Abrasive particle dispersion for semiconductor polishing process, abrasive slurry composition, and method for manufacturing semiconductor device

Abstract

An embodiment provides an abrasive particle dispersion, which comprises: water; ceria particles; a dispersant; a dispersion aid having a higher pKa than the dispersant; a low-molecular-weight stabilizer; a high-molecular-weight stabilizer; and a pH adjusting agent, and has a pH of 7 to 9 and a zeta potential of -25 mV to -50 mV.

Description

Abrasive particle dispersion for semiconductor polishing process, polishing slurry composition and method for manufacturing semiconductor devices

[0001] The present invention relates to a polishing particle dispersion for a semiconductor polishing process, a polishing slurry composition, and a method for manufacturing a semiconductor device.

[0002] Chemical Mechanical Polishing (CMP) is a technology that polishes a sample surface to a desired level by injecting a polishing slurry at the interface between the polishing pad and the target surface while causing friction between the pad and the target surface. Modern CMP has become an essential technology for the manufacturing of large-scale semiconductor integrated circuits, planarizing the surfaces of devices such as transistors and interlayer insulating films in multilayer wiring, planarizing various film types such as oxide and nitride films, and forming tungsten or copper wiring. As the integration of semiconductor devices increases and chip sizes decrease, the surface structure of semiconductor devices becomes more complex, and the steps between the layers become larger. Therefore, high-resolution lithography and atomic-level planarization technologies are required for the Chemical Mechanical Polishing (CMP) process applied to the semiconductor device manufacturing process. This CMP process utilizes both physical friction and chemical reactions to planarize the film. Even slight variations in the process components and / or process solutions used can produce drastically different polishing results. Consequently, the precision required for the manufacturing and design of these process components and / or process solutions is continually improving. This semiconductor polishing process is disclosed in Korean Patent No. 10-0946421, among others.

[0003] The present invention seeks to provide an abrasive particle dispersion having improved dispersion stability, resistance to pH shock, and appropriate control of polishing rate, selectivity, and polishing profile in a polishing process.

[0004] In addition, the present invention seeks to provide an abrasive particle dispersion having improved dispersion stability, improved long-term storage stability, and improved process stability, and appropriately controlling the polishing rate, selectivity, and polishing profile in a polishing process.

[0005] In one embodiment, an abrasive particle dispersion comprises water; ceria particles; a dispersant; a dispersing aid having a lower pKa than the dispersant; a stabilizer; and a pH regulator, and has a pH of 7 to 9 and a zeta potential of -25 mV to -50 mV.

[0006] In an abrasive particle dispersion according to one embodiment, the dispersing aid may include a pyridine derivative, and the dispersing agent may include polyacrylic acid.

[0007] In an abrasive particle dispersion according to one embodiment, the zeta potential change rate (ZR) expressed by the following mathematical formula 1 may be -7 mV to 0.

[0008] [Formula 1]

[0009] ZR = (Z8 - Z6) / 2

[0010] Here, Z8 is the zeta potential of the abrasive particle dispersion at pH 8, and Z6 is the zeta potential of the abrasive particle dispersion at pH 6.

[0011] In one embodiment, the abrasive particle dispersion may have a zeta potential of -33 mV to -43 mV at pH 7.

[0012] In the abrasive particle dispersion according to one embodiment, the dispersant may have a pKa that is 0.1 to 5 higher than the dispersing aid.

[0013] In the abrasive particle dispersion according to one embodiment, the dispersing aid may have a molecular weight of 10,000 to 100,000 and a pKa of 1 to 6.

[0014] In an abrasive particle dispersion according to one embodiment, the dispersant may surround the ceria particles, and the dispersing aid may surround the dispersant.

[0015] In the abrasive particle dispersion according to one embodiment, the pKa difference between the dispersant and the dispersing aid may be 0.4 to 1.5.

[0016] In the abrasive particle dispersion according to one embodiment, the dispersant may be included in an amount of 0.1 to 0.3 parts by weight based on 100 parts by weight of the water.

[0017] A polishing slurry composition according to an embodiment comprises water; ceria particles; a dispersant; a dispersing aid having a lower pKa than the dispersant; a stabilizer; and a pH regulator, and has a pH of 7 to 9 and a zeta potential of -25 mV to -50 mV.

[0018] A method for manufacturing a semiconductor device according to an embodiment comprises the steps of preparing a semiconductor substrate; spraying a polishing slurry composition onto the semiconductor substrate; and polishing the semiconductor substrate, wherein the polishing slurry composition comprises water; ceria particles; a dispersant; a dispersing aid having a lower pKa than the dispersant; a stabilizer; and a pH regulator, and has a pH of 7 to 9 and a zeta potential of -25 mV to -50 mV.

[0019] An abrasive particle dispersion according to one embodiment comprises water; ceria particles; an anionic dispersant; a nonionic dispersion stabilizer; and a pH regulator, and has a pH of 7 to 9 and a zeta potential of -25 mV to -50 mV.

[0020] In an abrasive particle dispersion according to one embodiment, the dispersion stabilizer may include polyethylene glycol or ethylene glycol, and the dispersant may include polyacrylic acid.

[0021] In the abrasive particle dispersion according to one embodiment, the pH change (△p) expressed by the following equation 1 may be 0.11 to 2.

[0022] [Formula 1]

[0023] △p = │p0 - p14│

[0024] Here, p0 is the initial pH of the abrasive particle dispersion, and p14 is the pH after the abrasive particle dispersion is left at a temperature of 60°C for 14 days.

[0025] In the abrasive particle dispersion according to one embodiment, the polyethylene glycol may have a molecular weight of 200 g / mol to 5000 g / mol.

[0026] In an abrasive particle dispersion according to one embodiment, the particle size change rate (SR) expressed by the following mathematical formula 2 may be 0.001 to 0.05.

[0027] [Formula 2]

[0028] SR = │S0 - S14│ / S0

[0029] Here, S0 is the initial particle diameter of the abrasive particle dispersion, and S14 is the particle diameter after the abrasive particle dispersion is left at a temperature of 60°C for 14 days.

[0030] In the abrasive particle dispersion according to one embodiment, the increase in agglomeration expressed by the following equation 3 may be only 3000 particles / ml.

[0031] [Formula 3]

[0032] △A = ( A7 - A0 )

[0033] Here, A0 is the number of aggregated ceria particles having a particle size of 0.69 μm to 1.01 μm in the abrasive particle dispersion, and A7 is the number of aggregated ceria particles having a particle size of 0.69 μm to 1.01 μm after the abrasive particle dispersion is left at a temperature of 60°C for 7 days.

[0034] A polishing slurry composition according to an embodiment comprises a polishing particle dispersion, wherein the polishing particle dispersion comprises water; ceria particles; an anionic dispersant; a nonionic dispersion stabilizer; and a pH regulator, and has a pH of 7 to 9 and a zeta potential of -25 mV to -50 mV.

[0035] In a polishing slurry composition according to one embodiment, the pH change (△ps) expressed by the following equation 4 may be 0.11 to 2.

[0036] [Formula 4]

[0037] △ps = │ps0 - ps14│

[0038] Here, ps0 is the initial pH of the polishing slurry composition, and ps14 is the pH after the polishing slurry composition is left at a temperature of 60°C for 14 days.

[0039] In a polishing slurry composition according to one embodiment, the particle size change rate (SRS) expressed by the following equation 5 may be 0.001 to 0.05.

[0040] [Formula 5]

[0041] SRS = │SS0 - SS14│ / SS0

[0042] Here, SS0 is the initial particle diameter of the polishing slurry composition, and SS14 is the particle diameter after the polishing slurry composition is left at a temperature of 60°C for 14 days.

[0043] A method for manufacturing a semiconductor device according to an embodiment comprises the steps of: preparing a semiconductor substrate; spraying a polishing slurry composition onto the semiconductor substrate; and polishing the semiconductor substrate, wherein the polishing slurry composition comprises a polishing particle dispersion, and the polishing particle dispersion comprises water; ceria particles; an anionic dispersant; a nonionic dispersion stabilizer; and a pH regulator, wherein the pH of the polishing particle dispersion is 7 to 9, and the zeta potential of the polishing particle dispersion is -25 mV to -50 mV.

[0044] The abrasive particle dispersion according to the embodiment comprises a dispersant and a dispersing aid having a lower pKa than the dispersing aid. Accordingly, the abrasive particle dispersion according to the embodiment can improve the dispersibility of ceria particles while simultaneously appropriately controlling the zeta potential by using the dispersant and the dispersing aid.

[0045] The abrasive particle dispersion according to the embodiment may have a negative zeta potential while improving the dispersibility of ceria particles. For example, the abrasive particle dispersion according to the embodiment may have a zeta potential of -25 mV to -50 mV at a pH of 7 to 9.

[0046] In addition, since the abrasive particle dispersion according to the embodiment includes the dispersant and the dispersing aid, it can have an appropriate zeta potential change rate. Accordingly, when an additive composition is added to the abrasive particle dispersion according to the embodiment to prepare a polishing slurry composition, the zeta potential change due to pH shock can be minimized.

[0047] In addition, the polishing slurry composition prepared using the polishing particle dispersion according to the embodiment can have low zeta potential change and low particle size change even when left at high temperatures for a long period of time. Accordingly, the polishing slurry composition according to the embodiment can have improved stability with respect to changes over time.

[0048] In addition, since the abrasive particle dispersion according to the embodiment has improved dispersibility, the abrasive slurry composition can suppress agglomeration of the abrasive particles. Accordingly, the abrasive particle dispersion according to the embodiment can prevent defects in the manufacturing process of semiconductor devices.

[0049] In addition, since the abrasive particle dispersion according to the embodiment includes the dispersant and the dispersing aid and has an appropriate pH and zeta potential, the polishing rate and selectivity of the abrasive slurry composition can be improved.

[0050] In addition, the abrasive particle dispersion according to the embodiment comprises ceria particles, an anionic dispersant, and a nonionic dispersion stabilizer in appropriate amounts. Accordingly, the abrasive particle dispersion according to the embodiment can have a negative zeta potential while improving the dispersibility of the ceria particles. For example, the abrasive particle dispersion according to the embodiment can have a zeta potential of -25 mV to -50 mV at a pH of 7 to 9.

[0051] In addition, since the abrasive particle dispersion according to the embodiment includes the dispersant and the nonionic dispersion stabilizer, it can have an appropriate zeta potential change rate. Accordingly, when an additive composition is added to the abrasive particle dispersion according to the embodiment to prepare a polishing slurry composition, the zeta potential change due to pH shock can be minimized.

[0052] In addition, the polishing slurry composition prepared using the polishing particle dispersion according to the embodiment can have low pH change, low increase in agglomeration, low zeta potential change, and low particle size change even when left at high temperatures for a long period of time. Accordingly, the polishing slurry composition according to the embodiment can have improved stability with respect to changes over time.

[0053] In addition, since the abrasive particle dispersion according to the embodiment has improved dispersibility, the abrasive slurry composition can suppress agglomeration of the abrasive particles. Accordingly, the abrasive particle dispersion according to the embodiment can prevent defects in the manufacturing process of semiconductor devices.

[0054] In particular, the polishing slurry composition including the abrasive particle dispersion according to the embodiment may be exposed to high temperatures due to frictional heat when used in a chemical mechanical polishing process. At this time, the abrasive particle dispersion according to the embodiment may have low pH change, low increase in agglomeration, low zeta potential change, and low particle size change even at high temperatures. Accordingly, the polishing slurry composition including the abrasive particle dispersion according to the embodiment may reduce defects and improve polishing uniformity in the manufacturing process of a semiconductor device.

[0055] In addition, since the abrasive particle dispersion according to the embodiment includes the dispersant and the dispersion stabilizer and has an appropriate pH and zeta potential, the polishing rate and selectivity of the abrasive slurry composition can be improved.

[0056] Figure 1 schematically illustrates a device configuration for a method for manufacturing the semiconductor device according to one embodiment.

[0057] Figure 2 is a schematic diagram illustrating the process of surrounding ceria particles with a dispersant and a dispersing aid.

[0058] The advantages and features of the present invention, and the methods for achieving them, will become clearer with reference to the embodiments or examples described below. However, the present invention is not limited to the embodiments or examples disclosed below and may be implemented in various different forms. The embodiments or examples specified below are provided solely to ensure that the disclosure of the present invention is complete and to inform those skilled in the art of the scope of the invention. The scope of the rights of the present invention is defined by the scope of the claims.

[0059] In the drawings, the thickness of some components is enlarged to clearly represent layers or regions, as needed. Additionally, in the drawings, the thickness of some layers and regions is exaggerated for convenience of explanation. Throughout the specification, the same reference numerals designate the same components.

[0060] In addition, when a part such as a layer, film, region, or plate is said to be "on," "on," or "above" another part in this specification, this is interpreted to include not only the case where it is "directly above" another part, but also the case where there is another part in between. When a part is said to be "directly above" another part, this is interpreted to mean that there is no other part in between. In addition, when a part such as a layer, film, region, or plate is said to be "below," "under," or "below" another part, this is interpreted to include not only the case where it is "directly below" another part, but also the case where there is another part in between. When a part is said to be "directly below" another part, this is interpreted to mean that there is no other part in between.

[0061] Hereinafter, implementation examples according to the present invention will be described in detail.

[0062] The abrasive particle dispersion according to the embodiment may include water, abrasive particles, a dispersant, a dispersing aid, a dispersion stabilizer, a fluorinated surfactant, and a pH regulator.

[0063] The above water may include deionized water.

[0064] The average particle diameter (D50) of the abrasive particles may be from about 10 nm to about 300 nm. The average particle diameter (D50) of the abrasive particles may be from about 20 nm to about 200 nm. The average particle diameter (D50) of the abrasive particles may be from about 30 nm to about 150 nm.

[0065] The particle size of the above abrasive particles can be measured by a Zetasizer from Malvern.

[0066] Since the average particle diameter of the above-mentioned abrasive particles is as above, the abrasive slurry composition according to the embodiment can have an improved polishing rate while reducing defects and dishing.

[0067] The abrasive particles may include ceria. The abrasive particles may be ceria particles.

[0068] The abrasive particles may be included in the abrasive particle dispersion in an amount of about 1 wt% to about 15 wt%, about 2 wt% to about 10 wt%, or about 3 wt% to about 8 wt%, based on the total weight of the abrasive particle dispersion.

[0069] Since the abrasive particles are included in the abrasive particle dispersion in the above range, the abrasive slurry composition can have an improved polishing rate and reduced defect generation.

[0070] The dispersant may include a polymer. The dispersant may include a polymer resin. The dispersant may be selected from the group consisting of polyacrylic acid, polyphosphoric acid, polymaleic acid, and polymethacrylic acid. The dispersant may include polyacrylic acid.

[0071] The above polyacrylic acid may include a repeating unit represented by the following chemical formula 1.

[0072] [Chemical Formula 1]

[0073]

[0074] Here, n can be 10 to 1000.

[0075] The weight average molecular weight of the dispersant may be from about 1000 g / mol to about 40,000 g / mol, from about 2000 g / mol to about 40,000 g / mol, from about 3000 g / mol to about 30,000 g / mol, from about 3000 g / mol to about 10,000 g / mol, from about 3000 g / mol to about 7,000 g / mol, from about 10,000 g / mol to about 50,000 g / mol, from about 20,000 g / mol to about 30,000 g / mol, or from about 25,000 g / mol to about 35,000 g / mol.

[0076] The pKa of the dispersant may be from about 3 to about 7, from about 2 to about 6, from about 3 to about 6, from about 3 to about 5, from about 3.5 to about 5.5, or from about 3.7 to about 5.3 at a temperature of about 25°C.

[0077] The above dispersant may have a carboxyl group.

[0078] The dispersant can surround the abrasive particles. The dispersant can improve the dispersibility of the abrasive particles.

[0079] The above abrasive particle dispersion may contain the dispersant in an amount of 0.1 wt% to about 1 wt%, in an amount of about 0.2 wt% to about 0.8 wt%, or in an amount of about 0.3 wt% to about 0.7 wt%, based on the total weight.

[0080] The dispersant may be included in the abrasive particle dispersion according to the embodiment in an amount of about 0.1 part by weight to about 0.3 part by weight, about 0.05 part by weight to about 0.5 part by weight, about 0.15 part by weight to about 0.25 part by weight, or about 0.07 part by weight to about 0.4 part by weight, based on 100 parts by weight of the water.

[0081] Since the above dispersant is included in the abrasive particle dispersion in the above range, the abrasive slurry composition can have an improved polishing rate and reduced defect generation.

[0082] The above dispersing aid may include an organic acid.

[0083] The above dispersing aid may include a pyridine derivative.

[0084] The above dispersing aid may be selected from the group consisting of 2-Pyridinecarboxylic acid (PA), 2-Picolinic acid, Pyridine-2,6-dicarboxylic acid, 4-Pyridinecarboxylic acid, 6-methyl-2-pyridinecarboxylic acid, or nicotinic acid.

[0085] The pKa of the dispersing aid may be from about 0.5 to about 4, from about 0.6 to about 3, from about 0.6 to about 2.5, from about 0.6 to about 2.0, from about 0.7 to about 1.5, or from about 0.8 to about 1.4 at a temperature of about 25°C.

[0086] The pKa of the dispersing aid may be lower than the pKa of the dispersant. The pKa of the dispersing aid may be lower than the pKa of the dispersant by about 0.1 to about 5, by about 0.2 to about 4, by about 0.3 to about 3, by about 0.4 to about 2, by about 0.4 to about 1.5, or by about 0.5 to about 1.5 at a temperature of about 25°C.

[0087] Since the above-mentioned dispersing aid has a pKa within the above-mentioned range, the above-mentioned dispersing aid, together with the above-mentioned dispersing agent, can improve the dispersibility of the above-mentioned abrasive particles. Since the above-mentioned dispersing aid has a pKa within the above-mentioned range, the above-mentioned dispersing agent can be bonded to the above-mentioned dispersing agent through electrostatic attraction.

[0088] For example, as illustrated in FIG. 2, the dispersant may surround the abrasive particles, and the dispersing aid may surround the abrasive particles, thereby surrounding the dispersant. Accordingly, the abrasive particles may have improved dispersibility.

[0089] The molecular weight of the dispersing aid may be from about 50 g / mol to about 1000 g / mol, from about 60 g / mol to about 800 g / mol, from about 70 g / mol to about 700 g / mol, from about 80 g / mol to about 500 g / mol, or from about 50 g / mol to about 400 g / mol.

[0090] The ratio of the molecular weight of the dispersing aid and the molecular weight of the dispersant may be about 1:5 to about 1:2000, about 1:10 to about 1:1000, about 1:20 to about 1:1000, about 1:30 to about 1:1000, about 1:40 to about 1:1000, or about 1:50 to about 1:1000.

[0091] Since the above-mentioned dispersing agent has a molecular weight within the above-mentioned range, the dispersing agent, together with the dispersing agent, can improve the dispersibility of the abrasive particles. Since the above-mentioned dispersing agent has a molecular weight within the above-mentioned range, the dispersing agent can surround the abrasive particles, and the dispersing agent can surround the abrasive particles while also surrounding the dispersing agent. Accordingly, the abrasive particles can have improved dispersibility.

[0092] The dispersing aid may be included in the abrasive particle dispersion in an amount of about 0.05 wt% to about 5 wt%, about 0.07 wt% to about 2.5 wt%, about 0.1 wt% to about 1 wt%, or about 0.1 wt% to about 0.5 wt%, based on the total weight of the abrasive particle dispersion.

[0093] Since the above dispersing aid is included in the abrasive particle dispersion in the above range, the abrasive slurry composition can have an improved polishing rate and reduced defect generation.

[0094] The above dispersion stabilizer may include a first dispersion stabilizer and a second dispersion stabilizer.

[0095] The first dispersion stabilizer may include at least one glycol selected from the group consisting of ethylene glycol, diethylene glycol, and polyethylene glycol.

[0096] The molecular weight of the first dispersion stabilizer may be from about 40 g / mol to about 1000 g / mol, from about 50 g / mol to about 900 g / mol, from about 50 g / mol to about 700 g / mol, from about 50 g / mol to about 500 g / mol, from about 50 g / mol to about 300 g / mol, or from about 50 g / mol to about 200 g / mol.

[0097] The above first dispersion stabilizer can be represented by the following chemical formula 2.

[0098] [Chemical Formula 2]

[0099]

[0100] In the above chemical formula 2, n may be 1 to 10.

[0101] The pKa of the first dispersion stabilizer may be from about 5 to about 30, from about 7 to about 25, from about 8 to about 20, or from about 9 to about 20 at a temperature of about 25°C.

[0102] The pKa of the first dispersion stabilizer may be greater than the pKa of the dispersant. The pKa of the first dispersion stabilizer may be greater than the pKa of the dispersant by about 1 to about 20, by about 2 to about 15, by about 3 to about 15, or by about 4 to about 13 at a temperature of about 25°C.

[0103] The weight ratio of the dispersant and the first dispersion stabilizer may be from about 1:3 to about 1:10. The weight ratio of the dispersant and the first dispersion stabilizer may be from about 1:4 to about 1:8.

[0104] The second dispersion stabilizer may have a higher molecular weight than the first dispersion stabilizer. The weight average molecular weight of the second dispersion stabilizer may be greater than the molecular weight of the first dispersion stabilizer by about 100 g / mol to about 50,000 g / mol, by about 500 g / mol to about 40,000 g / mol, by about 1,000 g / mol to about 30,000 g / mol, by about 2,000 g / mol to about 20,000 g / mol, or by about 2,000 g / mol to about 10,000 g / mol.

[0105] The weight average molecular weight of the second dispersion stabilizer may be from about 2000 g / mol to about 70000 g / mol, from about 3000 g / mol to about 60000 g / mol, from about 3500 g / mol to about 50000 g / mol, or from about 2000 g / mol to about 50000 g / mol.

[0106] The second dispersion stabilizer may include a nonionic stabilizer and / or a cationic stabilizer.

[0107] The above nonionic stabilizer may be selected from at least one group consisting of polyglycerine or polyvinylpyrrolidone.

[0108] The above polyglycerin can be represented by the following chemical formula 3.

[0109] [Chemical Formula 3]

[0110]

[0111] In the above chemical formula 3, n may be about 1 to about 3000, about 10 to about 2000, about 100 to about 1000, or about 150 to about 1500.

[0112] The weight average molecular weight of the polyglycerin may be from about 100 g / mol to about 3000 g / mol, from about 150 g / mol to about 2000 g / mol, from about 200 g / mol to about 1500 g / mol, or from about 100 g / mol to about 1000 g / mol.

[0113] The weight average molecular weight of the polyvinylpyrrolidone may be from about 3000 g / mol to about 30000 g / mol, from about 4000 g / mol to about 25000 g / mol, from about 5000 g / mol to about 15000 g / mol, or from about 6000 g / mol to about 14000 g / mol.

[0114] The pKa of the nonionic stabilizer may be from about 5 to about 30, from about 7 to about 25, from about 8 to about 20, or from about 9 to about 20 at a temperature of about 25°C.

[0115] The pKa of the nonionic stabilizer may be greater than the pKa of the dispersant. The pKa of the nonionic stabilizer may be greater than the pKa of the dispersant by about 1 to about 20, by about 2 to about 15, by about 3 to about 15, or by about 4 to about 13.

[0116] The cationic stabilizing agent may be at least one selected from the group consisting of polydiallyldimethylammonium chloride, polymethacrylate or polyoxyethylenestearylamine ether.

[0117] The above polydiallyldimethylammonium chloride can be represented by the following chemical formula 4.

[0118] [Chemical Formula 4]

[0119]

[0120] In the above chemical formula 4, n may be about 1 to about 3000, about 10 to about 2000, about 100 to about 1000, or about 150 to about 1500.

[0121] The weight average molecular weight of the above polydiallyldimethylammonium chloride may be about 3000 g / mol to about 30000 g / mol, about 4000 g / mol to about 25000 g / mol, about 5000 g / mol to about 15000 g / mol, or about 6000 g / mol to about 14000 g / mol.

[0122] The above polymethacrylate can be represented by the following chemical formula 5.

[0123] [Chemical Formula 5]

[0124]

[0125] In the above chemical formula 5, n may be about 1 to about 3000, about 10 to about 2000, about 100 to about 1000, or about 150 to about 1500.

[0126] The weight average molecular weight of the above polymethacrylate may be from about 4000 g / mol to about 40000 g / mol, from about 5000 g / mol to about 30000 g / mol, from about 8000 g / mol to about 25000 g / mol, or from about 9000 g / mol to about 20000 g / mol.

[0127] The above polyoxyethylene stearylamine ether can be represented by the following chemical formula 6.

[0128] [Chemical Formula 6]

[0129]

[0130] The pKa of the cationic stabilizer may be from about 3 to about 20, from about 4 to about 15, from about 5 to 12, or from about 6 to about 10 at a temperature of about 25°C.

[0131] The ratio of the pKa of the cationic stabilizer and the pKa of the dispersant may be about 1:0.5 to about 1:2, about 1:0.7 to 1:1.7, or 1:0.8 to 1:1.5 at a temperature of about 25°C.

[0132] The abrasive particle dispersion may contain the first dispersion stabilizer in an amount of 1 wt% to about 15 wt%, in an amount of about 2 wt% to about 15 wt%, or in an amount of about 3 wt% to about 13 wt%, based on the total weight.

[0133] The above abrasive particle dispersion may contain the second dispersion stabilizer in an amount of 1 wt% to about 15 wt%, in an amount of about 2 wt% to about 15 wt%, or in an amount of about 3 wt% to about 13 wt%, based on the total weight.

[0134] Since the first dispersion stabilizer and the second dispersion stabilizer are included in the abrasive particle dispersion in the above ranges, the polishing slurry composition can have an improved polishing rate and reduced defect generation.

[0135] The above fluorinated surfactant may include a nonionic fluorinated polymer compound. The above fluorosurfactant may be at least one selected from the group consisting of sodium sulfonate fluorosurfactant, phosphate ester fluorosurfactant, amine oxide fluorosurfactant, betaine fluorosurfactant, ammonium carboxylate fluorosurfactant, stearate ester fluorosurfactant, quaternary ammonium fluorosurfactant, ethylene oxide / propylene oxide fluorosurfactant, and polyoxyethylene fluorosurfactant.

[0136] The above fluorinated surfactant can be represented by the following chemical formula 7.

[0137] [Chemical Formula 7]

[0138]

[0139] In the above chemical formula 7, n may be 1 to 10, and m may be 1 to 10. In the above chemical formula 7, n may be 2 to 7, and m may be 2 to 7. In the above chemical formula 7, n may be 1 to 5, and m may be 1 to 5.

[0140] The weight average molecular weight of the above fluorinated surfactant may be from about 4000 g / mol to about 40,000 g / mol, from about 5000 g / mol to about 30,000 g / mol, from about 8000 g / mol to about 25,000 g / mol, or from about 9000 g / mol to about 20,000 g / mol.

[0141] The fluorinated surfactant may be included in the abrasive particle dispersion in an amount of about 0.001 to about 0.05 parts by weight, about 0.0001 to about 0.03 parts by weight, about 0.003 to about 0.01 parts by weight, or about 0.004 to about 0.01 parts by weight, based on 100 parts by weight of the water.

[0142] Since the fluorine-based surfactant is included in the abrasive particle dispersion in the above range, the abrasive slurry composition can have an improved polishing rate and reduced defect generation.

[0143] The abrasive particle dispersion according to the embodiment may further include a protective agent.

[0144] The above-mentioned protective agent can protect a semiconductor substrate to be polished. The protective agent can protect the surface of the semiconductor substrate. The protective agent can protect a non-target film on the semiconductor substrate. For example, the protective agent can protect a silicon nitride film included in the semiconductor substrate.

[0145] The protective agent may include an amphoteric substance. The protective agent may include an acidic group and a basic group. The protective agent may include an amine group and a carboxyl group. The protective agent may include glycine, taurine, proline, glutamic acid, serene, valine, or theanine.

[0146] The protective agent may be included in the abrasive particle dispersion in an amount of about 0.3 parts by weight to about 5 parts by weight, about 0.5 parts by weight to about 4 parts by weight, about 0.5 parts by weight to about 3 parts by weight, about 0.5 parts by weight to about 2 parts by weight, or about 0.7 parts by weight to about 1.5 parts by weight, based on 100 parts by weight of the water.

[0147] The pH regulator may include a first pH regulator and a second pH regulator.

[0148] The first pH adjusting agent may comprise a basic compound. The first pH adjusting agent may comprise a basic pH adjusting agent.

[0149] The first pH adjusting agent may be imidazole, alkyl amines, alcohol amines, quaternary amine hydroxides, ammonia, or a combination thereof. In particular, the first pH adjusting agent may be at least one selected from the group consisting of triethanolamine, tetramethylammonium hydroxide (TMAH or TMAOH), or tetraethylammonium hydroxide (TEAH or TEA-OH). In addition, examples of the pH adjusting agent may include at least one selected from the group consisting of ammonium methyl propanol (AMP), tetramethyl ammonium hydroxide (TMAH), potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, cesium hydroxide, sodium bicarbonate, sodium carbonate, triethanolamine, tromethamine, and niacinamide. The first pH adjusting agent may be triethanolamine or aminobutyric acid. The first pH adjusting agent may include triethanolamine.

[0150] The first pH regulator can be mixed with the dispersant to form a neutralized salt. That is, the first pH regulator and the dispersant can react to form the salt. The pH of the salt formed by the reaction of the first pH regulator and the dispersant can be about 8 to about 10. That is, the first pH regulator and the dispersant can react with each other in appropriate amounts to form a salt having a pH of about 8 to about 10.

[0151] The first pH adjusting agent may have a pKa of about 5 to about 10, a pKa of about 4 to about 15, a pKa of about 3 to about 20, a pKa of about 6 to about 10, a pKa of about 5 to about 9, or a pKa of about 6 to about 9 at a temperature of about 25°C.

[0152] The first pH adjuster may be included in the abrasive particle dispersion in an amount of about 0.5 parts by weight to about 5 parts by weight, about 0.3 parts by weight to about 4 parts by weight, about 0.7 parts by weight to about 4 parts by weight, or about 0.8 parts by weight to about 3 parts by weight, based on 100 parts by weight of the water.

[0153] The second pH adjusting agent may comprise an acidic compound. The second pH adjusting agent may comprise an acidic pH adjusting agent.

[0154] The second pH regulator may be selected from at least one group consisting of an inorganic acid selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, or an organic acid selected from the group consisting of acetic acid, citric acid, glutaric acid, gluconic acid, formic acid, lactic acid, malic acid, malonic acid, maleic acid, oxalic acid, phthalic acid, succinic acid, and tartaric acid. The second pH regulator may include nitric acid.

[0155] The second pH adjusting agent may be included in the abrasive particle dispersion in an amount of about 0.5 parts by weight to about 5 parts by weight, about 0.3 parts by weight to about 4 parts by weight, about 0.7 parts by weight to about 4 parts by weight, or about 0.8 parts by weight to about 3 parts by weight, based on 100 parts by weight of the water.

[0156] The pH of the abrasive particle dispersion can be adjusted by the first pH adjuster and the second pH adjuster. The pH of the abrasive particle dispersion can be about 6 to about 11, about 7 to about 10, about 7 to 9, or about 7.5 to about 9.5.

[0157] Since the pH of the above-mentioned abrasive particle dispersion is in the above-mentioned range, the above-mentioned abrasive slurry composition can have an improved polishing rate and reduced defect induction.

[0158] By the above dispersing aid, the zeta potential of the abrasive particle dispersion according to the embodiment can be controlled.

[0159] The zeta potential of the abrasive particle dispersion may be from about -55 mV to about -5 mV, from about -50 mV to about -10 mV, from about -45 mV to about -15 mV, from about -45 mV to about -20 mV, or from about -40 mV to about -25 mV.

[0160] Since the zeta potential of the above-mentioned abrasive particle dispersion is in the above-mentioned range, the above-mentioned abrasive slurry composition can have an improved polishing rate and reduced defect induction.

[0161] The abrasive particle dispersion according to the embodiment may have a first zeta potential change rate (ZR1).

[0162] The above first zeta potential change rate can be derived by the following equation 1.

[0163] [Formula 1]

[0164] ZR1 = (Z8 - Z6) / 2

[0165] In the above formula 1, Z8 is the zeta potential of the abrasive particle dispersion at pH 8, and Z6 is the zeta potential of the abrasive particle dispersion at pH 6.

[0166] The first zeta potential change rate may be from about -7 mV to about 0 mV, from about -6 mV to about 0 mV, from about -5 mV to about 0 mV, from about -4 mV to about 0 mV, or from about -3 mV to about 0 mV.

[0167] The abrasive particle dispersion according to the embodiment may have a second zeta potential change rate (ZR2).

[0168] The above second zeta potential change rate can be derived by the following equation 2.

[0169] [Formula 2]

[0170] ZR2 = (Z10 - Z8) / 2

[0171] In the above formula 2, Z8 is the zeta potential of the abrasive particle dispersion at pH 8, and Z10 is the zeta potential of the abrasive particle dispersion at pH 10.

[0172] The second zeta potential change rate may be from about -7 mV to about 0 mV, from about -6 mV to about 0 mV, from about -5 mV to about 0 mV, from about -4 mV to about 0 mV, or from about -3 mV to about 0 mV.

[0173] The abrasive particle dispersion according to the embodiment may have a third zeta potential change rate (ZR3).

[0174] The above third zeta potential change rate can be derived by the following equation 3.

[0175] [Formula 3]

[0176] ZR3 = (Z6 - Z4) / 2

[0177] In the above formula 3, Z6 is the zeta potential of the abrasive particle dispersion at pH 6, and Z4 is the zeta potential of the abrasive particle dispersion at pH 4.

[0178] The third zeta potential change rate may be from about -7 mV to about 0 mV, from about -6 mV to about 0 mV, from about -5 mV to about 0 mV, from about -4 mV to about 0 mV, from about -3 mV to about 0 mV, or from about -2 mV to about 0 mV.

[0179] The above Z4, the above Z6, the above Z8 and the above Z10 can be measured by the following process.

[0180] Nitric acid or ammonia may be added to the abrasive particle dispersion according to the embodiment. Accordingly, the pH of the abrasive particle dispersion according to the embodiment may be adjusted to about 4, about 6, about 8, or about 10. Thereafter, at the above pH, the zeta potential of the abrasive particle dispersion according to the embodiment may be measured.

[0181] For example, when the pH of the abrasive particle dispersion according to the embodiment is about 7, the nitric acid may be added little by little to the abrasive particle dispersion according to the embodiment. Accordingly, the pH of the abrasive particle dispersion according to the embodiment can be adjusted to about 4 or about 6.

[0182] Additionally, when the pH of the abrasive particle dispersion according to the embodiment is about 7, ammonia may be added little by little to the abrasive particle dispersion according to the embodiment. Accordingly, the pH of the abrasive particle dispersion according to the embodiment can be adjusted to about 8 or about 10.

[0183] The zeta potential of the abrasive particle dispersion according to the embodiment can be measured by a zetasizer of Malvern.

[0184] Additionally, the abrasive particle dispersion according to the embodiment may have a first pH change (△p). The first pH change may be a change in pH when the abrasive particle dispersion is left at a high temperature for a long period of time. The first pH change may be expressed by the following equation 4.

[0185] [Formula 4]

[0186] △p = │p0 - p14│

[0187] Here, p0 is the initial pH of the abrasive particle dispersion, and p14 is the pH after the abrasive particle dispersion is left at a temperature of about 60°C for about 14 days.

[0188] The first pH change may be from 0.1 to 2, from 0.11 to 2, from 0.2 to 1.5 or from 0.2 to 2.

[0189] Accordingly, the abrasive particle dispersion according to the embodiment can maintain a constant pH even when stored for a long period of time. Furthermore, the abrasive particle dispersion according to the embodiment can maintain a constant pH when used in a chemical mechanical polishing process. Accordingly, the abrasive particle dispersion according to the embodiment can achieve uniform polishing performance.

[0190] Additionally, the abrasive particle dispersion according to the embodiment may have a first particle size change rate (SR1). The first particle size change rate may be a change in the diameter of the ceria particles when the abrasive particle dispersion is left at a high temperature for a long period of time. The first particle size change rate may be expressed by the following mathematical expression 5.

[0191] [Formula 5]

[0192] SR1 = │S0 - S14│ / S0

[0193] Here, S0 is the initial diameter of the ceria particles in the abrasive particle dispersion, and S14 is the particle diameter of the ceria particles after the abrasive particle dispersion is left at a temperature of 60°C for 14 days.

[0194] The diameter of the above ceria particles can be measured by a Zetasizer from Malvern.

[0195] The above first particle diameter change rate may be from about 0.0001 to about 0.05, from about 0.001 to about 0.04, from about 0.001 to about 0.03, from about 0.001 to about 0.05, from about 0.001 to about 0.02, or from about 0.001 to about 0.01.

[0196] Accordingly, the abrasive particle dispersion according to the embodiment can maintain a constant particle diameter even when stored for a long period of time. Furthermore, the abrasive particle dispersion according to the embodiment can maintain a constant particle diameter when used in a chemical mechanical polishing process. Accordingly, the abrasive particle dispersion according to the embodiment can achieve uniform polishing performance and suppress defect generation.

[0197] Additionally, the abrasive particle dispersion according to the embodiment may have a first agglomeration increase (ΔA). The first agglomeration increase may be an increase in the number of agglomerated ceria particles when the abrasive particle dispersion is left at a high temperature for a long period of time. The first agglomeration increase may be expressed by the following mathematical expression 6.

[0198] [Formula 6]

[0199] △A = A7 - A0

[0200] Here, A0 is the number of aggregated ceria particles having a particle size of about 0.69 μm to about 1.01 μm initially in the abrasive particle dispersion, and A7 is the number of aggregated ceria particles having a particle size of 0.69 μm to 1.01 μm after the abrasive particle dispersion is left at a temperature of 60° C. for 7 days.

[0201] The number of the above aggregated ceria particles can be measured by a laser particle counter.

[0202] The first increase in aggregation may be less than about 3000 / mL, less than about 2500 / mL, less than about 2000 / mL, less than about 1500 / mL, or less than about 1000 / mL.

[0203] Additionally, the A0 may be from about 50 / ml to about 5000 / ml, from about 50 / ml to about 4500 / ml, from about 50 / ml to about 4000 / ml, from about 50 / ml to about 3500 / ml, from about 50 / ml to about 3000 / ml, or from about 50 / ml to about 2500 / ml.

[0204] Additionally, the A7 may be about 100 units / ml to about 5500 units / ml, about 100 units / ml to about 5000 units / ml, about 100 units / ml to about 4500 units / ml, about 10 units / ml to about 4000 units / ml, about 100 units / ml to about 3500 units / ml, or about 100 units / ml to about 3000 units / ml.

[0205] Accordingly, the abrasive particle dispersion according to the embodiment can minimize agglomeration of the ceria particles even when stored for a long period of time. Furthermore, the abrasive particle dispersion according to the embodiment can minimize agglomeration of the ceria particles when used in a chemical mechanical polishing process. Accordingly, the abrasive particle dispersion according to the embodiment can achieve uniform polishing performance and suppress defect generation.

[0206] An additive composition may be added to the polishing particle dispersion according to the embodiment, thereby producing a polishing slurry composition.

[0207] The above additive composition may include the water, the dispersant, the dispersion stabilizer, the reducing agent, the surfactant, the protective agent, and the pH regulator.

[0208] The dispersant may be included in the additive composition in an amount of about 0.03 parts by weight to about 1 part by weight, about 0.04 parts by weight to about 1.1 parts by weight, about 0.05 parts by weight to about 0.8 parts by weight, or about 0.05 parts by weight to about 0.5 parts by weight, based on 100 parts by weight of the water.

[0209] The first dispersion stabilizer may be included in the additive composition in an amount of about 0.1 to 5 parts by weight, about 0.1 to 3 parts by weight, about 0.2 to 2 parts by weight, about 0.3 to 1 part by weight, or about 0.2 to 0.8 parts by weight, based on 100 parts by weight of the water.

[0210] The second dispersion stabilizer may be included in the additive composition in an amount of about 0.1 to 5 parts by weight, about 0.1 to 3 parts by weight, about 0.2 to 2 parts by weight, about 0.3 to 1 part by weight, or about 0.2 to 0.8 parts by weight, based on 100 parts by weight of the water.

[0211] In the above additive composition, the weight ratio of the dispersant and the second dispersion stabilizer may be from about 1:3 to about 1:10. The weight ratio of the dispersant and the second dispersion stabilizer may be from about 1:4 to about 1:8.

[0212] Additionally, in the additive composition, the weight ratio of the first dispersion stabilizer and the second dispersion stabilizer may be about 1:0.5 to about 1:2, about 1:0.7 to about 1:1.5, or about 1:0.8 to about 1:1.3.

[0213] The reducing agent may include a sugar. The sugar may be at least one selected from the group consisting of dextrose, galactose, arabinose, ribose, xylose, maltitol, lactose, maltose, pullulan, or xylitol.

[0214] In addition, the above sugars are sucrose, lactulose, lactose, trehalose, maltose, cellobiose, kojibiose, nigerose, isomaltose, isotrehalose, neotrehalose, sophorose, laminaribiose, gentibiose, turanose, maltulose, paratinose, gentiobiurose, mannobiose, melibiose, melibiurose, neolactose, galactosucrose, sylabiose, rutinose, rutinurose, bicyanose, gyrobiose, primerose, trehalosamine, maltitol, cellobionic acid, lactosamine, lactosediamine, lactobionic acid, lactitol, hyalobiuronic acid, sucralose, nigerotriose, maltotriose, melecitose, Maltotriulose, raffinose, kestose, nystose, nigerotetraose, stachyose, amylose, dextran, dextrin, maltodextrin, cluster dextrin, cycloawaodorin, laminaran, callose, PGA, pectin, glucomannan, gellan gum, curdlan, psyllium, locust bean gum, pullulan, alginic acid, tamarind, carrageenan, CMC, xanthan gum, gum arabic, guar gum, pectin, soy polysaccharide, fructan, glycogen, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, isomaltooligosaccharide, galactooligosaccharide, xylooligosaccharide, soybean oligosaccharide, nigerooligosaccharide, At least one may be selected from the group consisting of oligosaccharides or fructooligosaccharides.

[0215] Additionally, the sugar may be at least one selected from the group consisting of amylose, dextran, dextrin, maltodextrin, cluster dextrin, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, maltose, isomaltose, maltotriose, or stachyose.

[0216] The above sugars may include at least one from the group consisting of dextrose, fructose or galactose.

[0217] The reducing agent may be included in the additive composition in an amount of about 1 part by weight to 10 parts by weight, about 0.5 parts by weight to about 7 parts by weight, about 1.5 parts by weight to about 8 parts by weight, about 2 parts by weight to about 10 parts by weight, or about 2 parts by weight to about 8 parts by weight, based on 100 parts by weight of the water.

[0218] The weight ratio of the dispersant and the reducing agent may be from about 1:50 to about 1:500. The weight ratio of the dispersant and the reducing agent may be from about 1:60 to about 1:300.

[0219] The fluorinated surfactant may be included in the additive composition in an amount of about 0.001 to about 0.05 parts by weight, about 0.0001 to about 0.03 parts by weight, about 0.003 to about 0.01 parts by weight, or about 0.004 to about 0.01 parts by weight, based on 100 parts by weight of the water.

[0220] The protective agent may be included in the additive composition in an amount of about 0.3 parts by weight to about 5 parts by weight, about 0.5 parts by weight to about 4 parts by weight, about 0.5 parts by weight to about 3 parts by weight, about 0.5 parts by weight to about 2 parts by weight, or about 0.7 parts by weight to about 1.5 parts by weight, based on 100 parts by weight of the water.

[0221] The first pH regulator may be included in the additive composition in an amount of about 0.5 parts by weight to about 5 parts by weight, about 0.3 parts by weight to about 4 parts by weight, about 0.7 parts by weight to about 4 parts by weight, or about 0.8 parts by weight to about 3 parts by weight, based on 100 parts by weight of the water.

[0222] The second pH adjusting agent may be appropriately added to adjust the pH of the additive composition. The second pH adjusting agent may be added to the additive composition in an appropriate amount so that the pH of the additive composition is about 7 to about 10.

[0223] The second pH adjusting agent may have a pKa of about -2 to about 1, a pKa of about -2 to about 5, a pKa of about -2 to about 3, a pKa of about -2 to about 0, a pKa of about -2 to about -1, a pKa of about 0 to about 4, or a pKa of about 2 to about 5 at a temperature of about 25°C.

[0224] The sum of the pKa of the first pH regulator and the pKa of the second pH regulator may be from about 4 to about 9, from about 3 to about 11, from about 3 to about 10, from about 4 to about 8, from about 5 to about 8, or from about 5 to about 7.5 at a temperature of about 25°C.

[0225] Since the first pH regulator and the second pH regulator have pKa in the above range, they can improve the performance of the dispersant, the dispersion stabilizer, the fluorine-based surfactant, the protective agent, and the reducing agent.

[0226] The above additive composition can be used in a process for manufacturing a semiconductor device. The above additive composition can be used in a chemical mechanical polishing process. The above additive composition can be uniformly mixed with the above polishing particle dispersion to form the above polishing slurry composition. The above polishing slurry composition can be used in the above chemical mechanical polishing process.

[0227] The above additive composition, deionized water, and the above polishing particle dispersion can be mixed to prepare the above polishing slurry composition.

[0228] In the above polishing slurry composition, the additive composition and the polishing particle dispersion may be mixed in a weight ratio of about 3:1 to about 1:3, a weight ratio of about 2.5:1 to about 1:2.5, a weight ratio of about 2:1 to about 1:2, or a weight ratio of about 1.5:1 to about 1:1.5.

[0229] The above polishing slurry composition can have an improved polishing rate and reduced defect generation because it includes the above additive composition and the above polishing particle dispersion in the above contents.

[0230] Alternatively, the polishing slurry composition may be formed by mixing deionized water and the polishing particle dispersion. That is, the polishing slurry composition may be formed by adding only deionized water to the polishing particle dispersion without adding the additive composition.

[0231] Additionally, in the polishing slurry composition, the deionized water and the polishing particle dispersion may be mixed in a weight ratio of about 3:1 to about 20:1, a weight ratio of about 5:1 to about 15:1, a weight ratio of about 7:1 to about 15:1, or a weight ratio of about 5:1 to about 15:1.

[0232] The above polishing slurry composition may include the abrasive particles in an amount of about 0.05 wt% to about 1 wt%, in an amount of about 0.1 wt% to about 1 wt%, or in an amount of about 0.15 wt% to about 0.8 wt%, based on the total weight.

[0233] The polishing slurry composition may include the dispersant in an amount of about 0.01 wt% to about 0.1 wt%, about 0.02 wt% to about 0.08 wt%, or about 0.03 wt% to about 0.08 wt%, based on the total weight.

[0234] The polishing slurry composition may include the dispersing aid in an amount of about 0.005 wt% to about 0.5 wt%, about 0.007 wt% to about 0.25 wt%, about 0.01 wt% to about 0.1 wt%, or about 0.01 wt% to about 0.05 wt%, based on the total weight.

[0235] The polishing slurry composition may contain the first dispersion stabilizer in an amount of from about 0.1 wt% to about 1.5 wt%, from about 0.2 wt% to about 1.5 wt%, or from about 0.3 wt% to about 1.3 wt%, based on the total weight.

[0236] The polishing slurry composition may include the second dispersion stabilizer in an amount of from about 0.1 wt% to about 1.5 wt%, from about 0.2 wt% to about 1.5 wt%, or from about 0.3 wt% to about 1.3 wt%, based on the total weight.

[0237] The fluorinated surfactant may be included in the polishing slurry composition in an amount of about 0.0001 to about 0.005 parts by weight, about 0.00001 to about 0.003 parts by weight, about 0.0003 to about 0.001 parts by weight, or about 0.0004 to about 0.001 parts by weight, based on 100 parts by weight of the water.

[0238] The above polishing slurry composition has an improved polishing rate and can reduce the occurrence of defects because it contains the polishing particles, the dispersant, the dispersing aid, the dispersion stabilizer, the fluorine-based surfactant, and the reducing agent in the above range of potentials.

[0239] The first pH adjuster may be included in the polishing slurry composition in an amount of about 0.05 parts by weight to about 0.5 parts by weight, about 0.03 parts by weight to about 0.4 parts by weight, about 0.07 parts by weight to about 0.4 parts by weight, or about 0.08 parts by weight to about 0.3 parts by weight, based on 100 parts by weight of the water.

[0240] The second pH adjuster may be included in the polishing slurry composition in an amount of about 0.05 parts by weight to about 0.5 parts by weight, about 0.03 parts by weight to about 0.4 parts by weight, about 0.07 parts by weight to about 0.4 parts by weight, or about 0.08 parts by weight to about 0.3 parts by weight, based on 100 parts by weight of the water.

[0241] The pH of the polishing slurry composition can be adjusted by the first pH adjuster and the second pH adjuster. The pH of the polishing slurry composition can be about 6 to about 11, about 7 to about 10, or about 7.5 to about 9.5.

[0242] Since the pH of the above polishing slurry composition is within the above range, it can have an improved polishing rate and reduced defect generation.

[0243] The reducing agent may be included in the polishing slurry composition in an amount of about 0.05 parts by weight to 0.5 parts by weight, about 0.025 parts by weight to about 0.35 parts by weight, about 0.07 parts by weight to about 0.4 parts by weight, about 0.1 parts by weight to about 0.5 parts by weight, or about 0.1 parts by weight to about 0.4 parts by weight, based on 100 parts by weight of the water.

[0244] The zeta potential of the polishing slurry composition may be from about -55 mV to about -5 mV, from about -50 mV to about -10 mV, from about -45 mV to about -15 mV, from about -45 mV to about -20 mV, or from about -40 mV to about -25 mV.

[0245] Since the zeta potential of the above polishing slurry composition has the above range, the above polishing slurry composition can have an improved polishing rate and reduce the occurrence of defects.

[0246] Additionally, the polishing slurry composition may have a second pH change (△ps). The second pH change may be a change in pH when the polishing slurry composition is left at a high temperature for a long period of time. The second pH change may be expressed by the following equation 7.

[0247] [Formula 7]

[0248] △ps = │ps0 - ps14│

[0249] Here, ps0 is the initial pH of the polishing slurry composition, and ps14 is the pH after the polishing slurry composition is left at a temperature of about 60°C for about 14 days.

[0250] The second pH change may be from 0.1 to 2, from 0.11 to 2, from 0.2 to 1.5 or from 0.2 to 2.

[0251] Accordingly, the polishing slurry composition can maintain a constant pH when used in a chemical mechanical polishing process. Accordingly, the polishing slurry composition can achieve uniform polishing performance.

[0252] Additionally, the polishing slurry composition may have a second particle size change rate (SR2). The second particle size change rate may be a change in the diameter of the ceria particles when the polishing slurry composition is left at a high temperature for a long period of time. The second particle size change rate may be expressed by the following mathematical formula 8.

[0253] [Formula 8]

[0254] SR2 = │SS0 - SS14│ / SS0

[0255] Here, SS0 is the initial diameter of the ceria particles in the polishing slurry composition, and SS14 is the particle diameter of the ceria particles after the polishing slurry composition is left at a temperature of 60°C for 14 days.

[0256] The diameter of the above ceria particles can be measured by a Zetasizer from Malvern.

[0257] The second particle diameter change rate may be from about 0.0001 to about 0.05, from about 0.001 to about 0.04, from about 0.001 to about 0.03, from about 0.001 to about 0.05, from about 0.001 to about 0.02, or from about 0.001 to about 0.01.

[0258] Accordingly, the polishing slurry composition can maintain a constant particle diameter when used in a chemical mechanical polishing process. Accordingly, the polishing slurry composition can achieve uniform polishing performance and suppression of defect induction.

[0259] Additionally, the polishing slurry composition may have a second agglomeration increase (△AS). The second agglomeration increase may be an increase in the number of agglomerated ceria particles when the polishing slurry composition is left at a high temperature for a long period of time. The second agglomeration increase may be expressed by the following mathematical formula 9.

[0260] [Formula 9]

[0261] △AS = AS7 - AS0

[0262] Here, AS0 is the number of aggregated ceria particles having a particle size of about 0.69 μm to about 1.01 μm initially in the polishing slurry composition, and AS7 is the number of aggregated ceria particles having a particle size of 0.69 μm to 1.01 μm after the polishing slurry composition is left at a temperature of 60° C. for 7 days.

[0263] The number of the above aggregated ceria particles can be measured by a laser particle counter.

[0264] The second increase in aggregation may be less than about 3000 / mL, less than about 2500 / mL, less than about 2000 / mL, less than about 1500 / mL, or less than about 1000 / mL.

[0265] Accordingly, the polishing slurry composition can minimize agglomeration of the ceria particles when used in a chemical mechanical polishing process. Accordingly, the polishing slurry composition can achieve uniform polishing performance and suppress defect generation.

[0266] Fig. 1 schematically illustrates a device configuration for a method for manufacturing a semiconductor device according to one embodiment. Referring to Fig. 1, the method for manufacturing a semiconductor device includes a step of arranging a polishing surface (111) of a polishing pad (110) so that the polishing surface of a polishing target (130) is in contact with the polishing surface; and a step of injecting a polishing slurry composition (150) onto the polishing surface (111).

[0267] The polishing target (130) may include a semiconductor wafer having a silicon nitride film and a silicon oxide film. Specifically, the polishing surface may include a surface requiring simultaneous polishing of the silicon nitride film and the silicon oxide film. Since the polishing target (130) and its polishing surface have these characteristics, the polishing slurry composition

[0268] The above polishing pad (110) may have a surface hardness measured on the polishing surface (111) of about 50 to about 70, for example, about 50 to about 65, for example, about 55 to about 65 in terms of Shore D hardness. A method for measuring the Shore D surface hardness on the polishing surface may be widely applied using a method commonly used in the relevant technical field, but for example, a sample may be prepared by cutting the polishing pad into a size of 2 cm × 2 cm (thickness: 2 mm), and then left to stand for 16 hours in an environment of a temperature of 25°C and a humidity of 50±5%, and then measured using a hardness meter (D-type hardness meter). When the hardness on the polishing surface (111) satisfies this range, the semiconductor process composition (150) can flow at the contact interface between the polishing surface (111) and the polishing target (130) to exhibit a physically appropriate elastic correlation with the polishing pad (110), and as a result, the semiconductor device manufactured by the method for manufacturing the semiconductor device can be more advantageous in exhibiting high polishing flatness without defects such as scratches.

[0269] The polishing pad (110) may include a groove or a groove on the polishing surface (111). The groove or groove is a configuration for controlling the fluidity of the semiconductor process composition (150) injected onto the polishing surface (111), and its shape is not particularly limited, but its depth may be, for example, about 300 ㎛ to about 900 ㎛, for example, about 300 ㎛ to about 850 ㎛, for example, about 400 ㎛ to about 850 ㎛, for example, about 450 ㎛ to about 850 ㎛, for example, about 500 ㎛ to about 800 ㎛, for example, about 550 ㎛ to about 800 ㎛, for example, about 600 ㎛ to about 800 ㎛. In addition, the width of the groove or the groove may be about 100 µm to about 600 µm, for example, about 200 µm to about 600 µm, for example, about 200 µm to about 550 µm, for example, about 300 µm to about 550 µm, for example, about 350 µm to about 550 µm. When the depth and width of the groove or the groove satisfy this range, it may be more advantageous in providing optimized fluidity to the composition for the semiconductor process.

[0270] The fact that the polishing surface (111) of the polishing pad (110) and the polishing target surface (130) come into contact with each other can be interpreted to include not only cases where they are in direct physical contact with each other, but also cases where they are indirectly in contact with each other through the semiconductor process composition.

[0271] The step of injecting the semiconductor process composition (150) onto the polishing surface (111) may be specifically performed by a method in which the semiconductor process composition (150) is injected onto the polishing surface (111) through a supply nozzle (140). In one embodiment, the flow rate of the semiconductor process composition (150) injected through the supply nozzle (140) may be about 10 ml / min to about 1,000 ml / min, for example, about 10 ml / min to about 800 ml / min, for example, about 50 ml / min to about 500 ml / min, for example, about 80 ml / min to about 400 ml / min, for example, about 100 ml / min to about 300 ml / min, for example, about 150 ml / min to about 300 ml / min. When the semiconductor process composition (150) is injected onto the polishing surface (111) at a flow rate within this range, the frictional behavior between the polishing surface (111) and the surface to be polished through this may be more advantageous in improving the polishing performance of the surface to be polished. More specifically, it may be more advantageous in achieving the desired polishing selectivity and simultaneously implementing the effect of preventing defects such as scratches due to the solid content in the semiconductor process composition.

[0272] The method for manufacturing the semiconductor device includes a step of polishing the surface to be polished while relatively rotating the polishing pad (110) and the polishing target (130). Referring to FIG. 1, the polishing pad (110) is mounted on a platen (120) so that the polishing surface (111) becomes the uppermost surface, and the polishing target (130) can be accommodated in a carrier (160) so that the surface to be polished becomes the lowermost surface. The polishing pad (110) and the polishing target (130) can rotate at the same speed and trajectory as the platen (120) and the carrier (160) rotate, respectively. Relative rotation of the polishing pad (110) and the polishing target (130) means that they rotate while the polishing surface and the surface to be polished are arranged to be in contact with each other. The rotation direction of the polishing pad (110) and the rotation direction of the polishing target (130) may be opposite to each other or may be in the same direction.

[0273] In one embodiment, the rotation speeds of the polishing pad (110) and the polishing target (130) may each independently be about 10 rpm to about 500 rpm, for example, about 30 rpm to about 200 rpm. When the polishing pad (110) and the polishing target (130) each rotate at a rotation speed within the above range, the frictional behavior of the polishing surface (111) and the surface to be polished due to the centrifugal force thereof is mutually linked with the semiconductor process composition (150) injected onto the polishing surface (111), so that the surface to be polished can be polished to have a high polishing flatness, and it may be more advantageous to polish without defects.

[0274] In one embodiment, the rotation speed of the polishing target (130) may be greater than the rotation speed of the polishing pad (110). By rotating the polishing target (130) at a higher speed than the polishing pad (110), polishing stability can be secured, and at the same time, the polishing surface of the polishing target (130) can be more advantageously polished without defects.

[0275] In one embodiment, the method for manufacturing the semiconductor device may relatively rotate the polishing pad (110) and the polishing target (130) under conditions in which the polishing surface is pressed against the polishing surface (111). The load applied to the polishing surface against the polishing surface (111) may be, for example, about 0.01 psi to about 20 psi, for example, about 0.1 psi to about 15 psi.

[0276] The method for manufacturing the semiconductor device may further include a step of processing the polishing surface (111) using a conditioner (170). The polishing surface (111) of the polishing pad (110) is subjected to a chemical influence as the semiconductor process composition (150) is continuously supplied, and at the same time, is subjected to a physical influence due to physical contact with the surface to be polished of the polishing object (130). If the state of the polishing surface (111) is modified due to such chemical / physical influences, it may be difficult to uniformly maintain polishing performance for the surface to be polished. The conditioner (170) serves as a means for processing the polishing surface (111) during the polishing process, and can contribute to uniformly maintaining the polishing surface (111) in a state suitable for polishing throughout the polishing process.

[0277] For example, the conditioner (170) may perform the function of roughening the polishing surface (111) while rotating at a predetermined speed. The rotation speed of the conditioner (170) may be, for example, about 10 rpm to about 500 rpm, for example, about 50 rpm to about 500 rpm, for example, about 100 rpm to about 500 rpm, for example, about 200 rpm to about 500 rpm, for example, more than about 200 rpm and less than about 400 rpm.

[0278] The conditioner (170) can rotate while applying a predetermined pressure to the polishing surface (111) of the polishing pad (110). For example, the pressure applied to the polishing surface (111) of the conditioner (170) may be about 1 psi to about 20 psi, for example, about 1 psi to about 15 psi, for example, about 5 psi to about 15 psi, for example, about 5 psi to about 10 psi.

[0279] By performing surface treatment under the process conditions described above through the conditioner (170), the polishing surface (111) can maintain an optimal surface state throughout the polishing process, and the effect of extending the polishing life can be obtained under the application conditions of the semiconductor process composition (150).

[0280] The abrasive particle dispersion according to the embodiment comprises a dispersant and a dispersing aid having a lower pKa than the dispersing aid. Accordingly, the abrasive particle dispersion according to the embodiment can improve the dispersibility of ceria particles while simultaneously appropriately controlling the zeta potential by using the dispersant and the dispersing aid.

[0281] The abrasive particle dispersion according to the embodiment may have a negative zeta potential while improving the dispersibility of ceria particles. For example, the abrasive particle dispersion according to the embodiment may have a zeta potential of -25 mV to -50 mV at a pH of 7 to 9.

[0282] In addition, since the abrasive particle dispersion according to the embodiment includes the dispersant and the dispersing aid, it can have an appropriate zeta potential change rate. Accordingly, when an additive composition is added to the abrasive particle dispersion according to the embodiment to prepare a polishing slurry composition, the zeta potential change due to pH shock can be minimized.

[0283] In addition, the polishing slurry composition prepared using the polishing particle dispersion according to the embodiment can have low zeta potential change and low particle size change even when left at high temperatures for a long period of time. Accordingly, the polishing slurry composition according to the embodiment can have improved stability with respect to changes over time.

[0284] In addition, since the abrasive particle dispersion according to the embodiment has improved dispersibility, the abrasive slurry composition can suppress agglomeration of the abrasive particles. Accordingly, the abrasive particle dispersion according to the embodiment can prevent defects in the manufacturing process of semiconductor devices.

[0285] In addition, since the abrasive particle dispersion according to the embodiment includes the dispersant and the dispersing aid and has an appropriate pH and zeta potential, the polishing rate and selectivity of the abrasive slurry composition can be improved.

[0286] Specific embodiments of the present invention are presented below. However, the embodiments described below are merely intended to specifically illustrate or explain the present invention, and the scope of the rights of the present invention is not construed as being limited thereby, and the scope of the rights of the present invention is determined by the claims.

[0287]

[0288] Manufacturing example

[0289] Polyacrylic acid (PAA, weight average molecular weight 30,000 g / mol, pKa 4.5) (Polyscience product)

[0290] Polyglycerine #1 (polyglycerine, PG #1, weight average molecular weight 310 g / mol) (Sigma-Aldrich product)

[0291] Polyglycerine #2 (polyglycerine, PG #2, weight average molecular weight 500 g / mol) (Sigma-Aldrich product)

[0292] Polyglycerine #3 (polyglycerine, PG #3, weight average molecular weight 750 g / mol) (Sigma-Aldrich product)

[0293] Polyvinylpyrrolidone (PVP, weight average molecular weight 10,000 g / mol, Sigma-Aldrich product)

[0294] Polydiallyldimethylammonium chloride (PDA, weight average molecular weight 10,000 g / mol, Sigma-Aldrich product)

[0295] Polymethacrylate (PMA, weight average molecular weight 15,000 g / mol, product of Pharmatron)

[0296] Polyoxyethylene Stearyl Amine Ether (SM-30, amine value 34-37 mg KOH / g, Green Chemical Co., Ltd.)

[0297] Polyethylene glycol #1 (polyethylene glycol, PEG #1, weight average molecular weight 200 g / mol)

[0298] Polyethylene glycol #2 (polyethylene glycol, PEG #2, weight average molecular weight 300 g / mol)

[0299] Polyethylene glycol #3 (polyethylene glycol, PEG #3, weight average molecular weight 600 g / mol)

[0300] Polyethylene glycol #4 (polyethylene glycol, PEG #4, weight average molecular weight 2000 g / mol)

[0301] Polyethylene glycol #5 (polyethylene glycol, PEG #5, weight average molecular weight 4000 g / mol)

[0302] ethylene glycol (EG)

[0303] triethylamine (TEA)

[0304] dextrose (DX)

[0305] 4,4,6,6,8,8,8-Heptafluorooctan-1-ol (FS)

[0306] Ceria particles (average particle size 140 nm, Solvay product)

[0307] 2-Pyridinecarboxylic acid (PA, Waco)

[0308] Nitric acid (9 wt% aqueous solution, pKa 1.3)

[0309] The pKa of the above raw materials was measured at a temperature of approximately 25°C.

[0310]

[0311] Abrasive Particle Dispersion #1

[0312] About 100 parts by weight of deionized water, about 2.4 parts by weight of ceria particles, about 0.5 parts by weight of polyacrylic acid, about 0.175 parts by weight of picolinic acid, about 8.3 parts by weight of ethylene glycol, and about 0.005 parts by weight of 4,4,6,6,8,8,8-heptafluorooctan-1-ol were uniformly mixed. Thereafter, ammonia was added to the mixture to adjust the pH to 8, thereby producing an abrasive particle dispersion.

[0313]

[0314] Abrasive particle dispersions #2 to #8

[0315] As shown in Table 1 below, each component was uniformly mixed, ammonia was added to adjust the pH, and abrasive particle dispersions #2 to #5 were prepared.

[0316] Polishing particle dispersion #1 (parts by weight) Polishing particle dispersion #2 (parts by weight) Polishing particle dispersion #3 (parts by weight) Polishing particle dispersion #4 (parts by weight) Polishing particle dispersion #5 (parts by weight) Polishing particle dispersion #6 (parts by weight) Polishing particle dispersion #7 (parts by weight) Deionized water 100 100 100 100 100 100 100 Ceria particle3.53.53.53.53.53.53.5PAA0.50.50.50.50.50.50.5PA0.1750.1750.0880.350.35EG8.38.38.38.38.38.38.3FS0.0050.0050.0050.0050.0050.0050.005pH8988989

[0317] Abrasive Particle Dispersion #8

[0318] About 100 parts by weight of deionized water, about 5.5 parts by weight of ceria particles, about 0.5 parts by weight of polyacrylic acid, about 5.5 parts by weight of ethylene glycol, about 0.005 parts by weight of 4,4,6,6,8,8,8-heptafluorooctan-1-ol, and about 1.2 parts by weight of triethylamine were uniformly mixed. Thereafter, nitric acid was added to the mixture to adjust the pH to 7.8, thereby producing an abrasive particle dispersion.

[0319]

[0320] Abrasive particle dispersions #9 to #14

[0321] As shown in Table 2 below, each component was uniformly mixed to prepare abrasive particle dispersions #9 to #14.

[0322] Polishing particle dispersion #8 (parts by weight) Polishing particle dispersion #9 (parts by weight) Polishing particle dispersion #10 (parts by weight) Polishing particle dispersion #11 (parts by weight) Polishing particle dispersion #12 (parts by weight) Polishing particle dispersion #13 (parts by weight) Polishing particle dispersion #14 (parts by weight) Deionized water 100 100 100 100 100 100 100 Ceria Particle5.55.55.55.55.55.55.5PAA0.50.50.50.50.50.50.5PEG#15.5PEG#25.5PEG#35.5PEG#45.5PEG#55.5E G5.5FS0.0050.0050.0050.0050.0050.0050.005TEA1.21.21.21.21.21.21.2pH7.87.87.87.87.87.87.8

[0323] <Examples and Comparative Examples>

[0324] Example 1

[0325] Abrasive particle dispersion #1 and deionized water were uniformly mixed at a weight ratio of about 1:10 at a speed of about 150 rpm for about 1 hour, thereby preparing abrasive slurry composition #1.

[0326] Examples 2 to 5 and Comparative Examples 1 to 2

[0327] As shown in Table 3 below, deionized water and abrasive particle dispersions were mixed to prepare polishing slurry compositions #2 to #7.

[0328] Distinctive components (weight ratio) Example 1 (Polishing slurry composition #1) Polishing particle dispersion #1: deionized water (1:10) Example 2 (Polishing slurry composition #2) Polishing particle dispersion #2: deionized water (1:10) Example 3 (Polishing slurry composition #3) Polishing particle dispersion #3: deionized water (1:10) Example 4 (Polishing slurry composition #4) Polishing particle dispersion #4: deionized water (1:10) Example 5 (Polishing slurry composition #5) Polishing particle dispersion #5: deionized water (1:10) Comparative example 1 (Polishing slurry composition #6) Polishing particle dispersion #6: deionized water (1:10) Comparative example 2 (Polishing slurry composition #7) Polishing particle dispersion #7: deionized water (1:10)

[0329] Example 6

[0330] Polishing particle dispersion #8 and deionized water were uniformly mixed at a weight ratio of about 1:10 at a speed of about 120 rpm for about 1 hour, thereby preparing polishing slurry composition #8.

[0331] Examples 7 to 12 and Comparative Example 3

[0332] As shown in Table 4 below, deionized water and abrasive particle dispersions were mixed to prepare polishing slurry compositions #9 to #14.

[0333] Distinctive components (weight ratio) Example 6 (Polishing slurry composition #8) Polishing particle dispersion #8 + deionized water (1:10) Example 7 (Polishing slurry composition #9) Polishing particle dispersion #9 + deionized water (1:10) Example 8 (Polishing slurry composition #10) Polishing particle dispersion #10 + deionized water (1:10) Example 9 (Polishing slurry composition #11) Polishing particle dispersion #11 + deionized water (1:10) Example 10 (Polishing slurry composition #12) Polishing particle dispersion #12 + deionized water (1:10) Example 11 (Polishing slurry composition #13) Polishing particle dispersion #13 + deionized water (1:10) Comparative example 3 (Polishing slurry composition #14) Polishing particles Dispersion #14 + deionized water (1:10)

[0334] Evaluation

[0335] Measurement Example 1: Measurement of hydrogen ion concentration (pH)

[0336] The pH of each of the polishing particle dispersions #1 to #7 and the polishing slurry compositions #1 to #7 was measured using a hydrogen ion concentration (pH) measuring device (Horiba, Laqua) while stirring at 200 rpm under room temperature conditions of 20°C to 24°C.

[0337] Measurement Example 2: Measurement of hydrogen ion concentration (pH)

[0338] The previously prepared abrasive particle dispersions #8 to #14 and polishing slurry compositions #8 to #14 were allowed to stand at a temperature of about 60°C for about 14 days. Thereafter, the abrasive particle dispersions, additive compositions, and polishing slurry compositions were each stirred at 200 rpm under room temperature conditions of 20°C to 24°C, and the pH was measured using a hydrogen ion concentration (pH) measuring device (Horiba, Laqua). The pH was measured initially and after 14 days, respectively.

[0339] Measurement Example 3: Polishing Rate Measurement

[0340] For each of the above examples and comparative examples, a silicon oxide wafer having a thickness of about 20,000 Å and a silicon nitride wafer having a thickness of about 2,000 Å were prepared. As illustrated in Fig. 1, the wafers were accommodated in a carrier (160) with the polishing surface facing downward as a polishing target (130). After positioning the carrier (160) so that the polishing surface and the polishing surface (111) are in contact with each other on a platen (120) on which a polishing pad (110, SK Enpulse HD-319B) is mounted so that its polishing surface (111) faces upward, each component is operated for 60 seconds at a pressing pressure of 2.0 psi on the polishing surface of the carrier (160), a rotation speed of 93 rpm of the carrier (160), and a rotation speed of 87 rpm of the platen (120), and polishing is performed while applying the polishing slurry compositions of each of the examples and comparative examples to the polishing surface at a flow rate of 250 ml / min. At the same time, the polishing surface is processed by operating a conditioner (170, Saesol Diamond SKC-CI45) under the conditions of a rotation speed of 250 rpm and a pressing pressure of 8 psi. The thickness of the above wafer after polishing was measured, and the polishing time and the thickness of the wafer before and after polishing were used to calculate the polishing rate value (Rox) in units of Å / min.

[0341] Measurement Example 4: Defect

[0342] The above silicon oxide wafer was prepared and polished using the same method as the polishing rate measurement. Thereafter, defects in the polished wafer were measured using an AIT XP from KLA / TENCOR.

[0343] Measurement Example 5: Zeta potential and ceria particle size measurement

[0344] Nitric acid or ammonia was added to the abrasive particle dispersions #1 to #7 manufactured in the manufacturing examples to adjust the pH as follows. Thereafter, the zeta potential and size of the ceria particles included in the abrasive particle dispersions #1 to #7 manufactured in the manufacturing examples were measured at each pH using a zeta potential meter (Malvern).

[0345] Measurement Example 6: Measurement of Zeta Potential and Ceria Particle Diameter

[0346] The previously prepared abrasive particle dispersions #8 to #14 and the polishing slurry compositions #8 to #14# were allowed to stand at a temperature of about 60°C for about 14 days. Thereafter, the zeta potential and particle diameter of the ceria particles included in the previously prepared abrasive particle dispersions and polishing slurry compositions were measured initially and after 14 days using a zeta potential meter (Malvern, Zetasizer). The abrasive particle dispersions #8 to #14 and the polishing slurry compositions #8 to #14 were stirred at about 200 rpm for about 5 minutes, and then the zeta potential and the particle diameter were measured.

[0347] Measurement Example 7: Measurement of the number of aggregated ceria particles

[0348] The previously prepared abrasive particle dispersion and polishing slurry composition were left at a temperature of about 60°C for about 14 days. Thereafter, the diameter distribution of the ceria particles included in the previously prepared abrasive particle dispersion and polishing slurry composition was measured initially and after 14 days using a laser particle counter (PSS, Accusizer FX A780). The abrasive particle dispersion and the polishing slurry composition were stirred at about 200 rpm for about 5 minutes, and then the diameter distribution was measured.

[0349] As shown in Table 5 below, the zeta potential of the abrasive particle dispersion was derived according to pH.

[0350] Classification pH 8 Particle size (nm) pH 9 Particle size (nm) pH 4 Zeta potential (mV) pH 6 Zeta potential (mV) pH 8 Zeta potential (mV) pH 9 Zeta potential (mV) pH 10 Zeta potential (mV) Polishing particle dispersion #1 131.9 150.2-35.7-39.6-30.3-41.1-63.4 Polishing particle dispersion #2 144.1 132.2-34.8-40.9-35.7-30.2-50.5 Polishing particle dispersion #3 134.5 150.7-37.0-41.8-32.9-43.8-64.1 Polishing particle dispersion #4132.4151.2-32.4-36.2-27.4-35.9-57.8Abrasive particle dispersion #5148.8133.6-31.9-37.3-32.6-28.1-49.0Abrasive particle dispersion #6133.9150.8-38-44.7-35.6-42.3-65.6Abrasive particle dispersion #7148.7134.5-39.1-46.8-40.7-36-57.1

[0351] As shown in Table 6 below, in the polishing slurry compositions according to the examples and comparative examples, the oxide film polishing rate, nitride film polishing rate, selectivity of the oxide film to the nitride film, and defects were measured.

[0352] ClassificationOxide film polishing rate (Å / min)Defect (△3.5 um)Defect (△10 um)Example 13388639218Example 23182715221Example 32976730235Example 43438751240Example 53330720218Comparative example 13077801284Comparative example 228991173375

[0353] As described in Table 6, the polishing slurry composition according to the examples can have improved polishing rates and low defects.

[0354] As shown in Table 7 below, the zeta potential, pH, and diameter of ceria particles of the abrasive particle dispersion were derived.

[0355] ClassificationInitial particle diameter (nm)After 14 daysParticle diameter (nm)Initial zeta potential (mV)After 14 daysZeta potential (mV)Initial pHAfter 14 daysPhysical polishing particle dispersion #8143.2144-37.9-35.97.66.91Magnetic polishing particle dispersion #9144.2146-36.8-34.27.87.02Magnetic polishing particle dispersion #10143.4144.9-35.4-33.37.77.23Magnetic polishing particle dispersion #11143.5145.3-36.2-34.97.87.52Magnetic polishing particle dispersion #12143.1147.6-34.6-32.07.416.648Magnetic polishing particle dispersion #13149.7147.6-36.1-32.87.86.82 Abrasive particle dispersion #14143.3148.0-36.4-31.47.87.05

[0356] As shown in Table 8 below, the zeta potential, pH, and diameter of ceria particles of the polishing slurry composition were derived.

[0357] ClassificationInitial particle diameter (nm)After 14 daysParticle diameter (nm)Initial zeta potential (mV)After 14 daysZeta potential (mV)Initial pHAfter 14 dayspHExample 6142.8140.9-43.7-44.17.527.27Example 7144.2146-46.8-44.27.487.22Example 8143.4144.9-45.4-43.37.477.23Example 9143.5145.3-46.2-44.97.487.22Example 10143.1147.6-44.6-42.07.517.48Example 11149.7147.6-46.1-42.87.487.42Comparative example 3143.3148.0-46.4-41.47.487.15

[0358] As shown in Table 9 below, the number of aggregated ceria particles was derived.

[0359] Number of initial aggregated particles (diameter, 0.6㎛~1.01㎛, number / ㎖) Number of initial aggregated particles (diameter over 1.01㎛, number / ㎖) Number of aggregated particles after 7 days (diameter, 0.6㎛~1.01㎛, number / ㎖) Number of aggregated particles after 7 days (diameter over 1.01㎛, number / ㎖) Polishing particle dispersion #8797953042197 Polishing particle dispersion #917871962048192 Polishing particle dispersion #1037844362858194 Polishing particle dispersion #1127742332859191 Polishing particle dispersion #1218751532889201 Polishing particle dispersion #1335152842926216 Polishing particle dispersion #1428151542829206

[0360] As shown in Table 10 below, in the polishing slurry compositions according to the examples and comparative examples, the oxide film polishing rate, nitride film polishing rate, selectivity of the oxide film to the nitride film, and defects were measured.

[0361] Section Oxide film polishing rate (Å / min) Defect (△3.5 um) Defect (△10 um) Example 6 35 38 9 9 20 Example 7 34 7 4 10 324 Example 8 33 42 15 6 27 Example 9 32 7 32 4 352 Example 10 31 5 5 3 13 118 Example 11 29 10 36 12 02 Comparative example 32 7 45 6 24 236

[0362] As described in Tables 5 to 10 above, the polishing slurry compositions according to the examples can have improved polishing rates and low defects.

Claims

1. Water; ceria particles; dispersant; A dispersing aid having a lower pKa than the above dispersing agent; stabilizers; and Contains pH adjuster, A polishing particle dispersion having a pH of 7 to 9 and a zeta potential of -25 mV to -50 mV.

2. An abrasive particle dispersion according to claim 1, wherein the dispersing aid comprises a pyridine derivative, and the dispersing agent comprises polyacrylic acid.

3. In the first paragraph, an abrasive particle dispersion having a zeta potential change rate (ZR) expressed by the following mathematical formula 1 of -7 mV to 0. [Formula 1] ZR = (Z8 - Z6) / 2 Here, Z8 is the zeta potential of the abrasive particle dispersion at pH 8, and Z6 is the zeta potential of the abrasive particle dispersion at pH 6.

4. In the third paragraph, an abrasive particle dispersion having a zeta potential of -33 mV to -43 mV at pH 7.

5. An abrasive particle dispersion according to claim 1, wherein the dispersant has a pKa that is 0.1 to 5 higher than that of the dispersing aid.

6. In the fifth paragraph, the dispersant is an abrasive particle dispersion having a molecular weight of 2000 g / mol to 100,000 g / mol and a pKa of 3 to 7.

7. In the 6th paragraph, the abrasive particle dispersion liquid in which the dispersant surrounds the ceria particles and the dispersing aid surrounds the dispersant.

8. A polishing particle dispersion in which the pKa difference between the dispersant and the dispersing aid is 0.4 to 1.5 in the fifth paragraph.

9. In the 8th paragraph, the abrasive particle dispersion liquid is comprised of the dispersant in an amount of 0.1 to 0.3 parts by weight based on 100 parts by weight of the water.

10. Water; ceria particles; Anionic dispersant; Nonionic dispersion stabilizers; and Contains pH adjuster, A polishing particle dispersion having a pH of 7 to 9 and a zeta potential of -25 mV to -50 mV.

11. An abrasive particle dispersion according to claim 10, wherein the dispersion stabilizer comprises polyethylene glycol or ethylene glycol, and the dispersant comprises polyacrylic acid.

12. In the 11th paragraph, an abrasive particle dispersion having a pH change (△p) of 0.11 to 2, expressed by the following mathematical formula 1. [Formula 1] △p = │p0 - p14│ Here, p0 is the initial pH of the abrasive particle dispersion, and p14 is the pH after the abrasive particle dispersion is left at a temperature of 60°C for 14 days.

13. In the 11th paragraph, the polyacrylic acid is an abrasive particle dispersion having a molecular weight of 2000 g / mol to 10000 g / mol.

14. In the 13th paragraph, the polyethylene glycol is an abrasive particle dispersion having a molecular weight of 200 g / mol to 5000 g / mol.

15. In the 11th paragraph, an abrasive particle dispersion having a particle size change rate (SR) expressed by the following mathematical formula 2 of 0.001 to 0.

05. [Formula 2] SR = │S0 - S14│ / S0 Here, S0 is the initial particle diameter of the abrasive particle dispersion, and S14 is the particle diameter after the abrasive particle dispersion is left at a temperature of 60°C for 14 days.

16. In the 15th paragraph, an abrasive particle dispersion having an increase in aggregation of only 3000 particles / mL, as expressed by the following mathematical formula 3. [Formula 3] △A = ( A7 - A0 ) Here, A0 is the number of aggregated ceria particles having a particle size of 0.69 μm to 1.01 μm in the abrasive particle dispersion, and A7 is the number of aggregated ceria particles having a particle size of 0.69 μm to 1.01 μm after the abrasive particle dispersion is left at a temperature of 60°C for 7 days.

17. Water; ceria particles; dispersant; A dispersing aid having a lower pKa than the above dispersing agent; stabilizers; and Contains pH adjuster An abrasive slurry composition having a pH of 7 to 9 and a zeta potential of -25 mV to -50 mV.

18. In paragraph 17, The above dispersant includes an anionic dispersant, A polishing slurry composition further comprising a nonionic dispersion stabilizer.

19. Step for preparing semiconductor substrate; A step of spraying a polishing slurry composition onto the semiconductor substrate; and Comprising a step of polishing the semiconductor substrate, The above polishing slurry composition water; ceria particles; dispersant; A dispersing aid having a lower pKa than the above dispersing agent; stabilizers; and Contains pH adjuster A method for manufacturing a semiconductor device having a pH of 7 to 9 and a zeta potential of -25 mV to -50 mV.

20. In paragraph 19, The above dispersant includes an anionic dispersant, A method for manufacturing a semiconductor device, wherein the polishing slurry composition further comprises a nonionic dispersion stabilizer.

Images