. It may be characterized by the fact that

[0017] The particle size of the secondary particles of the cerium oxide particles measured by a dynamic light scattering (DLS) particle size analyzer is The thickness may be 1 to 30 nm.

[0018] The particle size of the secondary particles of the cerium oxide particles measured by a dynamic light scattering (DLS) particle size analyzer is The thickness may be 1 to 20 nm.

[0019] In the X-ray diffraction (XRD) analysis, the particle size of the primary particles of the cerium oxide particles is 0.5 to 1 It may be characterized as being 5 nm.

[0020] When analyzed by transmission electron microscope (TEM), the particle size of the cerium oxide particles was found to be less than 10 nm. It may be characterized by a certain feature.

[0021] In small angle X-ray scattering (SAXS) analysis, the particle size of the cerium oxide particles is 0.5 to 15 nm. m.

[0022] In the spectrum measured by Fourier transform infrared (FT-IR) spectroscopy, 30 00cm-1 ~3600cm -1 Infrared transmittance is over 90% in the range of 720cm -1 ~770cm -1 The infrared transmittance is 96% or less within this range. Possible.

[0023] On the surface of the cerium oxide particles, X-ray photoelectron spectroscopy (XPS) analysis revealed that Ce 3+ Show The XPS peaks indicating the Ce-O bond energy are the first peaks at 900.2 to 902.2 eV. peak, the second peak at 896.4-898.4 eV, and the third peak at 885.3-887.3 eV. It is likely that the fourth peak appears at 880.1 to 882.1 eV. do.

[0024] During X-ray photoelectron spectroscopy (XPS) analysis, the Ce-O bond energy on the surface of the cerium oxide particles was The ratio of Ce to the sum of the XPS peak areas showing 3+ The Ce-O bond energy is The ratio of the sum of the XPS peak areas shown in the graph is 0.29 to 0.70. Ugh.

[0025] 455cm -1 ~460cm -1 characterized by having a first Raman peak in the band range of It is possible that this is the case.

[0026] 586cm -1 ~627cm -1 Further having a second Raman peak in the band range of It may be characterized by:

[0027] 712cm -1 ~772cm -1 Further, the third Raman peak is in the band range of It may be characterized by:

[0028] the ratio (A / B) of the first Raman peak intensity (A) to the second Raman peak intensity (B); may be characterized in that:

[0029] The ratio (A / C) of the first Raman peak intensity (A) to the third Raman peak intensity (C) may be characterized as being 50 or less.

[0030] Electron energy loss spectroscopy (EELS) spectra show the first peaks at 876.5 to 886.5 eV. The maximum intensity of the first peak is 894.5 to 904.5 eV. The intensity of the peak may be greater than the maximum intensity of the second peak.

[0031] The third peak at 886.5-889.5 eV and the fourth peak at 904.5-908.5 eV The sum of all areas of the peaks in the spectrum (P t ) for the third peak The ratio of the sum of the areas of the peak section (P1) to the sum of the areas of the fourth peak section (P2) ((P1 + P2) / P t ) may be less than or equal to 0.1.

[0032] X-ray absorption fine structure (XAFS) Ce by uture spectrum 3+ The area of ​​the peaks A3 and Ce 4+ Show Ce relative to the sum of the peak areas A4 3+ The ratio of the area A3 of the peaks (A3 / (A3+ A4)) may be 0.03 or greater.

[0033] XAFS (X-ray absorption fine structure) Ce by Kutl 3+ The area of ​​the peaks A3 and Ce 4+ The area of ​​the peak A4 Ce in contrast to Wa 3+ The ratio A3 / (A3+A4) of the area A3 of the peaks showing It may be characterized by a certain feature.

[0034] When measuring the XAFS spectrum, the first peak appears in the range of 5730 eV to 5740 eV. and the maximum light absorption coefficient of the first peak is 0.1 to 0.4. It may be characterized by:

[0035] When measuring the XAFS spectrum, a second peak appears in the range of 5740 eV to 5760 eV. and the maximum light absorption coefficient of the second peak is less than 0.6. This could be a sign.

[0036] The cerium oxide particles were analyzed by ultraviolet photoelectron spectroscopy (UPS). During photoelectron spectroscopy analysis, The maximum number of photoelectrons (Counts) is in the range of kinetic energy below 10 eV. The present invention may be characterized by the following.

[0037] The cerium oxide particles are used to measure the number of photoelectrons emitted per second (Cp) during UPS analysis. The maximum value of ts is in the range of kinetic energy 3 to 10 eV. Possible.

[0038] The cerium oxide particles have a work function value of may be characterized by exhibiting a valence of 3.0 eV to 10.0 eV.

[0039] The cerium oxide particles have a BET surface area of ​​50 m 2 / g or less It is possible that.

[0040] The cerium oxide particles have an apparent density of 2.00 to 5.00 g / It may be characterized as being ml.

[0041] The cerium oxide particles have an apparent density of 2.90 to 5.00 g as measured by a tapping method. / ml.

[0042] 325n for an aqueous dispersion in which the content of the cerium oxide particles was adjusted to 1.0 wt % When measuring photoluminescence (PL) at a wavelength of 4 m, The maximum intensity of the first peak (λ1) of wavelengths from 35 to 465 nm appears in the range of 0.1 to 30 The present invention may be characterized by the above.

[0043] The maximum intensity of the second peak (λ2) at wavelengths of 510 to 540 nm appears in the range of 0.1 to 10. It may be characterized in that

[0044] The intensity of the first peak (λ1) relative to the second peak (λ2) at wavelengths of 510 to 540 nm The optical fiber may be characterized by a degree ratio (λ1 / λ2) of 5 to 15.

[0045] The color of the aqueous dispersion in which the content of the cerium oxide particles was adjusted to 1.0 wt % was measured using L*a*b* When expressed in color space, the L* value is 95 or more, and the b* value is 10 to 25. It is possible that this is the case.

[0046] (L* indicates lightness, a* indicates redness, and b* indicates yellowness)

[0047] The a* may be in the range of -12 to -3.

[0048] The aqueous dispersion containing cerium oxide particles adjusted to 1.0 wt % was centrifuged at a centrifugal force of 4250 G. When centrifuged for 30 minutes under the above conditions, the sedimentation rate of cerium oxide particles is 25% by weight or less. The present invention may be characterized by the following.

[0049] Another aspect of the present invention is a method for producing a cerium oxide dispersion comprising: cerium oxide particles; and a solvent; In an aqueous dispersion in which the content of aluminum particles was adjusted to 1.0 wt%, the A chemical mechanical polishing slurry composition characterized by having a light transmittance of 50% or more. provide.

[0050] The cerium oxide particles are present in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total slurry composition. It may be characterized in that it is contained in an amount of 100 parts by weight.

[0051] The composition may be characterized in that the pH is 2-10.

[0052] The chemical mechanical polishing slurry composition is selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. One or more selected inorganic acids; acetic acid, citric acid, glutaric acid, glycolic acid, formic acid, lactic acid , malic acid, malonic acid, maleic acid, oxalic acid, phthalic acid, succinic acid, tartaric acid one or more organic acids selected from the group consisting of lysine, glycine, alanine, arginine, valine, Leucine, isoleucine, methionine, cysteine, proline, histidine, phenylalanine Lanine, serine, tricine, tyrosine, aspartic acid, tryptophan one or more amino acids selected from the group consisting of phan, aminobutyric acid; imidazole; Alkylamines; alcoholamines; quaternary amine hydroxides; ammonia; or and combinations thereof.

[0053] The solvent may be deionized water.

[0054] The chemical mechanical polishing slurry composition has a silicon dioxide rate of 1,000 to 5,000 Å / min. The polishing rate of the oxide film can be increased.

[0055] Another aspect of the present invention is a chemical mechanical polishing brush comprising: cerium oxide particles; and a solvent. The cerium oxide particles are produced by a wet process, and the slurry composition The content of precursor materials contained in the composition is 300 ppm or less by weight. The present invention provides a slurry composition for chemical mechanical polishing.

[0056] The cerium oxide particles are added in an amount of 0.00 based on the total weight of the slurry composition for chemical mechanical polishing. It is characterized by containing 1 to 5% or less.

[0057] Another aspect of the present invention is a method for producing a cerium oxide coating comprising: cerium oxide particles; a solvent; and a cationic polymer. The present invention provides a slurry composition for chemical mechanical polishing, characterized by:

[0058] The oxide film polishing rate increases depending on the content of the cationic polymer. It is possible.

[0059] The cationic polymer is characterized by increasing the polishing selectivity of the oxide film / polysilicon film. This could be a sign.

[0060] The content of the cationic polymer is 100% by weight of the total weight of the slurry composition for chemical mechanical polishing. The content may be 0.001 to 1% by weight.

[0061] The cationic polymer is a polymer or copolymer containing an amine group or an ammonium group. The method may be characterized in that:

[0062] The cationic polymer is polydiallyldimethylammonium chloride (polyd iallyldimethyl ammonium chloride), polyallyl Polyallylamine, polyethyleneimine neimine, polydiallylamine, polyp Propyleneimine, polyacrylamide-co -Diallyldimethylammonium chloride (polyacrylamide-co-d iallydimethyl ammonium chloride), polyacrylamide amide (polyacrylamide), poly(trimethylammonioethyl methacrylate) (Poly(trimethylammonio ethyl methacry) late), dicyandiamide-diethylenetriamine copolymer (dicyandiam ide-diethylenetriamine copolymer), diallyldimethicone Diallyldimethylamine / hydrochloride-acrylamide copolymer (diallyldimethylamine ne / hydrochloride-acrylamide copolymer), Cyandiamide-formaldehyde copolymer butyl acrylate copolymer), or a combination thereof. It is possible that this is the case.

[0063] The chemical mechanical polishing slurry composition has an oxide film / polysilicon ratio of 200 to 2,000. The polishing selectivity of the silicon film can be improved.

[0064] Another aspect of the present invention is a method for polishing a substrate using the above-mentioned chemical mechanical polishing slurry composition. The present invention provides a method for manufacturing a semiconductor device, the method comprising the steps of:

[0065] Another aspect of the present invention is a semiconductor device comprising: a substrate; and an insulating material on the substrate. a trench filled with a chemical mechanical polishing slurry composition; The film is formed by using a material selected from the group consisting of a silicon oxide film, a silicon nitride film, and a polysilicon film. The chemical mechanical polishing slurry is produced by polishing at least one film that is The composition includes cerium oxide particles; and a solvent; and the content of the cerium oxide particles is 1 In an aqueous dispersion adjusted to 0.0 wt%, the light transmittance for light with a wavelength of 500 nm is 50 % or more.

[0066] Another aspect of the present invention is a method for producing a compound comprising the steps of: preparing a raw material precursor; and Cerium oxide particles are ground or precipitated in a solution containing the raw material precursor, and then chemically and mechanically obtaining a dispersion of abrasive cerium oxide particles;

[0067] In an aqueous dispersion in which the content of the cerium oxide particles was adjusted to 1.0 wt %, 100 nm light transmittance of 50% or more for chemical mechanical polishing. A method for producing cerium oxide particles is provided. [Effects of the Invention]

[0068] In the case of the cerium oxide particles according to one embodiment of the present invention, Ce on the surface of the cerium oxide 3+ of By increasing the ratio, the amount of SiO2 contained in the chemical mechanical polishing slurry can be increased despite its small particle size. When the content of SiO2 is low, a high oxide film removal rate can be achieved.

[0069] Furthermore, according to one embodiment of the present invention, surface defects on the wafer can be minimized, which is superior to conventional methods. Surface defects and oxide film removal rate were previously considered to be in a trade-off relationship. Unlike the correlation with the surface defects, the oxide removal rate can be maximized while minimizing the surface defects. Cerium oxide particles for a slurry composition for chemical mechanical polishing and the slurry composition can be provided.

[0070] Furthermore, according to one embodiment of the present invention, the oxide film polishing rate is increased by adding a cationic polymer. It can be seen that the selectivity of the oxide film / polysilicon film increases at the same time. The addition of ionic polymers usually sacrifices the polishing rate to ensure other properties. Considering the current common technical knowledge, this can be said to be a unique effect of the present invention.

[0071] The effects of the present invention are not limited to the above-mentioned effects, and the detailed description or claims of the present invention will be omitted. It should be understood that the scope of the invention includes all effects that can be deduced from the structure of the invention as described in the claims. It is. [Brief explanation of the drawings]

[0072] [Figure 1] 1 shows an oxide film removal mechanism according to an embodiment of the present invention. [Figure 2] 1 is a cross-sectional view (1) illustrating a method for manufacturing a semiconductor device according to an embodiment of the present application. [Figure 3]1 is a cross-sectional view (2) illustrating a method for manufacturing a semiconductor device according to an embodiment of the present application. [Figure 4] 3 is a cross-sectional view (3) illustrating a method for manufacturing a semiconductor device according to an embodiment of the present application. [Figure 5] 4 is a cross-sectional view (4) illustrating a method for manufacturing a semiconductor device according to an embodiment of the present application. [Figure 6] 1A to 1C are cross-sectional views illustrating a method of manufacturing a semiconductor device according to an embodiment of the present disclosure. [Figure 7] 1 shows a stepwise process of chemical mechanical polishing (CMP) and the structure of a chemical mechanical polishing (CMP) equipment according to another embodiment of the present application (1). [Figure 8] 1 shows a stepwise process of chemical mechanical polishing (CMP) and the structure of a chemical mechanical polishing (CMP) equipment according to another embodiment of the present application (2). [Figure 9] This is an image obtained by visually observing a dispersion liquid containing conventional cerium oxide particles. [Figure 10] 1 is a visual image of a dispersion liquid in which cerium oxide particles according to an embodiment of the present invention are dispersed. [Figure 11] 1 is a TEM image (1) of cerium oxide particles according to an embodiment of the present invention. [Figure 12] TEM image (2) of cerium oxide particles according to an embodiment of the present invention. [Figure 13] 3 is a TEM image (3) of cerium oxide particles according to an embodiment of the present invention. [Figure 14] 1 is an SEM image of cerium oxide particles according to Comparative Example 1. [Figure 15] 1 is an SEM image of cerium oxide particles according to Comparative Example 2. [Figure 16] 1 shows SEM and TEM images of cerium oxide particles according to Comparative Example 3. [Figure 17] 1 is an SEM image of cerium oxide particles according to Comparative Example 4. [Figure 18] TEM images of Comparative Examples 1 to 3. [Figure 19]2 is a particle size analysis result of the cerium oxide particles according to an embodiment of the present invention by X-ray diffraction (XRD). [Figure 20] 1 shows the results of analysis of cerium oxide particles according to an embodiment of the present invention by small angle X-ray scattering (SAXS). [Figure 21] 1 is a result of dynamic light scattering (DLS) particle size analysis of cerium oxide particles according to an embodiment of the present invention. [Figure 22] 1 shows the results of spectral analysis of cerium oxide particles and cerium hydroxide particles according to an embodiment of the present invention by Fourier transform infrared (FT-IR) spectroscopy. [Figure 23] 1 shows the results of measuring the light transmittance of slurries containing cerium oxide particles according to an example of the present invention and conventional cerium oxide particles according to comparative examples 1 to 4 using ultraviolet-visible (UV-vis) spectroscopy. [Figure 24] 1 shows the intensity ratio and peak area results of XRD (X-ray diffraction) analysis of cerium oxide particles according to an embodiment of the present invention. [Figure 25] 1 is a result of X-ray photoelectron spectroscopy (XPS) analysis of cerium oxide particles according to an embodiment of the present invention. [Figure 26] 1 shows the results of X-ray photoelectron spectroscopy (XPS) analysis of cerium oxide particles according to Comparative Example 3. [Figure 27] 1 shows the results of Raman peak analysis of cerium oxide particles according to an embodiment of the present invention. [Figure 28] 1 shows the results of Raman peak analysis of cerium oxide particles according to Comparative Example 1. [Figure 29] 1 shows the results of Raman peak analysis of cerium oxide particles according to Comparative Example 3. [Figure 30] 1 shows the results of electron energy loss spectroscopy (EELS) analysis of cerium oxide particles according to an embodiment of the present invention. [Figure 31] 1 shows the results of electron energy loss spectroscopy (EELS) analysis of cerium oxide particles according to Comparative Example 3. [Figure 32] 1 shows the results of electron energy loss spectroscopy (EELS) analysis of cerium oxide particles according to Comparative Example 4. [Figure 33] 1 shows the results of X-ray absorption fine structure (XAFS) spectrum analysis of cerium oxide particles according to an embodiment of the present invention. [Figure 34] 1 shows the results of X-ray absorption fine structure (XAFS) spectrum analysis of cerium oxide particles according to Comparative Example 3. [Figure 35] 1 shows the results of ultraviolet photoelectron spectroscopy (UPS) analysis of an aqueous dispersion containing 1 mass % of cerium oxide particles according to an example of the present invention. [Figure 36] 1 shows the results of ultraviolet photoelectron spectroscopy (UPS) analysis of an aqueous dispersion containing 1 mass % of cerium oxide particles according to Comparative Example 3. [Figure 37] 1 shows the results of ultraviolet photoelectron spectroscopy (UPS) analysis of an aqueous dispersion containing 1 mass % of cerium oxide particles according to Comparative Example 4. [Figure 38] 1 shows the results of BET surface area measurement of cerium oxide particles according to an embodiment of the present invention. [Figure 39] 1 shows the results of BET surface area measurement of cerium oxide particles according to Comparative Example 1. [Figure 40] 1 shows the results of measuring photoluminescence (PL) of cerium oxide particles according to an example of the present invention. [Figure 41] 1 shows the results of measuring the luminescence intensity (PL) of cerium oxide particles according to Comparative Example 3. [Figure 42] 1 shows the results of measuring the luminescence intensity (PL) of cerium oxide particles according to Comparative Example 4. [Figure 43] 1 shows a dispersion containing 1% by mass of cerium oxide particles according to an example of the present invention, prepared for measuring a color system. [Figure 44] This is a dispersion containing 1 mass % of cerium oxide particles according to Comparative Example 3, prepared for measuring the color system. [Figure 45]1 shows scanned images (1) of an oxide wafer before and after CMP using a CMP slurry composition containing cerium oxide particles according to an embodiment of the present invention and a CMP slurry composition containing cerium oxide particles of 60 nm size. [Figure 46] 10 is a scanned image (2) of an oxide wafer before and after CMP using a CMP slurry composition containing cerium oxide particles according to an embodiment of the present invention and a CMP slurry composition containing cerium oxide particles of 60 nm size. [Figure 47] 1 shows the results of measuring the behavior of oxide film polishing rate depending on the addition of a cationic polymer to a CMP slurry composition containing cerium oxide particles according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0073] The present invention will be described in detail below so that those skilled in the art can easily carry out the invention. Although a specific embodiment will be described in detail, the present invention may be embodied in many different forms. The present invention is not limited to the embodiments described herein.

[0074] Production Example 1. Production of cerium oxide particles The cerium oxide particles according to one embodiment of the present invention are obtained by bottom up In the examples of the present application, the oxidized sesquioxanes shown below can be synthesized through chemical synthesis. cerium oxide particles are produced by any one of the methods selected from the following methods for producing cerium oxide particles. Ta.

[0075] According to one embodiment of the manufacturing method of the present application, approximately 100% cerium nitrate is first added to a sufficient amount of deionized water. 2 to 4 kg of nitric acid was added to the precursor solution and stirred. The pH was adjusted to 1.0 or less by adding nitric acid. Aqueous ammonia was added to the mixture and stirred until a precipitate formed. The pH of the resulting mixture was strongly acidic (less than 2), and when left to stand after stirring, the product quickly precipitated. After removing the supernatant liquid from which the precipitate was removed, a certain amount of deionized water was added. The resulting dispersion was mixed with water to produce a pale yellow cerium oxide particle dispersion. The mixture was recycled and filtered through a membrane filter to obtain a transparent yellow cerium oxide dispersion.

[0076] According to another embodiment of the present invention, first, cerium oxide or cerium hydroxide is 150 g of the mixture was dispersed in 3 kg of deionized water and stirred to a degree that the particles did not settle. Nitric acid was added until the pH was below 1.0. The mixture was added to a ring mill and milled while circulating at 4,000 rpm. As the process progresses, the white, opaque cerium oxide dispersion gradually turns into a yellow, transparent cerium oxide. After milling, the yellow transparent cerium oxide was produced. The dispersion is circulated and filtered through a membrane filter to produce a pure, yellow, transparent cerium oxide dispersion. The liquid was obtained.

[0077] According to another embodiment of the present invention, first, a sufficient amount of ethanol is added to the celery. Approximately 2 to 4 kg of ammonium nitrate was added and stirred. The imidazole solution was added and stirred until the pH of the stirred mixture was found to be strongly acidic. (2 or less), and it was confirmed that the product precipitated quickly when left to stand after stirring was completed. After removing the supernatant, a certain amount of deionized water was added to the mixture, and the cerium oxide particle dispersion was The produced dispersion was circulated and filtered through a membrane filter to produce a transparent oxide. A cerium dispersion was obtained.

[0078] According to another embodiment of the present invention, first, 1.1% cerium nitrate is added to a reaction vessel. 10 kg of deionized water was mixed with the reaction vessel. The stirring speed was maintained at 200 rpm. The temperature was maintained. 25% ammonia solution and deionized water After preparing a 1:1 mixture of the above, it was poured into a reaction vessel until the pH reached 7.0. Stirring was continued for 1 hour. After the reaction had progressed, a 1:1 mixture of 70% nitric acid and deionized water was added until the pH reached 1.0. The reactor temperature was raised to 100°C, and the reaction was carried out for 4 hours. The pale purple giant particles dissociated, and yellow transparent cerium oxide nanoparticles were produced. The pure water is removed by circulating the particles through a membrane filter, and pure cerium oxide nanoparticles are produced. A dispersion was obtained.

[0079] Production Example 2: Production of CMP slurry containing cerium oxide particles The cerium oxide particles prepared in Preparation Example 1 were added to deionized water to adjust the abrasive concentration to 0. 0.05 wt.% and triethanolamine was added to adjust the pH to 5.5. Larry was produced.

[0080] 9 and 10, in the case of the conventional slurry containing ceria particles, it is possible to visually (naked eye) It can be observed that the turbidity is high, whereas the slurry containing the cerium oxide particles of the present invention In the case of Lee, it can be observed that it is transparent, and it can be inferred that it has monodisperse properties. This can be done.

[0081] Comparative Examples 1 to 4. Preparation of conventional slurry compositions containing ceria particles Commercially available wet cerium oxide particles with average particle sizes of 10, 30, and 60 nm, respectively, and Separately, cerium oxide particles of 10 to 20 nm in size were obtained by calcination, and It was added to deionized water to make the abrasive concentration 0.05% by weight, and ammonia was used as a pH adjuster. The CMP slurry was prepared by adding 100% ethanol to a final pH of 5.5.

[0082] Experimental Example 1. SEM and TEM analysis of cerium oxide particles The dispersion liquid of Production Example 1 according to one embodiment of the present invention was dried at approximately 80 to 90°C to obtain a powder. Cerium oxide particles (primary particles) were prepared (Sample A). The cerium oxide particles used in the production of Sample B were prepared. B1, B2, B3 and B4). A TEM measurement was performed on each of the prepared samples. The image was taken using

[0083] 11 to 13 are TEM images of cerium oxide particles according to one embodiment of the present invention. .

[0084] 11 to 13, the cerium oxide particles produced according to one embodiment of the present invention The average particle size measured by TEM was approximately 4 nm or less (repeated measurements showed 3.9 nm and 3. It was confirmed that the diameters of the cerium oxide particles according to one embodiment of the present invention were 4.4 nm and 2.9 nm. It was confirmed that the average primary particle size of the cerium oxide was 4 nm or less. It was confirmed that the particles were spherical on average. In addition, spherical cerium oxide particles with a relatively uniform particle size distribution can have a large specific surface area. It is characterized by excellent dispersion stability and storage stability.

[0085] 14 to 17 show SEM images of conventional cerium oxide particles according to comparative examples. is.

[0086] 14 to 17, conventional commercially available cerium oxide particles have the following characteristics: The particle size indicates the particle size that matches the size grade of the product. It was found that all the primary particles had an average particle size of more than 10 nm. The average particle size of the cerium oxide particles according to one embodiment of the present invention as measured by TEM is 4 Compared with the conventional cerium oxide particles and the general calcined It can be seen that the cerium oxide particles produced by this method have a significantly coarse particle size. In contrast, the cerium oxide particles of the present invention are formed with small particle sizes (primary particles). As a result, the smaller the particle size of the cerium oxide, the less cerium oxide is generated on the surface of the film to be polished. It is expected that defects such as scratches can be reduced.

[0087] FIG. 18 shows a TEM image of conventional cerium oxide particles as a comparative example. Referring to FIG. 18, conventional cerium oxide particles with a particle size of 10 nm have edges. ge) and spherical particles, and is different from conventional cerium oxide particles with a particle size of 30 nm or more. It can be seen that the child consists of angular particles with edges. As explained above, the cerium oxide particles according to the embodiments of the present invention have a generally spherical shape. In view of this, the cerium oxide particles of the present invention have a spherical particle shape. However, since the grain size is fine, it can contain a large number of grains, and therefore, silicon oxide When polishing the film, the probability of surface defects occurring can be reduced and the global flatness can be increased.

[0088] Experimental Example 2: X-ray Diffraction (XRD) Analysis of Cerium Oxide Particles The dispersion liquid of Preparation Example 1 according to one embodiment of the present application was dried at about 80 to 90°C to obtain a powder form. Cerium oxide particles (primary particles) were prepared (Sample A). The analysis was carried out using an XRD device (Rigaku, Ultima IV). The XRD was performed under the conditions of Cu Kα (λ=1.5418 Å), 40 kV, and 40 mA. It's set.

[0089] FIG. 19 shows an XRD (X-ray Diff) of the cerium oxide particles according to one embodiment of the present invention. The cerium oxide was analyzed by XRD pattern analysis. The particle sizes are shown in Table 1 below.

[0090] [Table 1]

[0091] Referring to FIG. 19 and Table 1, the XRD analysis results for Sample A show that, as shown in FIG. XRD spectrum of this type (X axis: 2-theta (degree scattering angle), Y axis: signal intensity) The grain size calculated from the above spectrum was 3.25 nm. This is similar to the TEM analysis results of Experimental Example 1, and through this, It was confirmed that the particles were single crystals.

[0092] Experimental Example 3: Small-Angle X-ray Scattering (SAXS) Analysis of Cerium Oxide Particles Small angle X-ray scattering (SAXS) was performed on the cerium oxide particles according to one embodiment of the present invention. The particle size was analyzed using the method shown in FIG.

[0093] Referring to FIG. 20, the particle size of the cerium oxide particles according to the embodiment of the present invention is determined by the average particle radius It can be seen that the range is 2.41 nm and is 10 nm or less. The particle size of the cerium oxide particles according to the present example is much larger than that of conventional cerium oxide particles. Therefore, it can be confirmed that the cerium oxide particles according to the examples of the present invention are very fine. It can be seen that the rate of surface defects can be further reduced when polishing silicon oxide films using this method. .

[0094] Experimental Example 4: Dynamic Light Scattering (DLS) of Cerium Oxide Particles attering) particle size analyzer analysis Slurry composition of Production Example 2 according to one embodiment of the present application, slurries of Comparative Examples 1, 2, 3 and 4 The compositions were prepared as samples. Each of the prepared samples was analyzed by DLS. The analysis was carried out using the instrument.

[0095] FIG. 21 shows a dynamic light scattering (DLS) analysis of cerium oxide particles according to an embodiment of the present invention. The results are shown in Table 2. The dynamic properties of the cerium oxide particles according to the present embodiment and the cerium oxide particles according to the comparative example are shown in Table 1. The D50 values ​​obtained by DLS analysis are shown.

[0096] [Table 2]

[0097] Referring to FIG. 21 and Table 2, the cerium oxide particles according to the embodiment of the present invention have a viscosity of about 5. It has a secondary particle size D50 value of 78 nm, which is measured to be less than 10 nm. Compared with the particle size of the primary particles measured by TEM in Experimental Example 1 (see Figs. 11 to 13), The particle size is 148-199%, and the particles hardly aggregate in the slurry, are monodispersed, and the particle size is It was confirmed that there was almost no change in the level.

[0098] In contrast, the D50 particle measured by dynamic light scattering (DLS) of cerium oxide particles using conventional technology It was confirmed that the particle size exceeded 30 nm, and even in the case of 10 nm-class cerium oxide particles, The particle size of the primary particles measured by TEM is compared with that of the secondary particles measured by dynamic light scattering (DLS). The particle size D50 value is at the level of about 336%, which means that the cerium oxide particles of the prior art are much larger. It can be confirmed that a large amount of aggregation occurred because the secondary particles had a small particle size.

[0099] Therefore, the cerium oxide particles according to one embodiment of the present invention are more effective than the conventional cerium oxide particles according to one comparative example. The particles are less likely to aggregate in the slurry than the cerium oxide particles, and are more monodispersed in the slurry. It can be seen that the amount of data can be distributed.

[0100] Experimental Example 5: Confirmation of the formation of cerium oxide particles by Fourier transform infrared (FT-IR) spectroscopy recognition FIG. 22 shows a powder made of cerium oxide particles prepared according to an embodiment of the present invention, and 1 shows the results of FT-IR spectroscopic analysis of a powder made of ordinary cerium hydroxide particles.

[0101] As a result of analyzing the FT-IR spectrum of FIG. 22, it was found that the cerium oxide according to one embodiment of the present invention 3000cm for powders consisting of ammonium particles -1 ~3600cm -1 Infrared in the range The radiation transmittance is approximately 92-93%, and the 720cm -1 ~770cm -1 Infrared transmission in the range The passivation rate is about 93-95%. In the FT-IR spectrum of the powder consisting of particles, -1 ~3600cm-1 The infrared transmittance in the range of 75-90% is -1 ~770cm -1 Range In comparison with the infrared transmittance of 97 to 99% of the conventional glass, the glass produced according to the embodiment of the present invention The cerium oxide particles are -1 ~3600cm -1 Cerium hydroxide in the range The bands due to the OH groups of the cerium hydroxide particles are It appears weaker than that of the neutron particle, and -1 From 770cm -1 In the range of It was confirmed that a peak due to Ce-O stretching was formed. This can be done.

[0102] Experimental Example 6: Measuring the light transmittance of a slurry containing cerium oxide particles The same procedure was followed as in Example 1 except that the weight ratio of cerium oxide particles in the CMP slurry was 1 wt %. A slurry composition (sample A) was prepared in the same manner as in Example 2. On the other hand, a CMP slurry The weight ratio of cerium oxide particles in the composition was 1 wt %. Each of the slurry compositions was prepared in the same manner as in Samples B1, B2, and B3. 3 and B4). Each sample was analyzed using a UV-Vis spectrometer (JASCO). The transmittance for light of 200 to 1100 nm was measured.

[0103] FIG. 23 shows the results of comparing the cerium oxide particles according to an embodiment of the present invention with the conventional oxide particles of Comparative Examples 1 to 4. The light transmittance of the slurry containing cerium particles was measured using ultraviolet-visible (UV-vis) spectroscopy. This is the result of the above.

[0104] Cerium oxide particles according to the present invention and comparative examples were added to deionized water to form abrasives. The concentration was set to 1.0 wt%, and the CMP slurry was prepared and analyzed for light transmittance. The spectrum was measured in the range of 200–1,100 nm using a UV–vis spectrometer (Jasco U Measurements were made using a V-vis spectrophotometer.

[0105] Through the UV-Vis analysis graph, wavelengths of 500 nm, 600 nm and 700 nm The transmittance (%) of each of Sample A and Samples B1 to B4 is summarized as follows: Shown in Table 3.

[0106] [Table 3]

[0107] According to FIG. 23 and Table 3, in the case of the slurry containing the cerium oxide particles of the present invention, the wave It can be confirmed that the average light transmittance for light with a wavelength of 450 to 800 nm is 50% or more. In addition, the light transmittance for light with a wavelength of about 500 nm is 90% or more, and for light with a wavelength of about 600 nm and 700 nm, It was confirmed that the light transmittance for light with a wavelength of 95 nm was 95% or more.

[0108] In contrast, Comparative Examples 1 to 4 (conventional cerium oxides of 10 nm class, 30 nm class, and 60 nm class) The slurry containing cerium oxide particles of the prior art (cerium oxide particles, calcined ceria particles) The light transmittance was measured. Comparative Example 4 (calcined ceria particles) had a light transmittance of almost 0%. The light transmittance of the slurry of Comparative Example 1, which contains commercially available conventional cerium oxide particles of the nm order, is 8 0%, which indicates that the light transmittance at a wavelength of 500 nm is less than 50%. In the case of Comparative Examples 2 and 3, the particle diameters of the primary particles were also large at 30 and 60 nm, respectively, and the secondary particles were The particle size of the particles is also larger than that of the examples of the present invention (i.e., the cohesion in the slurry is reduced). is large), it can be seen that the transmittance is only less than 20% in the visible light region.

[0109] In contrast, the cerium oxide particles according to one embodiment of the present invention exhibit a luminous efficiency of 90% or more in the visible light region. It can be confirmed that the above light transmittance is exhibited, which is due to the cerium oxide particles of the present invention. In this case, the particle size of the primary particles is very small, and the aggregation of the secondary particles is not as strong as that of the conventional cerium oxide. This means that the secondary particles are smaller than the particles themselves. Normally, when the secondary particles exceed 20 nm, they are invisible to the naked eye. The opacity of the slurry composition can be observed even at wavelengths in the visible light range, and the light transmittance It is well known that the

[0110] According to the slurry composition of the present invention, the light transmittance is determined by the particle size of the primary particles of the cerium oxide particles. If the particle size is small and the tendency to agglomerate into secondary particles is small, the dispersion stability is high and the particles are likely to be distributed uniformly. When a film to be polished is polished using a slurry composition containing the particles, It is easy to predict that the probability of defects such as scratches occurring will be reduced. .

[0111] Experimental Example 7. Peak area ratio of cerium oxide particles by XRD analysis FIG. 24 shows an X-ray Diffraction (XRD) image of cerium oxide particles according to an embodiment of the present invention. The results are the intensity ratio and peak area obtained by the (action) analysis.

[0112] As a result of the XRD analysis of FIG. 24, the (111) of the cerium oxide particles according to one embodiment of the present invention The peak area of ​​the (200) plane is approximately 496.9, and the peak area of ​​the (200) plane is approximately 150.1. Here, the peak area of ​​the (111) plane relative to the peak area of ​​the (200) plane is It can be confirmed that the product ratio is approximately 3.3. When the main peak was examined using the library, It was confirmed that the particles produced in the above examples were cerium oxide particles.

[0113] Experimental Example 8. XPS analysis of cerium oxide particles 25 and 26 show the cerium oxide particles according to an example of the present invention and the cerium oxide particles according to Comparative Example 3. This is the result of XPS analysis of conventional cerium oxide particles of 0 nm class. Otoelectron spectroscopy (OSE) is a method of detecting soft X-rays. y), Ce 3+ The Ce-O bond energy is 900.2 to 902 .2eV, 896.4~898.4eV, 885.3~887.3eV and 880.1~ The peak appearing at 882.1 eV was measured and subjected to XPS fitting. g), the atomic percentage was analyzed to determine the amount of cerium oxide in the particles. Ce 3+ and Ce 4+ The content can be measured. Table 4 below shows the results of the present invention. 1 shows XPS result data of cerium oxide particles according to an example.

[0114] [Table 4]

[0115] From the XPS analysis results, Ce was identified according to the chemical formula described above. 3+ The result of calculating the content Fruit, Ce 3+ It can be seen that the content is 30% or more. 3 + This increases the polishing amount because the reactive sites It will be understood that the above method can be used to obtain the conventional cerium oxide particles. The comparative data is shown in Table 5 below.

[0116] [Table 5]

[0117] In the case of the cerium oxide particles according to one embodiment of the present invention, as shown in Table 5, Ce 3+ Contains The content is about 36.9 atomic %, and in Table 5, this is compared with the conventional 60 nm class oxide. Cerium particles Ce 3+ The content is less than 14 atomic % and is known from the literature. As reported, the nanoparticles are 10 nm in size and are produced by hydrothermal synthesis under supercritical or subcritical conditions. High Ce when compared to cerium oxide particles, which is about 16.8% 3+ Contains It can be confirmed that the surface contains Ce. 3+ The content of the examples of the present invention At such high levels, the chemical bond between silica and cerium forms Si-O-Ce. The polishing mechanism can enhance the polishing rate for silicon-containing substrates.

[0118] Experimental Example 9. Raman spectroscopy of cerium oxide particles Analysis by 27 to 29 show cerium oxide particles according to an embodiment of the present invention and 10 nm-class conventional particles, respectively. Raman spectroscopy of conventional cerium oxide particles and 60 nm class conventional cerium oxide particles The analysis results are shown in Table 1. As a result of the analysis, the samples of the Example, Comparative Example 1, and Comparative Example 3 were In contrast, the Raman spectra (X axis: Ra) of the forms shown in FIGS. 27, 28, and 29 are shown in order. man shift(cm -1), Y-axis: Counts) were derived. The analysis results for the Raman spectrum are shown in Table 6 below.

[0119] [Table 6]

[0120] 27 to 29 and Table 6, the conventional cerium oxide particles according to Comparative Examples 1 and 3 Child is 462cm -1 The first Raman peak is around 1000 nm, whereas the acid according to the present invention has a first Raman peak around 1000 nm. Cerium dioxide particles move at 457 cm -1 Nearby is the first lama It can be seen that the cerium oxide particles according to the embodiment of the present invention have a C peak. e 4+ Ce 3+ The cerium oxide particles are partially reduced to form cubic fluorite (C Defects are induced in the lattice structure of quasi-fluorite, creating oxygen vacancies. As the vacancies increase, the shift of the first Raman peak In addition, due to the difference in particle structure, the second lath of the example sample It can also be confirmed that the intensity of the Mann peak is higher than that of Comparative Example 1 and Comparative Example 3.

[0121] In addition, the cerium oxide particles according to the examples of the present invention have a surface roughness of 457, 607, and 742 cm -1 In contrast, in Comparative Examples 1 and 3, a peak at about 607 cm -1 of It was confirmed that the second peak was barely detectable or appeared with very weak intensity. Approximately 742cm -1 It was confirmed that the third peak of .

[0122] On the other hand, the ratio of the first Raman peak intensity (A) to the second Raman peak intensity (B) (A / B ) are 15.4, 46.0 and 66.4 in the Example, Comparative Example 1 and Comparative Example 3, respectively. It was confirmed that the A / B value for the sample of the example was higher than that of the comparative example 1 and the comparative example 2. It can be seen that the value is much smaller than that of Example 3. The ratio (A / C) of the first Raman peak intensity (A) to the third Raman peak intensity (C) is 50 or more. In the case of Comparative Examples 1 and 3, the third Raman peak is not detected, and A / C is calculated. This is because the Ce in cerium oxide particles 3+ With increased content This results in a higher ratio of defects (oxygen vacancies). This can be interpreted as a result of

[0123] From the above results, it can be seen that the cerium oxide particles according to the embodiment of the present invention are superior to the conventional cerium oxide particles according to the comparative example. High Ce content compared to lithium particles 3+ It can be expected that it contains

[0124] Experimental Example 10. Electron Energy Loss Spectroscopy (EELS) Spectral Analysis of Cerium Oxide Particles The slurry composition of Production Example 2 according to an embodiment of the present invention, the slurries of Comparative Examples 3 and 4 - A sample of each composition was prepared.

[0125] Each of the prepared samples was analyzed using an EELS measurement device. The EELS measurement was performed in the core-loss region, which is the energy loss region of 50 eV or more. The ionization edge observed in the core loss region was Using the ionization edge, peaks are determined according to the oxidation state of the sample being measured. This allows the separation of the cerium oxide particles. 4+ Quantitative content analyzed.

[0126] As a result of analyzing the samples using an EELS measurement device, the samples of Example and Comparative Examples 3 and 4 were For each of these, the EELS spectra (X axis: binding energy (eV), Y Axis: intensity (au; signal strength in arbitrary units) was derived.

[0127] As a result of the analysis, in the EELS spectrum of the example, the first peak of about 876.5 to 886.5 eV was observed. The maximum intensity of the first peak is 894.5 to 904.5. The maximum intensity of the Ce peak is greater than the maximum intensity of the Ce peak. 3+ EELS spectrum trends In contrast, the EELS spectra of Comparative Examples 3 and 4 The maximum peak intensity of the second peak is greater than that of the first peak. 4 + It can be seen that the EELS spectrum follows the trend of the cerium oxide of the example. The um particle is Ce 3+ The EELS spectra of Comparative Examples 3 and 4 follow the same trend. Cerium particles are Ce 4+ This means that the EELS spectrum follows the trend of

[0128] On the other hand, the EELS spectrum of the cerium oxide particles shows a peak at 886.5 to 889.5 eV. It may further include the third peak section and the fourth peak section of 904.5 to 908.5 eV. The peak areas of the third and fourth peak sections are determined by the Ce content of the cerium oxide particles.4+ Show It is possible that the peak indicates the oxidation state. Peak area for the binding energy range of The ratios were calculated and shown in Tables 7 to 9 (results for Example, Comparative Example 3 and Comparative Example 4, respectively). As a result of the EELS spectrum analysis, the oxide ceramic according to one embodiment of the present invention For the lithium particles, the sum of the total EELS peak area (P t ) for the third peak section The ratio of the sum of the areas (P1) (P1 / P t ) is calculated as 1%, 1%, 0% and 0% and compared The values ​​for Example 3 were calculated as 3%, 3%, 4% and 4%, and those for Comparative Example 4 were calculated as 3%, 3%, 3%. and was calculated to be 4%.

[0129] In addition, in the case of the cerium oxide particles according to an embodiment of the present invention, the total EELS peak area Sum(P t ) The area of ​​the third peak section (P1) and the area of ​​the fourth peak (P2) Product ratio ((P1+P2) / P t ) is about 5.8% or less on average, and that of Comparative Example 3 is 1 The value of the pore size distribution in Comparative Example 4 is about 3% or more, and that in Comparative Example 4 is about 12% or more. The cerium oxide particles according to this example have a smaller particle size than the cerium oxide particles of Comparative Examples 3 and 4. High Ce content 4+ It can be confirmed that it has the following.

[0130] [Table 7]

[0131] [Table 8]

[0132] [Table 9]

[0133] Experimental Example 11: XAFS (X-ray absorption finite element analysis) of cerium oxide particles e structure) Spectral analysis Slurry composition of Production Example 2 according to an embodiment of the present invention and slurry composition of Comparative Example 3 Each of these was prepared as a sample.

[0134] Each of the prepared samples was analyzed using an XAFS measuring instrument. XAFS is a method of irradiating a sample with high-intensity X-rays and measuring the intensity of the absorbed X-rays. It is an analytical method derived by measuring the optical absorption coefficient (xμ) according to the X-ray energy (eV). Based on the X-ray absorption spectrum, the Ce in the particles 3+ and Ce 4+ Weight ratio (w At this time, the absorption spectrum shows a sudden increase in X-ray absorption. XAFS spectra within 50 eV of the absorption edge X-ray absorption near edge structure (XANES) The near edge structure (NES) method was used.

[0135] The XAFS analysis results for the samples of Example and Comparative Example 3 are shown in FIG. 3. 3 and XAFS spectra as shown in Figure 34 (X axis: X-ray energy X (eV), Y axis: The X-ray absorption coefficient xμ(E) was derived. As shown in FIGS. 33 and 34, All of the samples of Comparative Example 3 had an absorption edge. was formed in the range of about 5745 to 5755 eV. 3+X-ray absorption by The peak (P1) where strong electronic transition occurs is formed in the range of approximately 5735 to 5740 eV. It was decided that Ce 4+ Peak (P2) where strong electronic transition occurs due to X-ray absorption by It was confirmed that it was formed in the range of approximately 5745 to 5755 eV.

[0136] As a result of examining the optical absorption coefficients for P1 and P2, in the case of the embodiment according to the present invention, In contrast, in the case of Comparative Example 3, It can be seen that the levels are less than 0.1 and more than 0.6, respectively.

[0137] Based on the analysis results, the Ce content of the samples of Example and Comparative Example 3 was 3+ and Ce 4+ The peak areas and area ratios of the compounds can be confirmed as shown in Table 10 below. do.

[0138] [Table 10]

[0139] Referring to Table 10, the Ce on the surface of the cerium oxide particles according to one embodiment of the present invention 3 + The area ratio of Ce on the surface of the cerium oxide particle according to Comparative Example 3 is 3+ Approximately 4 times the area ratio of It can be confirmed that the oxidation resistance of the examples of the present invention is higher than that of the conventional oxidation resistance of the comparative examples. It can be expected to have a higher polishing rate than cerium particles.

[0140] Experimental Example 12. UPS analysis of cerium oxide particles Cerium oxide particles according to an example of the present invention and samples of comparative examples 3 and 4 were prepared.

[0141] 35 to 37 show cerium oxide particles according to an embodiment of the present invention and 60 nm-class particles. Conventional cerium oxide particles and conventional cerium oxide particles produced by calcination method These are the results of the PS analysis.

[0142] Table 11 shows the results of the comparison between the cerium oxide particles according to an embodiment of the present invention and the conventional cerium oxide particles. This is a summary of the work function values ​​according to the classification.

[0143] In one embodiment, the cerium oxide particles according to an embodiment of the present disclosure are released per second. The maximum value of the photoelectron count (Y axis) is in the kinetic energy range of 8 to 10 eV. In contrast, in the cases of Comparative Examples 3 and 4, the kinetic energy is in the range of 11 to 13 eV. From these results, it was confirmed that in the example, the work function was 3.16 eV. In the case of Comparative Examples 3 and 4, the work functions were 2.37 eV and 2.37 eV, respectively. We were able to derive that.

[0144] In one embodiment, UPS analysis is performed using the measured kinetic energy (E kin ) through the value Binding energy (E b ) and from the derived binding energy graph, the Elmi level (E F ) and vacuum level (E cutoff ) could be derived. The Fermi level (E F ) and vacuum level (E cutoff ) value and apply it to the following equation 1 The work function φ value was calculated. In this case, hv is the value used when emitting ultraviolet light. Source energy refers to the energy of the incident light. However, helium (He) was used as the source (He|UPS=21.22 eV). The work function values ​​from the analysis are shown in Table 11 below.

[0145] [Formula 1] φ=hv-|E f -E cutoff |

[0146] [Table 11]

[0147] Referring to Table 11, the work function value of the cerium oxide particles according to an embodiment of the present invention is The smaller the particle size, the greater the energy between the sample orbits. The difference between the energy levels gradually increases, resulting in a high energy band gap. From this, it can be seen that the particle size of the cerium oxide particles according to one embodiment of the present invention is larger than that of the conventional cerium oxide particles. Since it is sufficiently small compared to the particle size of silicon particles, it has a high energy band gap. This affects the Fermi level and the vacuum level, changing the energy value of the work function. Therefore, it was possible to predict that the UPS analysis would lead to The calculated work function value is that the particle size of the cerium oxide particles according to the embodiment of the present invention is larger than that of the conventional cerium oxide particles. This shows that the particles are sufficiently small compared to sodium particles and have very little agglomeration. Since the cerium oxide particles according to an embodiment of the present application have the characteristics of being monodispersed with little aggregation, When used in a chemical mechanical polishing slurry, the particles that come into contact with the wafer This maximizes the number of particles, which increases the polishing speed of the oxide film and also reduces the particle size itself. The finer the pattern, the smaller the defects on the wafer surface.

[0148] Experimental Example 13. BET Surface Area Analysis of Cerium Oxide Particles To measure the BET surface area, powders of cerium oxide particles according to the present invention and ratios 1.0 g of each of the cerium oxide particle powders according to Comparative Example 1 was heated at 200°C for 1 hour each time. After pre-treatment by degassing until the distillation pressure was below a specified value, BET (Tristar II plus, Micrometrics) at 77K with increasing relative pressure The amount of nitrogen gas adsorbed was measured, and the BET surface area calculated from the amount of adsorption was shown in FIG. This is shown in Figure 39 and Table 12 below.

[0149] [Table 12]

[0150] Referring to Table 12, when general pretreatment conditions (200°C, 1 hour) were applied, When the cerium oxide particles according to the embodiment of the present invention were measured five times under the same conditions, the BE T surface area value is 50m 2 / g or less, whereas the powder of cerium oxide particles according to Comparative Example 1 When measured five times under the same conditions, the BET surface area was 80m 2 Check that the value exceeds / g. The numerical values ​​of such comparative examples are based on the 10 nm It can be seen that the BET surface area values ​​are similar to those of cerium oxide particles of the same grade.

[0151] From the above results, unlike the general tendency that the smaller the particle size, the larger the BET surface area value, The powder of cerium oxide particles according to the embodiment of the present invention is larger than that of Comparative Example 1, which has a coarser particle size. It can be seen that the BET surface area is smaller than that of the cerium oxide powder. The cerium oxide particles according to the examples of the present invention have a finer particle size than conventional cerium oxide particles. This means that when powdered, they can be packed more densely. It is also possible to synthesize them by self-assembly synthesis methods such as the sol-gel method and bottom-up method. Cerium oxide particles have less -OH than cerium oxide particles synthesized by other synthesis methods. This is in line with the phenomenon that the BET surface area and pore volume are smaller because the functional group is present. Can be captured.

[0152] Experimental Example 14. Analysis of apparent density of cerium oxide particles The dispersion liquid of Preparation Example 1 according to one embodiment of the present application was dried at about 80 to 90°C to obtain oxide in powder form. Cerium particles (Sample A) and powder-form acids according to Comparative Examples 3 and 4 dried under the same conditions. Cerium oxide particles (samples B and C, respectively) were prepared. The apparent density and the density of the prepared sample A according to the present embodiment and comparative examples 3 and 4 were The tap density was measured and shown.

[0153] [Table 13]

[0154] [Table 14]

[0155] Referring to Table 13, the apparent density of Sample A measured by the static method was 2.22 g / ml, whereas the apparent density of the 60 nm class cerium oxide particles in Comparative Example 3 was 1. The apparent density of the calcined cerium oxide particles of Comparative Example 4 was measured to be 1.30 g / ml. Furthermore, referring to Table 14, the results of the measurement of sample A by the tap method are as follows: The density of the cerium oxide particles of 60 nm class in Comparative Example 3 was 2.94 g / ml. The apparent density was 2.86 g / ml, and the apparent density of the calcined cerium oxide particles in Comparative Example 4 was 1. 60g / ml, and can be confirmed to have a value of less than 2.90g / ml. As a result, the cerium oxide particles according to one embodiment of the present application can be made into finer primary particles. Although the cerium oxide particles have a diameter of 1.0 mm, they are larger than the cerium oxide particles of the comparative example, which have a coarser particle diameter. Therefore, it can be confirmed that the apparent density of the cellulose acylate 100 is 0.01g / cm 2 . In the case of such cerium oxide particles, the particle size is 10 nm or less, which is finer than conventional cerium oxide particles. It has been confirmed that the apparent density is relatively high despite the fine particle size. can.

[0156] Experimental Example 15. Photoluminescence Intensity (PL) of Dispersion Liquid Containing Cerium Oxide Particles Scence) Measurement and Analysis 40 to 42 and Table 15 show the results of the cerium oxide particles according to an embodiment of the present invention and the conventional 6 10nm class cerium oxide particles and 10nm class cerium oxide particles by calcination method. The results of measuring the emission intensity for each aqueous dispersion containing 100% by mass of fluorine-containing ... The light intensity measurements were taken under the following test conditions:

[0157] (1) Test equipment: Perkin Elmer LS-55 Fluorescence Spectrometer ence Spectrometer) (2) Excitation wavelength: 325 nm (3) Emission filter: 350 nm (4) Excitation slit width: 10.0n m (5) Emission slit width: 10.0 nm

[0158] [Table 15]

[0159] 40 to 42 and Table 15, the excitation wavelength (λ excitation )325 Fluorescence spectrometer performed at nm Analysis revealed that the three samples all had an excitation peak (λ ) at a wavelength of approximately 325 nm. exc ), The first emission peak (λ ems1 ), the second emission at a wavelength of about 525 nm Light peak (λ ems2 ) can be seen to indicate

[0160] In the case of the cerium oxide particles of the present invention, the ratio of the first emission peak to the second emission peak (λ e ms1 / λ ems2 ) was found to be approximately 7.5, a value of 5 or more. Conventional 10 nm class cerium oxide particles by calcination method and commercially available 60 nm class cerium oxide particles All nanoparticles have a ratio of the first emission peak to the excitation peak (λ ems1 / λ exc ) is 3 It was confirmed that the ratio of the first emission peak to the second emission peak (λ ems 1 / λ ems2 ) was confirmed to be less than 5.

[0161] In the case of the cerium oxide particles of the present invention, Ce 3+ The intensity of the first emission peak, which indicates The conventional 10 nm class cerium oxide particles and commercially available 60 nm class cerium oxide particles were It can be seen that the particle size is smaller than that of the cerium oxide particles of the present invention. In this case, there is very little aggregation of secondary particles from the dispersion liquid, so light transmission is good. In addition, the cerium oxide particles of the present invention are judged to have a relatively weak luminescence intensity. Unlike 60 nm class particles or calcined cerium oxide particles, The ratio of the first emission peak to the ems1 / λ ems2 ) shows a value of 5 or more, The cerium oxide particles of the present invention have a relatively high Ce content on the surface. 3+ To indicate that it contains Therefore, from this experimental example, it can be seen that the cerium oxide particles of the present invention are chemically mechanically When used in slurries for mechanical polishing, Ce on the particle surface 3+ Although the content is high, the particles The particles themselves are very fine and have the property of hardly agglomerating in the slurry. The chemical polishing rate is increased by the Si-O-Ce bond between the sodium particles and the oxide film substrate. It can be seen that the oxide film polishing rate is improved.

[0162] Experimental Example 16. L*a*b* color system analysis of dispersion liquid containing cerium oxide particles 43 and 44 show the results of a water content of 1 mass % of cerium oxide particles according to an embodiment of the present invention. The two dispersions are an aqueous dispersion containing 1% by mass of conventional 60 nm class cerium oxide particles.

[0163] Tables 16 and 17 show dispersions containing 1% by mass of cerium oxide particles according to an embodiment of the present invention. The color of the dispersion liquid containing 1% by mass of conventional 60 nm-class cerium oxide particles was measured. This is a summary of values ​​shown in the L*a*b* color system.

[0164] In one embodiment, the L*a*b* color system analysis is performed using a CM-5 (KONICA MINO LTA, JAPAN) according to ASTM E1164 (Standard practice ce for obtaining spectrometric data for Object color evaluation: Spectral data for object color evaluation is obtained. The light source used was a Xenon lamp D65. The analysis was carried out in the wavelength range of 360 to 740 nm with wavelength intervals of 10 nm. The results are shown in Tables 16 and 17 below.

[0165] [Table 16]

[0166] [Table 17]

[0167] 43 and 44, it can be seen that the aqueous dispersion containing the cerium oxide particles of the present invention is It can be seen that the film takes on a yellowish color, which is different from the conventional 60nm oxide film. In the case of the aqueous dispersion containing cerium particles, it was found that although it was opaque, it was closer to white. It was.

[0168] Furthermore, referring to Tables 16 and 17, the cerium oxide particles according to one embodiment of the present invention In the case of a dispersion containing 1% by mass of the molecule, the average value of L* is approximately 99.7, and the average value of a* is approximately - It can be seen that the average value of b* is 5.9 and the average value of b* is about 11.7. However, in the case of a dispersion containing conventional 60 nm class cerium oxide particles, the average L* value was approximately 94. 7, and the average value of a* is approximately -2.2, and the average value of b* is approximately 0.1. Therefore, the cerium oxide particle dispersion according to the present invention has an L* value of 95 or more, and the b* value satisfies the range of 10 to 25, which is higher than the conventional 60n Compared with m-class cerium oxide particle dispersions, it has a larger L* value, so it is It has been found that the granular particles have excellent particle properties and have a larger b* value, so that it is suitable for one embodiment of the present invention. This can be interpreted as the reason why such a cerium oxide particle dispersion exhibits a higher yellow color. When the cerium oxide particles are expressed in an aqueous dispersion containing the particles in the L*a*b* color system, Those having each value within the above range and exhibiting particularly high yellowness are cerium oxide particles. The Ce on the surface of the cerium oxide particles is very fine and monodispersed. 3+ This can be interpreted as meaning that the content is relatively very high.

[0169] Experimental Example 17. Sedimentation rate of cerium oxide particles during centrifugation A slurry composition containing 1.0 wt % of cerium oxide particles according to an embodiment of the present invention, and a ratio The slurry compositions of Comparative Example 1 and Comparative Example 3 containing 1.0 wt % of cerium oxide particles were was prepared as a sample.

[0170] The sample was centrifuged in a high-speed centrifuge or an ultra-high-speed centrifuge (Supra R22 (Model name), manufactured by Hanil Science Industrial Co. Ltd. , Korea) and the temperature of the slurry composition was 25°C, and the centrifugal force was 210 Centrifugation was performed while changing the pressure to 0G, 3300G, 4265G, 26188G, and 398282G. The sedimentation rate of the cerium oxide particles at this time is shown in Table 18 below.

[0171] [Table 18]

[0172] Referring to Table 18, a slurry composition containing 1.0 wt % of each cerium oxide particle was prepared. When centrifuged, the sedimentation rate of the cerium oxide particles according to an embodiment of the present invention is It was confirmed that the sedimentation rate was lower than that of the cerium oxide particles in Comparative Examples 1 and 3. For example, when centrifuged at a centrifugal force of 4,265 G for 30 minutes, The inventive example exhibited a sedimentation rate of 0 wt. %, while Comparative Example 1 exhibited a sedimentation rate of 27.14 wt. %. In Comparative Example 3, the centrifugal force was 3,300 G, which was smaller than that, and the centrifugal force was 3,300 G for 10 minutes. It can be confirmed that the sedimentation rate is already 96.9% by weight. The particle size of the primary particles and / or secondary particles of the cerium oxide particles according to the examples of the present invention is This may mean that the particle size is finer than that of the cerium oxide particles of Comparative Example 1 and Comparative Example 3. It can also mean that the particles are monodispersed, and therefore, Since particles come into contact with the wafer during the chemical mechanical polishing process, the number of contact particles is large. It can be seen that the oxide film polishing rate is improved as a result of the above. When polishing is performed using a slurry composition containing cerium oxide particles according to the embodiment, the polished surface This means that the occurrence of polishing defects such as scratches on the wafer can be reduced. It can mean:

[0173] Experimental Example 18: Analysis of remaining amount of cerium oxide precursor The residual amount of precursor in the CMP slurry containing cerium oxide particles produced in Production Example 2 was The slurry sample of Production Example 2 was evaluated to measure the particle size. After being dried at high temperature to produce powder, the remaining powder is dissolved again in pure water. The precursor content in the solution dissolved in pure water was analyzed by ICP-MS. When converted into a weight ratio of cerium powder, most of the substances, such as basic substances, solvents, and ammonia, were It was confirmed that almost no traces were detected and that the levels were below 300 ppm. "Not contained" means that the amount contained is significantly less than the unit of PPM or less. Therefore, the cerium oxide particles are properly dispersed in the slurry. Due to the characteristics of the wet process, cerium precursors, base substances and other Since the cerium oxide particles according to an embodiment of the present disclosure contain almost no impurities, they can be easily processed by a wet process. After being produced in the form of a dispersion liquid, it is converted into a slurry solvent through a separate separation or pulverization process. It could be expected that a redispersion step would not be necessary.

[0174] [Table 19]

[0175] Experimental Example 19. Comparison of oxide film removal rate of cerium oxide particles The slurry composition of Production Example 2 according to one embodiment of the present invention, the slurry compositions of Comparative Example 1 and Comparative Example 3 Each of the compositions was prepared as a sample.

[0176] The oxide film wafer using the sample was polished using a polishing machine (Reflexion (registered trademark) The test was carried out using a standard LK CMP (Applied Materials). A PE-TEOS silicon oxide wafer (300 mm P E-TEOS Wafer) was placed on the surface of the wafer and the pad (IC10 The sample was then contacted with the slurry composition at 200 mL / ml. n speed and the platen and the polisher pad are not rotating. During this process, the rotation speed of the platen and the rotation speed of the head were The speed was 67 rpm / 65 rpm, the polishing pressure was 2 psi, and the polishing time was 60 seconds. Meanwhile, the thickness of the silicon oxide film on the wafer was measured by ST5000 (Spectra T The results are shown in Table 20 below. Ta.

[0177] [Table 20]

[0178] As shown in Table 20, when the slurry compositions of the Examples were used, Comparative Examples 1 and 3 It was confirmed that the silicon oxide film removal rate was approximately six times faster than that of the slurry composition of This is because, in the case of the cerium oxide particles contained in the slurry composition of the example, the particles Because the diameter is small, the number of particles that effectively work for polishing is large compared to the content, and the Ce on the surface 3+ Contains The amount (molar ratio and / or weight ratio) is high, which increases the chemical reactivity with the silicon oxide film surface. It is presumed that this is to add to the

[0179] Experimental Example 20. Evaluation of defects in cerium oxide particles 45 and 46 show a CMP slurry containing cerium oxide particles according to one embodiment of the present invention. and a CMP slurry composition containing 60 nm cerium oxide particles. Scanned images of a wafer before and after CMP.

[0180] The surface analysis of the oxide wafer was performed by full wafer scanning using an AIT-XP instrument ( The data was collected using the full wafer scan method.

[0181] 45 and 46, the C containing cerium oxide particles according to the embodiment of the present invention is The surface of an oxide wafer that has been CMPed using an MP slurry composition is analyzed before and after CMP. As a result, the number of defects before CMP was calculated as 6, and the number of defects after CMP was calculated as 1. From this, it can be seen that the defects on the oxide wafer surface are The surface roughness is reduced after CMP. Furthermore, scratches are generated during the CMP process. In contrast, it can be confirmed that no cerium oxide particles are generated in the prior art. The surface of an oxide wafer that had been CMPed using a CMP slurry composition containing The analysis showed that the number of defects before CMP was 34, but after CMP the number of defects increased to 64. It was confirmed that the cerium oxide particles of the prior art were added to the surface of the wafer. It can be seen that scratches have been generated on the surface. This is one embodiment of the present invention. The particle size of the cerium oxide particles according to the present invention is smaller than that of the cerium oxide particles according to the prior art. This suggests that the probability of defects occurring on the surface of the oxide wafer being polished is significantly reduced. do.

[0182] Experimental Example 21. Behavior of oxide film polishing rate and oxide film / polysilicon ratio with the addition of cationic polymer Analysis of polishing selectivity of KO film Cerium oxide particles prepared according to an embodiment of the present invention and conventional commercially available 60 nm class cerium oxide particles Cerium oxide particles were added to deionized water, the pH was adjusted to 5.8, and then the cationic polymer was added. The additives were added as shown in Table 21 below, and the oxide film (Oxid e) The polishing rate (Å / min) of the polysilicon film and the polishing rate (Å / min) of the silicon dioxide film were measured. did.

[0183] [Table 21]

[0184] Referring to Table 21, the commercially available 60 nm class cerium oxide particles of Comparative Examples 2 to 8 were used. In the slurry, 0.01 wt% of cationic polymer was added, and the polishing of the silicon oxide film was It was confirmed that the polishing speed was significantly reduced. In the case of slurries containing ammonium particles, the results of Examples 2 to 8 in Table 21 show that the cationic polymer It was confirmed that the oxide film removal rate increases because the material contains This is a feature not seen in CMP slurries that use cerium oxide particles.

[0185] Furthermore, when Example 1 in Table 21 is compared with Examples 2 to 8 containing cationic polymers, The polishing rate of the silicon oxide film increases, while the polishing rate of the polysilicon film decreases significantly. It was confirmed that the polishing selectivity of the oxide film / polysilicon film was reduced by approximately 200. It was confirmed that the range of 900 or less satisfies the range of 2000 or less.

[0186] Furthermore, the content of the cationic polymer in the samples of the examples and comparative examples in Table 21 was gradually increased. The behavior of the oxide film polishing rate (Å / min) was investigated by gradually increasing the temperature. A cationic polymer of a CMP slurry composition containing cerium oxide particles according to an embodiment The graph shows the results of measuring the behavior of the oxide film polishing rate depending on the addition of HCl.

[0187] Referring to FIG. 47 and Table 21, the polishing rate of the CMP slurry of the present invention is As the content of the polymer increases, the polishing rate also increases. In the case of slurry, if the concentration continues to increase above 0.001%, the polishing rate gradually decreases. This is because in the case of the conventional wet ceria slurry, the cation The polymer simply acts as a pH buffer and is added to stabilize the particles. Increasing the content of ionic polymers may prevent the abrasive particles from performing the polishing process. In contrast, in the case of the CMP slurry of the present invention, the cationic polymer provides particle stability. It was also found that it acts as a polishing accelerator.

[0188] [Mode for carrying out the invention]

[0189] DETAILED DESCRIPTION OF THE INVENTION The present invention may, however, be embodied in many different forms. The present invention is not limited to the embodiments described herein, but is defined by the claims below. It is simply done.

[0190] It should be noted that the terms used in the present invention are merely used to describe specific embodiments. The singular expression is used unless the context clearly indicates otherwise. Throughout the specification of this application, when a component is referred to as "comprising," the term "comprises" or "includes" is used. When a component is included in a system, this does not exclude other components unless otherwise specified. This means that it may contain further elements.

[0191] The term "monodisperse" as used herein means that when the cerium oxide particles are dispersed in a slurry, This means that aggregation into secondary particles is suppressed and the particle size of the primary particles is relatively maintained. This means that the particle size (D50) of secondary particles measured by dynamic light scattering (DLS) is The particle size of the primary particles is 3.0 times or less, 2.8 times or less, 2.5 times or less, 2.2 times or less, It can mean having a magnitude of 2.0 times or less, or advantageously 1.9 times or less. When examining particle size distribution, etc., it is important to consider the inclusion of relatively large unavoidable impurities. It's not about excluding it.

[0192] The term "transparent" as used in the present invention means that the cerium oxide particles are dispersed in the slurry. When the slurry composition is visually observed, it means that the slurry composition is observed to be transparent. More specifically, the average light transmittance for light in the visible light region is 50% or more, preferably 70%. This means that the oxidation rate of the present invention is more preferably 80% or more. Cerium particles are prevented from agglomerating into secondary particles, and the particle size of the primary particles is relatively maintained. This means that

[0193] Polishing compositions are characterized according to their polishing rate (i.e., removal rate) and their planarization efficiency. The polishing rate refers to the rate at which material is removed from the surface of a substrate and is usually expressed as a percentage per unit time. It is expressed in units of length (thickness) per minute (e.g., angstroms (Å) / minute). In this case, the polishing surface, e.g., the polishing pad, first contacts the "high points" of the surface and then the flat material must be removed to create a smooth surface. The process of achieving a flat surface requires removing more material to achieve flatness. Some processes are considered more efficient than others.

[0194] Often, the removal rate of silicon oxide patterns is higher than that of dielectric polishing in STI processes. It is possible to limit the rate for the step and therefore the silicon oxide pa A high removal rate of the turn is desirable to increase device throughput. Too fast a chip removal rate can lead to trench corrosion due to over-polishing of oxide in the exposed trench. This leads to erosion and increases the number of element defects.

[0195] The present invention will be described in detail below.

[0196] A first aspect of the present invention is cerium oxide particles for chemical mechanical polishing, the cerium oxide particles comprising: In an aqueous dispersion in which the content of rubber particles was adjusted to 1.0 wt%, the cerium oxide particles for chemical mechanical polishing, characterized in that the light transmittance is 50% or more. to provide.

[0197] The cerium oxide particles for chemical mechanical polishing according to one aspect of the present application will be described in detail below. do.

[0198] FIG. 1 shows an oxide film removal mechanism according to one embodiment of the present invention. As shown in Fig. 1, the surface of the cerium oxide particles is coated with Ce. 3+ If the ions are not activated, they will not bond smoothly to SiO2. unable to respond to

[0199] In one embodiment of the present application, the particle size of the cerium oxide particles is determined by X-ray diffraction (XRD) analysis. In one embodiment of the present application, the particle size may be measured by X-ray diffraction (XRD) analysis (primary particles). The particle size of the cerium oxide particles as measured by may be 11 nm or less. 10.8nm or less, 10.5nm or less, 10.2nm or less, 10nm or less, 9.5nm m or less, 9.0nm or less, 8.5nm or less, 8.0nm or less, 7.5nm or less, 7.0n m or less, 6.5nm or less, 6.0nm or less, 5.5nm or less, 5.0nm or less, 4.5n It may be 0.3 nm or more, 0.5 nm or more, or 0. 7nm or more, 1.0nm or more, 1.1nm or more, 1.2nm or more, 1.3nm or more, 1. 4nm or more, 1.5nm or more, 1.6nm or more, 1.7nm or more, 1.8nm or more, 1. 9nm or more, 2.0nm or more, 2.1nm or more, 2.2nm or more, 2.3nm or more, or When the particle size of the cerium oxide particles is less than 0.3 nm, the particle size may be 2.4 nm or more. However, the crystallinity may be reduced, the polishing speed for the target film may be excessively hindered, and the polishing efficiency may be reduced. On the other hand, if it exceeds 11 nm, there is a risk of a large number of surface defects such as scratches occurring. In one embodiment of the present application, the oxide cerium oxide measured by X-ray diffraction (XRD) analysis The average particle size of the lithium particles is 0.5 to 10 nm, preferably 1 to 10 nm, and more preferably It may be characterized as being 2 to 9 nm.

[0200] In another embodiment of the present disclosure, the particle size of the cerium oxide particles is measured using a transmission electron microscope (TE M) (primary particles). In one embodiment of the present application, the primary particles may be measured by a transmission electron microscope ( The particle size of the cerium oxide particles as measured by TEM may be 11 nm or less. In the example, 10.8nm or less, 10.5nm or less, 10.2nm or less, 10nm or less Bottom, 9.5nm or less, 9.0nm or less, 8.5nm or less, 8.0nm or less, 7.5nm or less Bottom, 7.0nm or less, 6.5nm or less, 6.0nm or less, 5.5nm or less, 5.0nm or less It may be 0.3 nm or more, 0.5 nm or less, 4.5 nm or less, or 4.0 nm or less. m or more, 0.7nm or more, 1.0nm or more, 1.1nm or more, 1.2nm or more, 1.3n m or more, 1.4nm or more, 1.5nm or more, 1.6nm or more, 1.7nm or more, 1.8n m or more, 1.9nm or more, 2.0nm or more, 2.1nm or more, 2.2nm or more, 2.3n The particle size of the cerium oxide particles may be 0.3 nm or more, or 2.4 nm or more. If it is less than m, the crystallinity will decrease, the polishing speed for the target film will be excessively hindered, and the polishing efficiency will decrease. On the other hand, if the thickness exceeds 11 nm, a large number of surface defects such as scratches will occur. In addition, in one embodiment of the present application, the transmission electron microscope (TEM) The average particle size of the cerium oxide particles is 0.5 to 10 nm, preferably 1 to 10 nm, More preferably, it can be characterized as being 2 to 9 nm.

[0201] In another embodiment of the present application, the particle size of the cerium oxide particles is determined by small angle X-ray scattering (SAX In one embodiment of the present application, small angle X-ray scattering (SAXS) may be used to measure the particle size (primary particles). The particle size of the cerium oxide particles measured by the SAXS method may be 15 nm or less. In other embodiments, the thickness is 14 nm or less, 13 nm or less, 12 nm or less, 11 nm or less, 10nm or less, 9.5nm or less, 9.0nm or less, 8.5nm or less, 8.0nm or less, 7 .5nm or less, 7.0nm or less, 6.5nm or less, 6.0nm or less, 5.5nm or less, 4 It may be 0.5nm or less, or 4.0nm or less, and may be 0.3nm or more, 0.5nm or more , 0.7nm or more, 1.0nm or more, 1.1nm or more, 1.2nm or more, 1.3nm or more , 1.4nm or more, 1.5nm or more, 1.6nm or more, 1.7nm or more, 1.8nm or more , 1.9nm or more, 2.0nm or more, 2.1nm or more, 2.2nm or more, 2.3nm or more The particle size of the cerium oxide particles may be less than 0.3 nm, or 2.4 nm or more. In this case, the crystallinity is reduced, the polishing speed for the target film is excessively hindered, and the polishing efficiency is reduced. On the other hand, if the thickness exceeds 15 nm, there is a risk of a large number of surface defects such as scratches occurring. In addition, in one embodiment of the present application, the small angle X-ray scattering (SAXS) method is measured. The average particle size of the cerium oxide particles is 0.5 to 15 nm, preferably 1 to 12 nm, more preferably 1.5 to 1.5 nm. More preferably, it may be characterized as being 1.5 to 10 nm.

[0202] In one embodiment of the present disclosure, the particle size of the cerium oxide particles in the slurry is determined by dynamic light scattering. The secondary particles may be measured by dynamic light scattering (DLS) analysis. This may be done by analytical equipment well known to practitioners, preferably by particle size analysis by Anton Parr. This may be done using a spectrometer or a Malvern Zetasizer Ultra. , this is only a non-limiting example and is not intended to be limiting.

[0203] In one embodiment of the present application, the cerium oxide was measured using a dynamic light scattering (DLS) particle size analyzer. The particle size of the rubber particles may be 1 to 30 nm. Below, 27nm or less, 25nm or less, 23nm or less, 22nm or less, 20.8nm or less, 20.5nm or less, 20.2nm or less, 20nm or less, 19.8nm or less, 19.5nm Even if it is 19.2nm or less, 18nm or less, 17nm or less, or 15nm or less Often, 1.2nm or more, 1.4nm or more, 1.5nm or more, 1.8nm or more, 2nm or more The particle size of the secondary particles may be greater than or equal to 3 nm, or greater than or equal to 4 nm. This means that the aggregation of primary particles occurs frequently in the slurry composition. If the particle size of the secondary particles is less than the above range, The polishing rate for the target film may be excessively hindered, resulting in a decrease in polishing efficiency.

[0204] In one embodiment, the cerium oxide particles are analyzed by a dynamic light scattering (DLS) particle size analyzer. The particle diameter of the cerium oxide particles measured by the method described above is defined as a, and the particle diameter of the cerium oxide particles measured by the method described above is defined as a. When the particle diameter of the cerium oxide particles is b, the following formula 2 is satisfied: .

[0205] [Formula 2] a≦2.2b

[0206] Such a property is due to the fact that the cerium oxide particles of the present invention do not aggregate when dispersed in a slurry. If the coefficient b exceeds 2.2, there is a lot of aggregation in the slurry. This means that the grain size becomes larger, so defects on the wafer surface are less likely to appear during polishing. This could mean that it becomes more difficult to suppress the

[0207] In another embodiment of the present application, the cerium oxide particles are dispersed in a crystalline form by dynamic light scattering (DLS) particle size analysis. The particle size of the cerium oxide particles measured by the analyzer is defined as a, and the small angle X-ray scattering (SAXS) method is used to determine the particle size. When the measured particle diameter of the cerium oxide particles is defined as b, the following formula 3 is satisfied: It is possible.

[0208] [Formula 3] a≦2.5b

[0209] Such a property is due to the fact that the cerium oxide particles of the present invention do not aggregate when dispersed in a slurry. If the coefficient b exceeds 2.5, there is a lot of aggregation in the slurry. This means that the grain size becomes larger, so defects on the wafer surface are less likely to appear during polishing. This could mean that it becomes more difficult to suppress the

[0210] In one embodiment of the present application, Ce on the surface of the cerium oxide particles 3+ The content is XPS can be analyzed using, for example, Thermo Fisher Scientific The theta probe base system manufactured by Fic Co. can be used. The surface of the cerium oxide abrasive particles can be 3+ The content is expressed by the following chemical formula 1 obtain.

[0211] [Chemical formula 1] Ce 3+ Content (%)=(Ce 3+ Peak area) / [(Ce 3+ Peak area) + (Ce 4+ Peak area)]

[0212] In one embodiment, X-ray photoelectron spectroscopy (XPS) analysis is performed on the surface of the cerium oxide particles. When doing so, Ce 3+ The XPS peak indicating the Ce-O bond energy is 900.2~ 902.2eV, 896.4~898.4eV, 885.3~887.3eV and 880 Specifically, the oxide may be characterized by appearing at 0.1 to 882.1 eV. On the surface of cerium particles, during X-ray photoelectron spectroscopy (XPS) analysis, Ce 3+ Ce-O crystals showing The XPS peaks showing combined energy are the first peak at 900.2 to 902.2 eV, the second peak at 896 The second peak at 898.4-898.4 eV, the third peak at 885.3-887.3 eV and the It may be characterized by the appearance of a fourth peak at 0.1 to 882.1 eV.

[0213] In one embodiment, the area of ​​the first peak relative to the total XPS peak area is , 3% or more, or 4% or more, and the areas of the second peak and the fourth peak are , may be 5% or more, 7% or more, or 10% or more, respectively, and the surface of the third peak The product may be 4% or more, 5% or more, or 6% or more.

[0214] In one embodiment of the present application, the cerium oxide was analyzed by X-ray photoelectron spectroscopy (XPS). The ratio of Ce to the sum of the XPS peak areas showing the Ce-O bond energy on the surface of the silicon particles 3+ The ratio of the sum of the XPS peak areas showing the Ce-O bond energy is 0.29 to 0.70. In another embodiment of the present invention, the cerium oxide The ratio of Ce to the sum of the XPS peak areas showing the Ce-O bond energy on the surface of the silicon particles 3+ The ratio of the sum of the XPS peak areas indicating the Ce-O bond energy is 0.18 or more, 0. 19 or more, 0.192 or more, 0.195 or more, 0.198 or more, 0.20 or more, 0.20 2 or more, 0.205 or more, 0.208 or more, 0.21 or more, 0.22 or more, 0.24 or more , 0.25 or more, 0.27 or more, 0.28 or more, 0.30 or more, 0.32 or more, or 0 May be 0.35 or more, 0.90 or less, 0.88 or less, 0.85 or less, 0.83 or less , 0.80 or less, 0.77 or less, 0.75 or less, 0.72 or less, 0.71 or less, 0.70 5 or less, 0.70 or less, 0.695 or less, 0.69 or less, 0.68 or less, 0.67 or less, 0.66 or less, 0.65 or less, 0.64 or less, 0.63 or less, 0.62 or less, 0.61 or less If the ratio is less than the above range, the surface of the cerium oxide particles may be Ce in sufficient quantity 3+ The oxide film removal rate is expected to increase sufficiently. If the oxidation number is exceeded, the cerium oxide particles Being a child can be difficult to interpret.

[0215] That is, in one embodiment of the present application, when analyzed by X-ray photoelectron spectroscopy (XPS), The surface of cerium oxide particles for mechanical polishing is coated with Ce. 3+ 18 atomic % or more, 19 atomic % or more, 20 atomic % or more, 22 atomic % or more, 24 atomic % or more, 25 atomic % or more, 27 atomic % or more, Even if it contains 28 atomic % or more, 30 atomic % or more, 32 atomic % or more, or 35 atomic % or more Often, 90 atomic % or less, 88 atomic % or less, 85 atomic % or less, 83 atomic % or less, 80 atomic % Contains 77 atomic % or less, 75 atomic % or less, 72 atomic % or less, or 70 atomic % or less It's fine.

[0216] In the case of cerium oxide particles according to an embodiment of the present application, Ce on the particle surface 3+ The content is high This is because the particle synthesis process is carried out in the liquid phase under acidic conditions using a wet process. This is presumed to be due to the presence of Ce on the particle surface. 3+ When the content is relatively high This can improve the oxide film removal rate.

[0217] In one embodiment of the present application, the cerium oxide particles according to an embodiment of the present invention are Ce on the particle surface distinguishes it from other abrasive particles. 3+ It implies that a large amount of an ingredient is included Specifically, the cerium oxide particles exhibit two or more Raman spectral features. The optical fiber may be characterized by having a peak spectrum.

[0218] In one embodiment, the cerium oxide particles have a particle size of 455 cm -1 ~460cm -1 In another embodiment, the first Raman peak may be in the band range of Cerium oxide particles have a molecular mass of 586 cm -1 ~627cm -1 A second Raman peak in the band range of In yet another embodiment, the cerium oxide particles may have a surface area of ​​712 cm -1 ~772cm -1 The third Raman peak may be in the band range of The band range is the Raman shift, which is the X-axis of the Raman spectrum. It may refer to a range of numbers.

[0219] In one embodiment, the cerium oxide particles have the second Raman peak intensity (B) The ratio (A / B) of the first Raman peak intensity (A) to the second Raman peak intensity (B) is 35 or less. The A / B ratio is preferably 30 or less, more preferably 25 or less, and even more preferably The lower limit of the A / B ratio is not particularly limited, but may be The second Raman peak may be 5 or more, 10 or more, or 15 or more. 3+ Contains As the amount of oxygen increases, the proportion of oxygen vacancies increases. This can be interpreted as the Raman shift that occurs when The smaller the ratio (A / B), the more the Ce in the cerium oxide particles. 3+ This means that the content increases This can be achieved by chemical polishing using Si-O-Ce bonding with an oxide film wafer. This promotes the effect of the present invention, and the particle size of the present invention is smaller than that of conventional cerium oxide particles. It can be suggested that the polishing rate can be improved when the cerium oxide particles according to the embodiment are used.

[0220] In one embodiment, the cerium oxide particles have a third Raman peak intensity (C The ratio (A / C) of the first Raman peak intensity (A) to the second Raman peak intensity (A) is 50 or less. The A / C may be preferably 45 or less, more preferably 43 or less. The lower limit of the A / C is not particularly limited, but is preferably 5 or more, 10 or more, or 15 or more. may be.

[0221] As described above, the cerium oxide particles according to an embodiment of the present application have a higher molecular weight than conventional cerium oxide particles. Ce 3+ It contains a high content of cerium oxide, so despite its small particle size, It is possible to provide a slurry composition having a superior polishing rate compared to the amount of the additive, and also to prevent polishing scratches. The occurrence of can be suppressed.

[0222] In one embodiment of the present application, Ce on the surface of the cerium oxide particles 3+ Content and related and can be analyzed using electron energy loss spectroscopy (EELS), e.g. For example, 2 or more, Ce 4+ The EELS peak indicates an oxidation state of Ugh.

[0223] The cerium oxide particles (and / or a slurry composition containing the same) are as shown in FIGS. 23 to 25. Such an EELS spectrum can be shown.

[0224] The EELS spectrum of the cerium oxide particles according to one embodiment of the present application is 876.5 to 8 The first peak of 86.5 eV and the second peak of 894.5 to 904.5 eV are included, The maximum intensity of the first peak may be greater than the maximum intensity of the second peak. This phenomenon is due to the Ce of cerium oxide particles. 3+ The higher the content, the more trivalent cerium oxide This may mean that the EELS spectrum is similar to that of

[0225] In one embodiment of the present application, the spectrum has a third peak at 886.5 to 889.5 eV. The sample may further include a fourth peak at 904.5 to 908.5 eV. In the case of the third and fourth peaks, it is possible to distinguish the peaks according to their oxidation states. 4+ Oxidation of The area of ​​the peak section that appears depending on the state is calculated to determine the cerium oxide particles of the present invention. A distinction can be made between the cerium oxide particles and conventional cerium oxide particles.

[0226] In one embodiment of the present application, the sum of the total areas of the peaks in the spectrum (P t ) The ratio (P1 / P t ) is 0.025 or less It may be 0.024 or less, more preferably 0.022 or less, 0.018 or less, 0. It may be 0.015 or less, 0.012 or less, 0.011 or less, or 0.01 or less. In contrast, conventional cerium oxide particles exhibit a minimum value of 0.03 or more, and This will be illustrated by the following experimental examples.

[0227] In one embodiment of the present application, the sum of all areas of the peaks in the spectrum (P t ) The ratio of the sum of the areas of the third peak section (P1) to the sum of the areas of the fourth peak section (P2) ( (P1+P2) / P t ) may be 0.1 or less. The area ratio is preferably is 0.099 or less, 0.098 or less, 0.096 or less, 0.095 or less, 0.094 or less , 0.092 or less, or 0.090 or less. For example, when the same sample is measured n times, the ratio of sodium particles is calculated by the n measurements. The ratio of the areas ((P1 + P2) / P t ) are other examples The values ​​shown are 0.01 or more, 0.012 or more, 0.014 or more, 0.016 or more, or 0.0 When the area ratio is 0.1 or less, the cerium oxide particles Ce relative to the total cerium oxide content at the surface of the 3+ It means that the content is high It is higher than Ce 3+ The content is Si-O-Ce relative to the silicon oxide film. The bonding promotes the chemical polishing action, thereby increasing the polishing rate.

[0228] The cerium oxide particles according to one embodiment of the present application are distinguished from conventional abrasive particles. Ce on the particle surface 3+ XAFS (Xr ay absorption fine structure) spectral characteristics. Specifically, the cerium oxide particles have two or more peaks in the XAFS spectrum. It may be characterized by the fact that

[0229] In one embodiment of the present application, cerium oxide particles (and / or a slurry composition containing the same) The XAFS spectrum of the SiO2-based ...

[0230] In one embodiment, the cerium oxide particles have an XAFS spectrum of 5730 eV or more. The maximum optical absorption coefficient of the first peak may be in the range of less than 5740 eV, Ku is Ce 3+ It may also be one which exhibits the oxidation state of

[0231] In yet another embodiment, the cerium oxide particles have a 574 The second peak may have a maximum optical absorption coefficient in the range of 0 eV or more and less than 5760 eV, The second peak is Ce 4+ It may also be one which exhibits the oxidation state of

[0232] In one embodiment of the present application, the maximum optical absorption coefficient of the first peak (maximum value of the peak) is 0. In another embodiment, the maximum light absorption of the first peak may be 1 to 0.4. The coefficients are 0.11 or more, 0.12 or more, 0.13 or more, 0.14 or more, 0.15 or more, 0 It may be 0.2 or more, or 0.25 or more, and may be 0.38 or less, 0.35 or less, 0.32 or less, or may be 0.30 or less.

[0233] In one embodiment, the maximum optical absorption coefficient of the second peak (maximum value of the peak) is 0 In another embodiment of the present application, the maximum optical absorption coefficient of the second peak may be less than 0.6. The numbers are 0.11 or more, 0.12 or more, 0.13 or more, 0.14 or more, 0.15 or more, 0.2 or more, or 0.25 or more, and may be 0.58 or less, 0.55 or less, or 0.52 or less , or may be 0.50 or less.

[0234] When the optical absorption coefficient of the first peak is less than 0.1 and when the optical absorption coefficient of the second peak is When the ratio of Ce to the total weight of the cerium oxide surface is more than 0.6, 3+ Weight reduction This means that the polishing rate may be further inhibited.

[0235] In one embodiment, the area of ​​the second peak (A2 The ratio (A1 / A2) of the area of ​​the first peak (A1) to the area of ​​the second peak (A2) may be 0.03 or more. The peak area ratio (A1 / A2) is 0.03 or more, 0.05 or more, or 0.07 or more. , 0.09 or more, or 0.1 or more, more preferably 0.11 or more, and even more preferably It may be 0.12 or more. on fine structure) spectrum 3+ The area of ​​the peak A 3 and Ce 4+ The sum of the areas A4 of the peaks showing Ce 3+ The area of ​​the peak A3 The ratio (A3 / (A3 + A4)) may be 0.1 or more (10% or more). When is less than 0.03, the Ce on the surface of the cerium oxide particle 4+ Compared to the content of Ce 3+ Content This may result in a decrease in the polishing rate.

[0236] In one embodiment of the present application, the cerium oxide particles are subjected to photoelectron spectroscopy. Specifically, UV photoelectron spectroscopy (UPS) uses light in the UV region. t photoelectron spectroscopy (PET) analysis can be performed Photoelectron spectroscopy techniques have traditionally been based on X-ray photoelectron spectroscopy (XPS), which uses a single wavelength of light in the X-ray range. :X-ray photoelectron spectroscopy) and UV region UV photoelectron spectroscopy (UPS) using light XPS is divided into 1000-1500e X-rays with energies of about V are used to detect the core level of atoms inside the sample. The electrons emitted from the sample are analyzed to determine the type, chemical state, concentration, etc. of the elements in the sample. Many commercial devices are available for sale, and the analytical methods and usage are widely known. While the UPS is well known for its extreme ultraviolet radiation of about 10-20 eV, The electrons in the valence electron region of the sample are charged using light in the UV region. The number of electrons that can be present in a solid that directly participate in chemical bonds by releasing electrons In particular, the so-called angle-resolved UPS ( ved UPS, ARUPS / ARPES) can directly measure the band structure of single crystal samples. Therefore, such measurements are an important factor in understanding the unique properties of materials, such as high-temperature superconductivity. It can be used to understand the physical properties of conductors and colossal magnetoresistive materials. When light with an energy of 1000 keV is shone on the electron, the electrons move while satisfying the law of conservation of energy and momentum. At this time, the kinetic energy of the electrons that leave the sample is The value of is given as follows:

[0237] E kin =hv-φ-|E b |

[0238] where Ekin is the kinetic energy of the emitted electron, and φ is the work function of the sample (work function), E b is the binding energy when the emitted electron is bound to the sample (binding energy). By measuring the intensity of the kinetic energy of the emitted electrons, the binding energy of the electrons inside the sample can be determined. The density of states due to energy can be grasped. Therefore, referring to the equation above, the binding energy can be derived from the measured kinetic energy: At this time, the work function φ of the sample is determined by the hv value of the source energy and the Lumi level (E F ) and vacuum level (E cutoff ) can be expressed as

[0239] φ=hv-|E f -E cutoff |

[0240] When the UPS results are plotted on a graph, the zero on the x-axis is the Fermi level of the sample. (E F ) and E cutoff is expressed by the vacuum level hv is the source energy used to emit ultraviolet light. e energy) and indicates the energy of incident light, but universally, as a source Helium (He) can be used.

[0241] In one embodiment of the present application, the band structure of the cerium oxide varies depending on the grain size (particle size). Therefore, the smaller the particle size (particle size), the greater the energy difference between the sample orbits. The difference between the energy levels becomes larger and larger, resulting in a high energy band gap. On the other hand, as the particle size increases, the difference in energy levels gradually decreases, and the lower the energy level, the Therefore, as mentioned above, the smaller the grain size, the larger the valence band gap. The energy gap between the conduction band and the Fermi level (E F ) and vacuum level (va The energy (eV) of the derived work function is calculated by changing the value of the It can be increased.

[0242] In one embodiment, the cerium oxide particles are released per second during UPS analysis. The maximum number of photoelectron counts is in the range of kinetic energy below 10 eV. Such a property is a characteristic that is in contrast to that of conventional ceria particles. The maximum number of photoelectrons emitted per second is The potential can be in the range of 6 to 10 eV, or 7 to 10 eV, preferably 8 to 10 eV. V range.

[0243] In one embodiment of the present application, the cerium oxide particles are The work function value may be in the range of 2.5 eV or higher. The work function value is preferably in the range of 2.7 eV or more, more preferably 3.0 e The upper limit of the work function value is not particularly limited, and The work function value may be less than 10 eV, 9 eV or less, or 8 eV or less. is a feature that is in contrast to conventional cerium oxide particles, and This means that the particle size of the cerium oxide particles dispersed in the This indicates that the particles have small aggregation and are monodispersed. The cerium oxide particles according to one embodiment of the present disclosure are contained in a slurry for chemical mechanical polishing. When used, it can maximize the number of particles that come into contact with the wafer, thereby increasing the oxide film polishing rate. At the same time, the grain size itself becomes finer, minimizing defects on the wafer surface. It is expected that this will be possible.

[0244] In one embodiment of the present application, the specific surface area of ​​1 g of the powder made of cerium oxide particles is When measured, the BET surface area value was 50m 2 In another embodiment, the ionic liquid may be 0.15g or less. The BET surface area value is 49 m 2 / g or less, 48m 2 / g or less, 47m 2 / g or less, 46m 2 / g or less, 45m 2 / g or less, 44m 2 / g or less, 43m 2 / g or less, preferably is 42m 2 / g or less, since the smaller the particle size, the larger the BET surface area. This shows a tendency different from that of conventional cerium oxide particles, which have a high sol-sol ratio. -Cerium oxide particles synthesized by self-assembly synthesis methods such as the gel method and bottom-up method , which has a smaller specific surface area and pore volume than cerium oxide particles produced by other synthetic methods. This is thought to be due to the low ratio of -OH functional groups present on the surface of cerium oxide particles. In addition, the particle size is smaller than that of conventional cerium oxide particles. When 1.0 g of the powder was analyzed by BET under the same conditions, the conventional oxide ceramic according to Comparative Example 1 The powder sample is more densely aligned than the sodium particles, and the measured BET surface area is smaller. Therefore, the cerium oxide particles according to the examples of the present invention are comparable to those of Comparative Example 1. Although the particle size is finer than the conventional 10 nm class cerium oxide particles, It was confirmed that the BET surface area was smaller than that of the cerium oxide particles of Comparative Example 1. The results are comparable to those of the cerium oxide particles according to the present invention compared with the conventional cerium oxide particles. Compared with the crystalline silicon, it has a finer particle size and at the same time, Ce is present on the particle surface. 4+ and -O The content of Ce compared to the content of H functional groups 3+ The same tendency as the surface chemical characteristics of high content It can be understood in context.

[0245] In one embodiment of the present application, the apparent density of the cerium oxide particles measured by a static method The concentration may be 2.00 to 5.00 g / ml, preferably 2.00 to 5.00 g / ml. 4.00 g / ml, more preferably 2.00 to 3.00 g / ml. Good too.

[0246] In another embodiment of the present application, the apparent viscosity of the cerium oxide particles measured by the Tab method is It can be characterized by a density of 2.90 to 5.00 g / ml, preferably 3. 0.00 to 5.00 g / ml, more preferably 3.20 to 5.00 g / ml. It is possible.

[0247] The slurry of cerium oxide particles having an apparent density of more than 5.00 g / ml dispersed in water When Lee is used for polishing, scratches are generated on the polished surface due to the particle size of the coarse primary and secondary particles. In one embodiment of the present application, the cerium oxide particles are less than 2.00 g / ml. When using a particle size reduction agent, the polishing speed becomes extremely slow as the particle size of the primary particles decreases. Even if the particle size is small, such as 10 nm or less, the polishing effect may not be achieved. It is preferable to maintain an apparent density of 0 g / ml or greater. The cerium oxide particles according to the present invention have a fine particle size, but are more effective than conventional cerium oxide particles. It can be seen that there is a difference in the apparent density of the material. It is expected that this will also have a certain effect on the polishing rate of the oxide film.

[0248] In one embodiment of the present application, the content of the cerium oxide particles is adjusted to 1.0 wt %. The photoluminescence intensity (PL) was measured at a wavelength of 325 nm based on the dispersion. When measuring the luminescence intensity, the maximum intensity of the first peak (λ1) at wavelengths of 435 to 465 nm is 0 It is important to note that the ranges are expressed as 0.1 to 30, 0.2 to 20, 0.3 to 10, or 0.5 to 7. In the case of conventional coarse cerium oxide particles, the maximum peak intensity was 3 Although it exceeds 0, the cohesion in the slurry is also strong, so light emission occurs more strongly than transmission. This could mean:

[0249] In one embodiment of the present application, the content of the cerium oxide particles is adjusted to 1.0 wt %. Based on the dispersion, the maximum intensity of the second peak (λ2) at wavelengths of 510 to 540 nm is 0.1 to 1 It may be characterized by being expressed in the range of 0, 0.1 to 7.5, 0.1 to 5, or 0.1 to 3. In the case of conventional coarse cerium oxide particles available on the market, the maximum peak intensity is 10 However, the cohesion in the slurry is also strong, so light emission occurs more strongly than transmission. It can mean:

[0250] In one embodiment of the present application, the content of the cerium oxide particles is adjusted to 1.0 wt %. The photoluminescence intensity (PL) of the dispersion was measured at a wavelength of 325 nm. ce) can be measured to understand the characteristics of the particles. Fluorescence spectroscopy was performed at 325 nm. When analyzing r), the excitation peak (λ exc ) appears, and 435 The first peak (λ1) appears at wavelengths of up to 465 nm, and the second peak appears at wavelengths of 510 to 540 nm. The excitation peak (λ2) may appear. The first peak is Ce 3+ The second peak indicates Ce. 4+ of This could be interpreted as indicating

[0251] In one embodiment of the present invention, the content of the cerium oxide particles is adjusted to 1.0 wt %. For aqueous dispersion, the photoluminescence intensity (PL) was measured at a wavelength of 325 nm. When measuring the excitation peak (λ exc ) , the intensity ratio of the first peak (λ1) at wavelengths of 435 to 465 nm (λ1 / λ exc ) but 30 less than 27, preferably 25 or less, more preferably 23 or less, and even more preferably Preferably, it is 18 or less, 15 or less, and even more preferably, it may be 10 or less.

[0252] In one embodiment of the present application, the pre-treatment for the second peak (λ2) of 510 to 540 nm wavelength is The intensity ratio (λ1 / λ2) of the first peak (λ1) is 4 or more, preferably 5 or more, more preferably It may be 5.5 or more, more preferably 6 or more, and may be 20 or less, preferably 18 or less. or less, more preferably 15 or less, even more preferably 12 or less, and even more preferably 10 It may be the following:

[0253] The cerium oxide particles according to an embodiment of the present disclosure have the excitation peak (λ exc ) to the first Peak (λ1) intensity ratio (λ1 / λ exc ) and the second peak (λ2) When the intensity ratio (λ1 / λ2) of the peak (λ1) is satisfied within the above range, the cerium oxide The surface of the titanium particles contains a high content of Ce. 3+ Although it contains The Ce content on the particle surface is very low, resulting in good light transmission. 3+ Content In the case of the cerium oxide particles of the present invention, When used in a chemical mechanical polishing slurry, Ce on the particle surface 3+ High content, but particles The cerium oxide particles themselves are very fine and have very little agglomeration in the slurry. The chemical polishing rate is increased by the Si-O-Ce bond between the molecule and the oxide film substrate, It can be seen that the rate improves.

[0254] In one embodiment, the yellowness index of the dispersion containing the cerium oxide particles is L*a The L*a*b color system was established in 1976 by the CIE (Commission Internationable de Eclairage) It is defined by the CIE1976 L*a*b* color space established by the International Commission on Illumination (CIE1976). This color space is defined in a rectangular coordinate system by the quantities L*, a*, and b*, which are determined by the following formula: It is a color space that has

[0255] L*=116(Y / Y0) 1 / 3 -16 a*=500[(X / X0) 1 / 3 -(Y / Y0) 1 / 3 ] b*=200[(Y / Y0) 1 / 3 -(Z / Z0) 1 / 3 ] (However, X / X0, Y / Y0, Z / Z0>0.008856, X, Y, Z are the three values ​​of the object color. The stimulus values, X0, Y0, and Z0, are the tristimulus values ​​of the light source that illuminates the object color, and are standardized to Y0=100. It is standardized.

[0256] L* indicates brightness, also known as the "lightness index." Also, a* and b* indicate hue and saturation. It is also called the "chromaticity index." In the *a*b* color system, the larger the L* value, the closer to white the color is, and the smaller the L* value, the closer to black the color is. The larger the a* value is on the positive side, the stronger the reddish color becomes, and the smaller the a* value is on the negative side, the stronger the reddish color becomes. The greener the color, the more the b* value increases. The yellow color becomes stronger, and the smaller it becomes (towards the - side), the blue color becomes stronger. Furthermore, if both the a* and b* values ​​are 0, the color is achromatic.

[0257] In one embodiment of the present application, the content of the cerium oxide particles is adjusted to 1.0 wt %. When the color of the dispersion is expressed in the L*a*b* color system, the L* value is 80 or more, preferably 85 or more. , more preferably 90 or more, even more preferably 95 or more, and even more preferably 98 or more If the L* value is smaller than the above range, the particle growth of the cerium oxide abrasive particles may be The polishing is too advanced, resulting in a large number of coarse particles that cause defects on the wafer during polishing. The L* value is preferably 100 or less, more preferably 99.9 or less. The present invention may be characterized by the above.

[0258] In one embodiment of the present application, the b* value is 8 or more, preferably 10 or more, and more preferably may be 11 or more, but less than 30, preferably 25 or less, more preferably 20 or less, More preferably, the b* value is in the range of 15 or less. If it is smaller than this, the necessary chemical reaction during polishing will not occur, and the fine irregularities on the polished surface will not be polished smoothly. There is a risk that it will not be polished.

[0259] In one embodiment of the present application, the a* value is less than -3, preferably less than -4, more preferably may be -5 or less, and is -8 or more, more preferably -7 or more. It may also be possible to use the following.

[0260] Therefore, the color of the aqueous dispersion in which the content of the cerium oxide particles was adjusted to 1.0 wt % was When expressed in the L*a*b* color system, if each value is within the above range, the dispersion is yellow. The more yellow the dispersion is, the more improved the removal rate is. In particular, the cerium oxide particles according to one embodiment of the present application are fine particles. Regardless of particle size, when included in a chemical mechanical polishing slurry, oxide ceramics Ce on the surface of sodium 3+ The high ratio of SiO2 makes the polishing speed of oxide film extremely high, and the polishing speed of fine oxide film is high. The particles can minimize defects on the wafer surface, and the L*a When expressed in the *b* color system, each value is within the above range, or the yellowness is particularly high. This means that compared to conventional cerium oxide particles, the surface of cerium oxide particles has a higher Ce content. 3+ ratio of This can be interpreted as meaning that the level is relatively very high.

[0261] In one embodiment of the present application, the content of the cerium oxide particles is adjusted to 1.0 wt %. The dispersion was centrifuged at a centrifugal force of 4265G (6,000 rpm) for 30 minutes. The sedimentation rate of the cerium oxide particles may be 25% by weight or less. The sedimentation rate is 20% by weight or less, 15% by weight or less, 10% by weight or less, and more preferably 5% by weight or less. It may be the following:

[0262] In one embodiment of the present application, the content of the cerium oxide particles is adjusted to 1.0 wt %. The aqueous dispersion was centrifuged at a centrifugal force of 2100G (3,200 rpm) for 10 minutes. In another embodiment, the sedimentation rate of the cerium oxide particles may be 0.6 wt % or less. The sedimentation rate is preferably 0.55% by weight or less, more preferably 0.5% by weight or less, even more preferably 0.45% by weight or less. Preferably, it may be 0.4% by weight or less.

[0263] In another embodiment of the present application, the content of the cerium oxide particles is 1.0 wt %. The prepared aqueous dispersion was centrifuged at a centrifugal force of 3300G (4,000 rpm) for 30 minutes. When the cerium oxide particles are mixed, the sedimentation rate of the cerium oxide particles may be 5.0 wt % or less. In this case, the sedimentation rate is preferably 4.8% by weight or less, 4.5% by weight or less, 4.2% by weight or less, and more preferably Preferably, it may be 4.0% by weight or less.

[0264] In another embodiment of the present application, the content of the cerium oxide particles is 1.0 wt %. The prepared aqueous dispersion was centrifuged at a centrifugal force of 26188G (12,000 rpm) for 30 minutes. The sedimentation rate of the cerium oxide particles when separated may be 45.0% by weight or less. In one embodiment, the settling rate is 42% by weight or less, 40% by weight or less, 38% by weight or less, or more preferably ... Preferably, it may be 35% by weight or less.

[0265] In another embodiment of the present application, the content of the cerium oxide particles is 1.0 wt%. The aqueous dispersion was centrifuged at a centrifugal force of 39,282 G (18,000 rpm) for 30 minutes. The settling rate of the cerium oxide particles after centrifugation may be 90.0% by weight or less. In one embodiment, the sedimentation rate is 80% by weight or less, 70% by weight or less, 65% by weight or less, or more preferably 100% by weight or less. More preferably, it may be 60% by weight or less.

[0266] In one embodiment of the present application, the liquid viscosity of the aqueous dispersion is 0.3 to 2.0 mPa·s, 0. 5 to 1.8 mPa·s, 0.55 to 1.5 mPa·s, or 0.6 to 1.2 mPa·s In a preferred embodiment, the solution is centrifuged under conditions of 0.65 to 1.2 mPa·s. This can be done.

[0267] In this way, when the mixture was centrifuged under various conditions from weak to severe centrifugal force, When the settling rate of the cerium oxide particles is within the above ranges, it is possible to provide an embodiment of the present invention. The cerium oxide particles have a finer particle size than conventional cerium oxide particles and are monodispersed. Therefore, the chemical mechanical polishing process can be performed with monodisperse particles on the wafer. As the number of contacting particles increases, the oxide film polishing speed can be expected to improve. When polishing is performed using the embodiment of the present invention having a fine particle size, the occurrence rate of polishing defects can be reduced. You can see that.

[0268] In one embodiment of the present application, the cerium oxide primary particles are spherical, cubic, shape, tetragonal shape, orthorhombic Shape, Rhombohedral shape, Monoclini c) Shape, hexagonal shape, triclinic shape and one selected from the group consisting of cuboctahedron shape The particles may be larger than 10 ...

[0269] In one embodiment of the present application, the cerium oxide particles are grown by chemical synthesis. It can be produced by a method such as the bottom-up method. The cerium oxide particles may be synthesized by a method such as sol-gel ) method, supercritical reaction, hydrothermal reaction, coprecipitation method, etc. can be used. The bottom-up method is a type of chemical synthesis that has been attracting attention in recent years, and is It is a method of growing starting materials such as molecules or atoms into nanometer-sized particles through chemical reactions. .

[0270] In one embodiment, the polishing composition includes wet cerium oxide particles. The cerium particles can be any suitable wet cerium oxide particles. For example, wet cerium oxide particles The cerium oxide particles include colloidal cerium oxide particles, precipitated cerium oxide particles or polycondensed cerium oxide particles. It may also be cerium particles.

[0271] In one embodiment of the present application, the wet cerium oxide particles also preferably have no defects on the surface of the particles. Without wishing to be bound by any particular theory, the cerium oxide particles Milling can introduce defects on the surface of the cerium oxide particles, and these defects can also It also affects the performance of the cerium oxide particles in the chemical mechanical polishing composition. Cerium particles can be fractured during milling, exposing less favorable surface conditions. This process is known as relaxation. , limited restructuring ability and limited more favorable surface area around the cerium oxide particles. Atoms with the ability to return to their original state cause defects to form on the particle surface.

[0272] In one embodiment of the present application, in generating secondary particles of the abrasive, each solvent has a specific dielectric constant The dielectric constant of the solvent determines the surface energy The aggregation and growth of nuclei are affected by changing the particle size and surface charge. The dielectric constant of the solvent and the surface of the particles dispersed in the solvent affect the particle size and shape. The potentials (zeta potentials) are proportional to each other, If the surface potential is low, the surface repulsion between the fine particles or between the nuclei generated by the reaction Because they are small, they are unstable and aggregation between fine particles or nuclei occurs at a very fast rate. In this case, the magnitude of the surface repulsion force is about the same between the fine particles or between the nuclei, It is possible to form agglomerates of uniform size. The agglomerated secondary particles react to temperature, concentration, etc. Depending on the application conditions, the strong agglomeration of the primary fine particles and nuclei and Oswald ripening Through particle merging processes such as opening, the particles grow into relatively large particles.

[0273] A second aspect of the present invention is a method for producing a cerium oxide particle-containing composition comprising: cerium oxide particles; and a solvent; In an aqueous dispersion in which the content was adjusted to 1.0 wt%, the light transmittance to light with a wavelength of 500 nm was A slurry composition for chemical mechanical polishing is provided, characterized in that the passivity is 50% or more. do.

[0274] Detailed explanations of parts that overlap with the first aspect of the present application will be omitted, but The contents described above can be applied to the second aspect even if the description is omitted.

[0275] The chemical mechanical polishing slurry composition according to the second aspect of the present application will be described in detail below. do.

[0276] According to one embodiment of the present disclosure, the chemical mechanical polishing slurry composition comprises cerium oxide particles and Contains a solvent.

[0277] In one embodiment of the present application, the cerium oxide particles contained as abrasive particles in a slurry is a positive zeta potential value, preferably 1 to 80 mV, 5 to 60 mV, 1 in the pH range of 2 to 8 The zeta potential value of the cerium oxide particles may be positive. When the polarity of the silicon oxide film surface is negative, the cerium oxide particles and silicon oxide The polishing efficiency can be increased by the attractive force between the surface of the oxide film and the surface of the metal oxide.

[0278] In one embodiment of the present application, the cerium oxide particles are more preferable than silica particles or alumina particles. It has low hardness, but the chemical bond formed between silica and cerium is Si-O-Ce. The polishing mechanism allows for extremely fast polishing of silicon-containing surfaces such as glass and semiconductor substrates. This is advantageous for polishing semiconductor substrates.

[0279] In one embodiment, the content of the precursor material in the slurry composition is In another embodiment of the present application, the slurry composition may contain 300 ppm or less based on the total amount of ammonium nitrate. The content of precursor substances contained in the above is 200 ppm or less, 150 ppm or less, by weight. 100ppm or less, 75ppm or less, 50ppm or less, 25ppm or less, 15ppm or less , 10ppm or less, 7.5ppm or less, 5ppm or less, 2.5ppm or less, 2ppm or less , 1.75ppm or less, 1.5ppm or less, 1.25ppm or less, 1ppm or less, 0.7 The slurry composition may contain 5 ppm or less, or 0.5 ppm or less. The precursor material may be a cerium precursor material, a basic Substances, solvents, and ammonia used in the wet process to produce cerium oxide particles and the precursor materials produced.

[0280] In one embodiment of the present application, the chemical mechanical polishing slurry composition contains The present invention may be characterized in that the cerium oxide particles are contained in an amount of 5% by weight or less. In some embodiments, the chemical mechanical polishing slurry composition may comprise the acid based on the total weight of the composition. Cerium oxide particles are 4% by weight or less, 3% by weight or less, 2% by weight or less, 1.5% by weight or less, % or less, 0.8% by weight or less, 0.5% by weight or less, 0.4% by weight or less, 0.3% by weight or less , 0.2% by weight or less, less than 0.2% by weight, 0.19% by weight or less, 0.15% by weight or less, 0 .12% by weight or less, 0.10% by weight or less, 0.09% by weight or less, or 0.07% by weight or less It may be below 0.001% by weight or above or may be 0.001% by weight or above. The chemical mechanical polishing slurry composition of the present invention is used in a manner that allows the use of slurries having the same polishing rate. However, the amount of cerium oxide based on the total weight of the slurry composition for chemical mechanical polishing is It is characterized by the fact that it can achieve high oxide film polishing efficiency even when added in an amount smaller than that of rubber particles. Good too.

[0281] In one embodiment of the present invention, the content of the cerium oxide particles is adjusted to 1.0 wt %. In aqueous dispersion, the average light transmittance for light with wavelengths of 450 to 800 nm is 50% or more. or 60% or more, preferably an average light transmittance of 70% or more, More preferably, it may be 80% or more, and even more preferably, it may be 90% or more. In another embodiment, the light transmittance for light with a wavelength of 500 nm is 50% or more, 55% or more above, 60% or more, 65% or more, 70% or more, 75% or more, or 80% or more The optical transmittance for light with a wavelength of 600 nm may be 75% or more, and 80% or more. Furthermore, the wavelength of 70 The light transmittance for 0 nm light is 87% or more, 90% or more, 93% or more, or 95% or more. The light transmittance of the slurry composition may be in the above range. That is, the particle size of the primary particles of the cerium oxide particles according to an embodiment of the present invention is small, This may also mean that the agglomeration into secondary particles is less than that of conventional ceria particles. When the agglomeration is low, the particles can be uniformly distributed due to high dispersion stability, and the particles can be easily contacted with the wafer. Since the particles come into contact with the surface of the oxide film, the polishing speed is excellent. When a film to be polished is polished using a slurry composition containing It is easy to estimate that the probability of occurrence will decrease. In the case of the cerium oxide particles shown below, the higher the light transmittance in the visible light region, the better the silicon oxide film It can be predicted that the polishing rate will be good.

[0282] In one embodiment of the present application, the powder made of cerium oxide particles is subjected to Fourier transform infrared radiation. External line (Fourier-transformation infrared, FT-IR ) spectroscopy, the 30 in the spectrum identified by the FT-IR spectroscopy 00cm -1 ~3600cm -1 In the range of The transmittance is 90% or more, or 100% or less, 97% or less, or 95% or less. In one embodiment of the present application, -1 ~770c m -1 In the range of 8, the infrared transmittance of the powder may be 96% or less, 5% or more, 88% or more, more preferably 90% or more, and even more preferably 92% or more. The FT-IR spectrum of 3000 cm -1 ~3600cm -1 In the range of The infrared transmittance having a value within the above range means that the band due to the OH group is relatively weak. This can be seen from the FT-IR spectrum of the powder made of cerium hydroxide particles. Furthermore, the FT-I of the powder made of cerium oxide particles according to one embodiment of the present application is shown. R spectrum 720 cm -1 ~770cm -1 In the range, the peaks showing the infrared transmittance in the range are The presence of this gap indicates that Ce-O stretching occurs in the above range. This may mean that the particles produced according to one embodiment of the present invention are oxidized cerium. It can also mean that the material exhibits the properties of lithium particles.

[0283] In one embodiment of the present application, the chemical mechanical polishing slurry composition has dispersion stability and From the viewpoint of polishing efficiency, the pH is 10 or less, preferably 1 to 9, 1 to 8, or 2 to 7. More specifically, if the pH is less than 1, the removal rate of the silicon oxide film decreases rapidly. and may exhibit undesirable abrasive properties, and a pH above 10 may The polishing properties are not satisfactory, or the pH stability and dispersion stability are reduced, causing aggregation. This can cause micro-scratches and defects.

[0284] In one embodiment of the present disclosure, the chemical mechanical polishing slurry composition comprises a final polishing step. One or more acids or bases that can adjust the pH taking into consideration H, polishing rate, polishing selectivity, etc. The pH adjusting agent may contain a pH adjusting agent and a buffering agent. The present invention relates to a method for adjusting the pH of a chemical mechanical polishing slurry composition without affecting its properties. In one embodiment of the present application, the pH adjusting agent can be used to achieve a suitable pH. The pH adjusting agent may be an acidic or basic pH adjusting agent for achieving the desired pH.

[0285] In one embodiment of the present application, examples of the pH adjuster include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and the like. one or more inorganic acids selected from the group consisting of acetic acid, citric acid, glutaric acid, glycolic acid , formic acid, lactic acid, malic acid, malonic acid, maleic acid, oxalic acid, phthalic acid, succinic acid, tartaric acid one or more organic acids selected from the group consisting of lysine, glycine, alanine, arginine, leucine, valine, leucine, isoleucine, methionine, cysteine, proline, histidine , phenylalanine, serine, tricine, tyrosine, aspartic acid, tryptophan ( Tryptophan, one or more amino acids selected from the group consisting of aminobutyric acid; Midazole; Alkylamines; Alcoholamines; Quaternary amine hydroxides; Ammonium or a combination thereof. In particular, the pH adjusting agent is triethanoic acid. amine, tetramethylammonium hydroxide (TMAH or TMAOH) or may be tetraethylammonium hydroxide (TEAH or TEA-OH). Examples of the pH adjuster include ammonium methylpropanol (AMP). mmonium methyl propanol), tetramethylammonium hydrochloride Tetra methyl ammonium hydroxide (TMAH) ), potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, hydroxide Cesium chloride, sodium bicarbonate, sodium carbonate, triethanolamine, tromethamine At least one selected from the group consisting of niacinamide and niacinamide is preferred. Alternatively, the pH adjusting agent may be triethanolamine or aminobutyric acid.

[0286] In one embodiment of the present application, the solvent is used in a slurry composition for chemical mechanical polishing. Any suitable water can be used, for example, deionized water. However, the present invention is not limited to this. Preferably, ultrapure water is used. The content of the solvent in the entire slurry composition for chemical mechanical polishing is The remaining amount excluding the content of the cerium oxide particles and other additional additives is In one embodiment of the present application, the solvent is water (e.g., deionized water) as an aqueous carrier. and may contain one or more water-miscible organic solvents. Examples of organic solvents that can be used include alcohols (e.g., propenyl alcohol, isopropyl alcohol, Alcohol, ethanol, 1-propanol, methanol, 1-hexanol, etc.); Dehydes (e.g., acetylaldehyde, etc.); ketones (e.g., acetone, diacetone aldehyde, etc.); ethanol, methyl ethyl ketone, etc.); esters (e.g., ethyl formate, propyl formate, mate, ethyl acetate, methyl acetate, methyl lactate, butyl lactate, ethyl lactate, etc.); sulfoxides (e.g., dimethyl sulfoxide (DMSO)); Ethers (e.g., tetrahydrofuran, dioxane, diglyme, etc.); amides (e.g., N,N-dimethylformamide, dimethylimidazolidinone, N-methylpyrrolidone, etc.) Polyhydric alcohols and their derivatives (e.g., ethylene glycol, glycerol (glycerol) glycerin), diethylene glycol, diethylene glycol monomethyl ether, etc.); and nitrogen-containing organic compounds (e.g., acetonitrile, amylamine, isopropylamine) , dimethylamine, etc.) may be included.

[0287] In one embodiment of the present application, the polishing composition optionally further contains one or more other additives. The polishing composition further comprises a thickener and a coagulant (e.g., a polymer such as a urethane polymer). surfactants and / or rheology modifiers, including biocides (e.g., KATHON TMLX). Suitable surfactants include, for example, cationic surfactants Surfactants, anionic surfactants, anionic polyelectrolytes, nonionic surfactants, amphoteric surfactants, fluorinated surfactants, mixtures thereof, and the like.

[0288] In one embodiment of the present application, the chemical mechanical polishing slurry composition has excellent dispersion stability. It is characterized by a particularly high polishing rate for silicon oxide films.

[0289] The chemical mechanical polishing slurry composition comprises cerium oxide particles, a solvent, and other additives. It may be provided in the form of a one-liquid slurry composition containing all the components such as the agent, and if necessary These ingredients are stored in two or more containers, and then used at the time of use or are provided in the form of two-component or three-component slurry compositions that are mixed near the point of use. The selection of such a presentation form and the combination of storage components are within the knowledge of one skilled in the art. The overall polishing characteristics and polishing rate can be adjusted by changing the mixing ratio. This can be done.

[0290] In one embodiment of the present disclosure, the chemical mechanical polishing slurry composition has a thickness of 1,000 Å / min or more, preferably 2,000 Å / min or more, more preferably 3,000 Å / min or more n or more silicon oxide film polishing rate, and basically the oxide film polishing rate is high. The lower the flow rate, the better. There is no particular upper limit, but it is preferably 10,000 Å / min or less, and 900 0Å / min or less, 8000Å / min or less, 7000Å / min or less, 6000Å / m It is characterized by a silicon oxide film polishing rate of 5000 Å / min or less. In particular, the chemical mechanical polishing using cerium oxide particles according to an embodiment of the present disclosure may be performed. In the case of a slurry composition for use, even if the content of cerium oxide particles is low, the particle size (particle size) Since the particle size is small, the particles contained are smaller than those in conventional slurry compositions containing cerium oxide particles. The number of atoms is large, and the surface Ce 3+ The Si-O-Ce bond increases with the content, This significantly improves the polishing rate of the silicon oxide film.

[0291] In one embodiment of the present application, the chemical mechanical polishing slurry composition has a pH of 50 to 100. The polishing selectivity of the oxide film / polysilicon film is 0 or more, 150 or more, or 200 or more. It is acceptable to have 3,000 or less, 2,000 or less, 1,500 or less, 1,000 or less, 900 or less, or a polishing selectivity of an oxide film / polysilicon film of 800 or less. In the case of oxide film / polysilicon film selectivity, the content of cationic polymer should be appropriately adjusted. It cannot be excluded that selectivity ratios of 3,000 or more can be achieved by adjusting the It would be.

[0292] When the cerium oxide is used as an abrasive, only the hydrated layer formed on the surface is removed. Unlike mechanical polishing, the high reactivity of cerium oxide and silicon oxide allows for the formation of Si-OC The chemical bond e occurs, and cerium oxide peels off the silicon oxide clumps on the surface of the silicon oxide film. The silicon oxide film is polished by removing it as follows. The powder has low strength due to its small particle size, and therefore has excellent wide-area flatness during polishing. In addition, it has the advantage of being able to solve the problem of micro-scratches formed by large particles. be.

[0293] Another aspect of the present invention is a method for producing a cerium oxide coating comprising: cerium oxide particles; a solvent; and a cationic polymer. The present invention provides a slurry composition for chemical mechanical polishing, characterized by:

[0294] In one embodiment of the present application, the oxide film polishing rate increases depending on the content of the cationic polymer. This may be characterized by the fact that the chemical mechanical polishing method of the present invention is improved compared to the prior art. These are the main technical features of the slurry composition and will be described in detail below.

[0295] In one embodiment of the present application, the cationic polymer is a compound selected from the group consisting of hydroxyl groups, hydroxypropyl ... The cationic polymer may serve two purposes in the composition. First, it may contribute to the stability of the slurry composition. It can act as a stabilizer and as a pH buffer to stabilize particles. The cationic polymer of the present invention can ensure dispersibility and dispersion stability. In conventional polishing slurries, the dispersion stability is high. In order to prevent this, cationic polymers are added, and the field oxide film (FOD) is removed during step removal. In order to protect the ion exchange reaction, cationic polymers were used. To obtain these characteristics, it was necessary to sacrifice some of the oxide film polishing speed. The cationic polymer added to the polishing slurry of the present invention not only enhances the dispersion stability, but also The more the amount of cationic polymer added, the more the polishing speed of the entire oxide film can be increased. This will be possible.

[0296] In one embodiment of the present application, the content of the cationic polymer is 0.001% by weight or more, 0.002% by weight or more, 0.00% by weight or more, based on the total weight of the composition It may be 3% by weight or more, 0.004% by weight or more, or 0.005% by weight or more, Weight % or less, 0.5 weight % or less, 0.1 weight % or less, 0.05 weight % or less, 0.03 weight % % or less, or 0.01% by weight or less. If the content is less than 0.001% based on the total weight of the chemical mechanical polishing slurry composition, If the amount is too small, it cannot fully function as a polishing accelerator, which affects the polishing rate. On the other hand, if it exceeds 1%, the added cationic polymer will not react with cerium oxide. This may interfere with the polishing process and may even reduce the polishing rate.

[0297] In one embodiment of the present application, the cationic polymer has an amine group or an ammonium group. For example, in one embodiment of the present application, The cationic polymer is polydiallyldimethylammonium chloride (pol ydiallyldimethyl ammonium chloride), polyaryl Polyallylamine, polyethyleneimine leneimine), polydiallylamine, poly Polypropyleneimine, polyacrylamide co-diallyldimethylammonium chloride (polyacrylamide-co -diallydimethyl ammonium chloride), polyacrylic polyacrylamide, or a combination thereof. Preferably, polydiallyldimethylammonium chloride (poly diallyldimethyl ammonium chloride), polyallyl Amine (polyallylamine), polyethyleneimine (polyehthyl eneimine), polyacrylamide-co-diallyldimethylammonium chloride polyacrylamide-co-diallydimethyl ammo sodium chloride), polyacrylamide , poly(trimethylammonioethyl methacrylate) ammonio ethyl methacrylate), dicyandiamide-diethyl Diethylenetriamine copolymer (dicyandiamide-diethylenetriamine Diallyldimethylamine / hydrochloride-acrylamide copolymer, Polymer(dialyldimethylamine / hydrochloride-a crylamide copolymer), dicyandiamide-formaldehyde copolymer Copolymer (dicyandiamide-formaldehyde copolymer) or a combination thereof.

[0298] A third aspect of the present invention is a step of polishing using the above-mentioned chemical mechanical polishing slurry composition. A method for manufacturing a semiconductor device including a chip is provided.

[0299] Detailed explanations of the parts overlapping with the first and second aspects of the present application will be omitted. The contents explained in the first and second aspects are equally applicable to the third aspect even if the explanation is omitted. It is possible.

[0300] The method for manufacturing a semiconductor device according to the third aspect of the present application will be described in detail below.

[0301] First, shallow trench isolation (STI) The routine process for insulating film planarization is explained as follows: Among the processes for this purpose, photolithography, etching, and polishing are commonly used. These can be classified as basic processes used in

[0302] The first step is a photo process to separate the elements. The circuit pattern is formed by exposing the light to an auxiliary device called a track. First, a photosensitive material (Photo R) is applied to the wafer. However, since the photosensitive agent has high viscosity, the wafer is rotated while the insulating layer is applied. The photoresist is applied thinly onto the insulating film. The applied photoresist is applied in a manner that allows the photoresist to have an appropriate depth. It must be of uniform height. If the photoresist is not deep enough during exposure, it may become too thick during development. Residues of photoresist remain on the surface, and the underlying film (insulating layer) is not sufficiently removed in the subsequent etching process. After exposure, the wafer is returned to the track device and the exposed area is removed. A development process is carried out.

[0303] In the second step, STI etching is performed on the developed area (where the photoresist film is removed). The process involves removing the insulating layer (oxide layer + nitride layer) directly below the insulating layer (the part that has been removed) and a part of the substrate. The etching process can be a dry or wet process. The chipping method is a method of digging down using a plasma state. Compared to the (liquid) method, the side walls are not etched (anisotropic etching) and the hole is dug downwards In this case, over-etching can be advantageous for adjusting the shape of the trench. Over-etching may occur, so it is important to accurately calculate the etching end point. After etching, residues will remain, so it is necessary to deal with them. This can be done.

[0304] After the trench shape is etched, the photosensitive layer is no longer useful and is removed by ashing. In the ashing process, it is preferable to In this case, plasma can be used, and high-precision ashing can be performed. The shape of the semiconductor element up to the bonding process is shown in Figure 2.

[0305] According to an embodiment of the present disclosure, there is provided a method for manufacturing a semiconductor device, comprising: simultaneously polishing the silicon oxide film, the silicon nitride film, and the polysilicon film using may also include:

[0306] 2 to 6 are cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment of the present application.

[0307] Referring to FIG. 2, a trench 13 may be formed in an upper film 11 on a lower film 10. For example, An upper film 11 is formed on the lower film 10, and a nitride film (polishing stop film) 12 is formed on the upper film 11. The lower film 10 may comprise a film of any material. For example, the lower film 10 may be an insulating film. The upper film 11 may be an insulating film, a conductive film, a semiconductor film, or a semiconductor wafer (substrate). , an insulating film (oxide film), a conductive film, a semiconductor film, or a combination thereof. .

[0308] When the upper film 11 includes a plurality of laminated insulating films, the insulating films may be of the same type but different. For example, the upper film 11 may be a film of silicon oxide and a silicon dioxide film alternately stacked. The upper film 11 may include a silicon oxide film and a silicon nitride film. The semiconductor layer and the lower insulating layer may be further included under the oxide layer. It may be disposed below the semiconductor film.

[0309] The nitride film (polishing stop film) 12 is made of, for example, silicon nitride (e.g., SiN), polysilicon, A relatively large thickness (e.g., 100 Å) is deposited on the substrate by vapor deposition of silicon, metal nitride (e.g., TiN), metal, etc. The trench 13 may be formed to have a thickness of about 4,000 Å or less. The trench 13 may be formed by a drilling process. 2 and the upper film 11 to reach the lower film 10. The wrench 13 may be deep enough to expose the underlying membrane 10 .

[0310] Referring to Figure 3, STI can form two oxide layers. First, a space is created. Before the insulating material is fully filled into the trench 13, a liner is formed as a first insulating film 14. (Liner) A thin oxide film is applied by diffusion. In the subsequent step, CVD deposition is performed. It is determined that this is to ensure that the second insulating film using According to another embodiment of the present application, trenches are formed by high density plasma CVD (HDPCVD). When implanting 13, it also serves to prevent damage from high-energy plasma. According to an embodiment of the present application, the first insulating film (liner oxide film) can be formed in a diffusion furnace (F By injecting oxygen gas into the urnace and heating it to a high temperature, thin films such as gate oxide are formed. According to another embodiment of the present disclosure, a nitride film may be used instead of an oxide film. You may do so.

[0311] Referring to FIG. 4, a first insulating film 14 is formed by depositing a plurality of insulating materials to fill the trench 13. The first insulating film 14 and the second insulating film 15 may be formed. According to an embodiment of the present invention, the first insulating film 14 may have a high density. The first insulating film 15 may be formed by depositing an insulating material, and the second insulating film 16 may be formed by depositing a low-density insulating material. For example, the first insulating film 14 is formed by depositing and patterning a high density plasma (HDP) oxide. The first insulating film 14 may be formed by forming a thin film on the inner surface of the trench 13. For example, the first insulating film 14 may be formed in an upwardly open U-shape or a pipe shape. It may have a round shape.

[0312] Since the first insulating film 14 has a high density, voids are unlikely to occur within the first insulating film 14. This eliminates or significantly reduces cracks caused by voids during subsequent heat treatment processes. The second insulating film 15 is polished while filling the trench 13 in which the first insulating film 14 is formed. A tetraethyl orthosilicate (TEOS) oxide film was formed to a thickness sufficient to cover the stop film 12. The second insulating film 15 can be formed by evaporation. The evaporation rate of the second insulating film 15 is faster than that of the first insulating film 14. Since the deposition rate of the second insulating film 15 is fast, the trench 13 may be formed by the second insulating film 15. 15 and can be filled relatively quickly.

[0313] According to another embodiment of the present application, although not shown, a second insulating film 15 is formed on the trench 13. The second insulating film 15 can be partially removed to leave the insulating film 15. For example, a photolithography process and and etching processes to define or define specific areas such as cell memory areas of semiconductor devices. In order to open the second insulating film 15, the second insulating film 15 may be selectively removed. A part or all of the second insulating film 15 on the polishing stop film 12 is removed, and a second insulating film 15 is formed on the trench 13. The insulating film 15 may be left. The step of opening the specific region is selectively performed. It may be performed, but is not necessarily executed.

[0314] Referring to FIG. 5, a planarization process may be performed on the second insulating film 15. For example, a chemical The second insulating film 15 may be planarized using a chemical mechanical polishing (CMP) process. The polishing process may be continued until the nitride film (polishing stop film) 12 is exposed. This step may be performed after forming the second insulating film 15 shown in FIG. The surface of the protective film 12 is relatively flat, or if not flat, the unevenness is large. Therefore, the chemical mechanical polishing process can be easily carried out.

[0315] 6, the nitride film may then be removed to form the STI. The purpose of this is to protect the upper film 11 so that it is not affected by the first insulating film 14. The upper film 11 is a gate oxide film that is required to be thin and reliable, so it is difficult to handle. When removing the nitride film by wet etching, the wafer must be chemically dissolved. It is also possible to immerse the substrate in a liquid to etch only the nitride film without etching the oxide film. A solution having a high selectivity (etching ratio) to the nitride film can be used. In another embodiment of the present application, the nitride film can also be removed by CMP. Although etching the oxide film is not necessary, it may cause physical damage to the oxide film. Therefore, it is preferable to chemically treat the nitride film by etching to protect the oxide film.

[0316] According to another embodiment of the present application, the chemical mechanical polishing (CMP) process is a gap fill process. After polishing, the first insulating film 14 and the second insulating film 15 on the nitride film (polishing stop film, 12) are completely removed. This removes the active area and the field area. As shown in Figure 7, it can be divided into three steps. can be done.

[0317] In the first step, a bulk of the second insulating film 15 is formed on a platen. Local planarization is performed while CMP is being performed. In the second step, the platen The second insulating film 15 with the reduced difference is cleaned or polished (Polishing), and the nitride film (polishing) is removed. The polishing is stopped when the polishing stop film 12 is exposed. End Point Detection (EPD) is used to detect the exposure of different types of film. In the third step, the platen is used to detect the time when the nitride film (polishing stop film) 12 is polished. The residue of the second insulating film 15 that may remain is removed, and the nitride film and oxide film are polished. Targeting may also be performed.

[0318] FIG. 8 shows the structure of a chemical mechanical polishing (CMP) equipment according to one embodiment of the present application. The equipment is characterized by the fact that it is composed of three platens. The STI CMP polishing may be performed step by step through steps 1, 2, and 3. After polishing, the product is moved to the cleaning section, where cleaning is completed and the process ends.

[0319] In addition, in a method for manufacturing a semiconductor device according to an embodiment of the present disclosure, the chemical mechanical The polishing slurry composition is used to polish silicon oxide films, silicon nitride films, and polysilicon films. The polishing method is not limited, and may be any conventional polishing method commonly used. Any of these can be used as long as the conditions are met, and the present invention is not particularly limited.

[0320] The chemical mechanical polishing slurry composition according to an embodiment of the present application has high dispersion stability. The cerium oxide particles contained in the slurry composition have a high Ce content on their surfaces. 3+ The content Therefore, the chemical polishing mechanism between silica and cerium to form Si-O-Ce is used. It can increase the polishing rate on silicon-containing substrates, even under conditions with a low ceria content. It is particularly effective in removing silicon oxide films from the surface of semiconductor devices in the CMP process. It can be used for the following purposes.

[0321] A fourth aspect of the present invention is a semiconductor device, comprising: a substrate; and an insulating material filled on the substrate. a trench formed by polishing the surface of the substrate with a chemical mechanical polishing slurry composition; At least one selected from the group consisting of a silicon oxide film, a silicon nitride film, and a polysilicon film The chemical mechanical polishing slurry composition is produced by polishing at least one film, cerium oxide particles; and a solvent; wherein the content of the cerium oxide particles is 1.0 wt %. In the prepared aqueous dispersion, the light transmittance for light with a wavelength of 500 nm is 5550% or more. The present invention provides a semiconductor device characterized by:

[0322] Detailed explanations of the parts that overlap with the first to third aspects of the present application will be omitted. The contents explained in the third aspect may be applied to the fourth aspect even if the explanation is omitted. do.

[0323] A fifth aspect of the present invention provides a method for producing a precursor of a material, the method comprising the steps of: preparing a precursor of a material; and The cerium oxide particles are crushed or precipitated to prepare cerium oxide particles for chemical mechanical polishing. obtaining a dispersion; and adjusting the content of the cerium oxide particles to 1.0 wt %. In aqueous dispersion, the light transmittance for light with a wavelength of 500 nm is 50% or more. The present invention provides a method for producing cerium oxide particles for chemical mechanical polishing.

[0324] Detailed explanations of the parts overlapping with the first to fourth aspects of the present application will be omitted. The contents explained in the fourth aspect may be applied to the fifth aspect even if the explanation is omitted. do.

[0325] In one embodiment of the present application, the step of preparing a source precursor may be included. The precursor material is any precursor material capable of producing cerium oxide particles as a product. It can be used without restrictions.

[0326] In one embodiment of the present application, cerium oxide particles are milled or precipitated in a solution containing a raw material precursor. to obtain a dispersion of cerium oxide particles for chemical mechanical polishing. The step of pulverizing the cerium oxide particles in the solution containing the raw material precursor may be, for example, The crushing method can be determined within the scope of the common technical knowledge of a person skilled in the art. The cerium oxide particles are precipitated in a solution containing a raw material precursor. In the case of the step of obtaining a dispersion of cerium oxide particles by subjecting the mixture to a reaction, a step of removing the supernatant liquid or The method may further include a filtering step.

[0327] In one embodiment of the present application, the cerium precursor is cerium ammonium nitrate, cerium nitrate, Cerium, ammonium cerium sulfate, cerium acetate, cerium chloride, cerium hydroxide, acid The metal oxide may be at least one selected from the group consisting of cerium oxide and cerium chloride.

[0328] In one embodiment of the present application, the filtering step may be performed using a non-limiting filtering device, such as: More preferably, it may be carried out using a filter device to which a membrane is applied. In the case of cerium oxide particles manufactured by the method according to one embodiment of the present invention, the cerium oxide particles Not only is the synthesis itself highly efficient, but most of the cerium precursor material can be synthesized without additional filtration steps. It can be understood that it is removed by step.

[0329] The above description of the present invention is given by way of example only and is intended to be illustrative and not restrictive of the principles of the present invention. Any person skilled in the art would be able to easily understand the technical concept and essential features of the present invention without changing the specific features. It will be understood that the above-described embodiments can be easily modified into various forms. It should be understood that the examples are intended in all respects to be illustrative and not restrictive. For example, components described as unitary may also be implemented in a distributed manner. Similarly, each component described as distributed is also a combined component. It can be implemented in the form.

[0330] The scope of the present invention is defined by the claims that follow, and the meaning of the claims All modifications and variations derived from the concept of equivalents are included in this must be construed as being within the scope of the invention. [Industrial Applicability]

[0331] In the case of the cerium oxide particles according to one embodiment of the present invention, Ce on the surface of the cerium oxide 3+ of By increasing the ratio, the amount of SiO2 contained in the chemical mechanical polishing slurry can be increased despite its small particle size. When the content of SiO2 is low, a high oxide film removal rate can be achieved.

[0332] Furthermore, according to one embodiment of the present invention, surface defects on the wafer can be minimized, which is superior to conventional methods. Surface defects and oxide film removal rate, which were previously considered to be in a trade-off relationship, Unlike the correlation between Cerium oxide particles for a slurry composition for chemical mechanical polishing and the slurry composition can be provided.

[0333] Furthermore, according to one embodiment of the present invention, the oxide film polishing rate is increased by adding a cationic polymer. It can be seen that the selectivity of the oxide film / polysilicon film increases at the same time. The addition of ionic polymers usually sacrifices the polishing rate to ensure other properties. Considering the current common technical knowledge, this can be said to be a unique effect of the present invention.

[0334] The effects of the present invention are not limited to the above-mentioned effects, and the detailed description or claims of the present invention will be omitted. It should be understood that the scope of the invention includes all effects that can be deduced from the structure of the invention as described in the claims. It is.

Claims

1. Cerium oxide particles for chemical mechanical polishing, comprising: 455 cm －１ ~460cm －１ and having a first Raman peak in the band range of 586 cm －１ ~627cm －１ and further having a second Raman peak in the band range of The ratio (A / B) of the first Raman peak intensity (A) to the second Raman peak intensity (B) is 25 or less. In an aqueous dispersion in which the content of the cerium oxide particles is adjusted to 1.0 wt %, the light transmittance for light with a wavelength of 500 nm is 50% or more, Cerium oxide particles for chemical mechanical polishing, characterized in that the particle size of the cerium oxide particles measured with a dynamic light scattering (DLS) particle size analyzer is defined as a and the particle size of the cerium oxide particles measured with a transmission electron microscope (TEM) is defined as b, and the particle size of the cerium oxide particles satisfies the following formula 1: [Formula 1] a≦2.2b.

2. 2. The cerium oxide particles for chemical mechanical polishing according to claim 1, wherein an average light transmittance for light having a wavelength of 450 to 800 nm is 50% or more in an aqueous dispersion in which the content of the cerium oxide particles is adjusted to 1.0 wt %.

3. 2. The cerium oxide particles for chemical mechanical polishing according to claim 1, wherein the secondary particle diameter of the cerium oxide particles is 1 to 30 nm as measured by a dynamic light scattering (DLS) particle size analyzer.

4. 2. The cerium oxide particles for chemical mechanical polishing according to claim 1, wherein the secondary particle diameter of the cerium oxide particles is 1 to 20 nm as measured by a dynamic light scattering (DLS) particle size analyzer.

5. 2. The cerium oxide particles for chemical mechanical polishing according to claim 1, wherein the primary particle diameter of the cerium oxide particles is 0.5 to 11 nm when analyzed by X-ray diffraction (XRD).

6. 712 cm －１ ~772cm －１ 2. The cerium oxide particles for chemical mechanical polishing according to claim 1, further having a third Raman peak in the band range of .beta.

7. 7. The cerium oxide particles for chemical mechanical polishing according to claim 6, wherein the ratio (A / C) of the first Raman peak intensity (A) to the third Raman peak intensity (C) is 50 or less.

8. Cerium oxide particles for chemical mechanical polishing, comprising: Ce by X-ray absorption fine structure (XAFS) spectroscopy ３＋ The area of ​​the peak (A ３ ) and Ce ４＋ The area of ​​the peak (A ４ ) for the sum of Ce ３＋ The area of ​​the peak (A ３ ) ratio (A ３ / (A ３ +A ４ ) is 0.03 or more, In an aqueous dispersion in which the content of the cerium oxide particles is adjusted to 1.0 wt %, the light transmittance for light with a wavelength of 500 nm is 50% or more, Cerium oxide particles for chemical mechanical polishing, characterized in that the particle size of the cerium oxide particles measured with a dynamic light scattering (DLS) particle size analyzer is defined as a and the particle size of the cerium oxide particles measured with a transmission electron microscope (TEM) is defined as b, and the particle size satisfies the following formula 2: [Formula 2] a≦2.2b.

9. 9. The cerium oxide particles for chemical mechanical polishing according to claim 8, wherein the cerium oxide particles have a first peak with a maximum optical absorption coefficient in the range of 5730 eV to 5740 eV when measured by X-ray absorption fine structure (XAFS) spectroscopy, and the first peak has a maximum optical absorption coefficient of 0.1 to 0.

4.

10. 9. The cerium oxide particles for chemical mechanical polishing according to claim 8, wherein the maximum optical absorption coefficient of the second peak is in the range of 5740 eV to 5760 eV when measured by X-ray absorption fine structure (XAFS) spectroscopy, and the maximum optical absorption coefficient of the second peak is less than 0.

6.

11. The cerium oxide particles according to claim 1 or claim 8, a solvent; 1. A chemical mechanical polishing slurry composition comprising:

12. 12. The chemical mechanical polishing slurry composition of claim 11, wherein the cerium oxide particles are present in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total slurry composition.

13. 12. The chemical mechanical polishing slurry composition of claim 11, wherein the pH of the composition is 2 to 10.

14. 12. The chemical mechanical polishing slurry composition of claim 11, wherein the chemical mechanical polishing slurry composition comprises one or more inorganic acids selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; one or more organic acids selected from the group consisting of acetic acid, citric acid, glutaric acid, glycolic acid, formic acid, lactic acid, malic acid, malonic acid, maleic acid, oxalic acid, phthalic acid, succinic acid, and tartaric acid; one or more amino acids selected from the group consisting of lysine, glycine, alanine, arginine, valine, leucine, isoleucine, methionine, cysteine, proline, histidine, phenylalanine, serine, tricine, tyrosine, aspartic acid, tryptophan, and aminobutyric acid; imidazole; alkylamines; alcoholamines; quaternary amine hydroxides; ammonia; or combinations thereof.

15. 12. The chemical mechanical polishing slurry composition of claim 11, wherein the solvent is deionized water.

16. 12. The chemical mechanical polishing slurry composition of claim 11, wherein the chemical mechanical polishing slurry composition has a polishing rate of silicon oxide film of 1,000 to 5,000 Å / min.

17. A method for manufacturing a semiconductor device, comprising a step of polishing with the chemical mechanical polishing slurry composition of claim 11.

18. providing a feedstock precursor; grinding or precipitating cerium oxide particles in a solution containing the raw material precursor to obtain a dispersion of cerium oxide particles for chemical mechanical polishing; Including, 9. The method for producing cerium oxide particles for chemical mechanical polishing according to claim 1, wherein the aqueous dispersion in which the content of the cerium oxide particles is adjusted to 1.0 wt % has a light transmittance of 50% or more for light with a wavelength of 500 nm.

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