Polishing slurry composition and method for manufacturing semiconductor device

Abstract

An embodiment provides a polishing slurry composition comprising: water; abrasive particles; and a pH adjuster, wherein the abrasive particles comprise titanium. The abrasive particles have improved strength and improved hardness, and the polishing slurry composition may maintain polishing performance for a long period of time even after being mixed with hydrogen peroxide.

Description

Polishing slurry composition and method for manufacturing a semiconductor device

[0001] The examples relate to a polishing slurry composition and a method for manufacturing a semiconductor device.

[0002] Chemical Mechanical Polishing (CMP) is a technique that polishes the surface of a sample to a desired level by injecting a polishing slurry into the interface between the polishing pad and the target while frictionally rubbing the pad against the target surface. As modern CMP is applied to the manufacturing of large-scale semiconductor integrated circuits, it is utilized as an essential technique for devices such as transistors, the planarization of interlayer insulating film surfaces in multilayer wiring, the planarization of various film materials such as oxide and nitride films, and the formation of tungsten or copper wiring. As the integration density of semiconductor devices increases and chip sizes decrease each year, the surface structure of semiconductor devices becomes more complex, and the step height between interlayer films becomes larger. Therefore, high-resolution lithography and atomic-level planarization technology are required for the Chemical Mechanical Polishing (CMP) process applied in the manufacturing process of semiconductor devices. This CMP process is a process that flattens a film by simultaneously utilizing physical frictional force and chemical reaction, and can produce vastly different polishing results even due to minute differences in the process components and / or process solutions used. Therefore, the precision required for the manufacturing and design of such process components and / or process solutions is currently being improved to a higher level. Regarding such semiconductor polishing processes, Korean Registered Patent No. 10-0946421, etc., is disclosed.

[0003] The embodiments aim to provide a polishing slurry composition having improved dispersion stability and long-term storage stability, and improved polishing performance, and a method for manufacturing a semiconductor device using the same.

[0004] The polishing slurry composition according to the example comprises water; polishing particles; and a pH adjuster, and the polishing particles comprise titanium.

[0005] In a polishing slurry composition according to one embodiment, the polishing particles may further include sodium.

[0006] In a polishing slurry composition according to one embodiment, the polishing particles may further include calcium.

[0007] In a polishing slurry composition according to one embodiment, the polishing particles include silica, and the polishing particles may further include iron.

[0008] In a polishing slurry composition according to one embodiment, the polishing particles may further include aluminum.

[0009] In a polishing slurry composition according to one embodiment, the polishing particles may further include zirconium.

[0010] In a polishing slurry composition according to one embodiment, the polishing particles may further include magnesium.

[0011] The polishing slurry composition according to the example comprises water; polishing particles; and a pH adjuster, and contains titanium in an amount of 0.1 ppm to 5 ppm based on the total weight.

[0012] A polishing slurry composition according to one embodiment may further include aluminum in an amount of 0.1 ppm to 5 ppm based on the total weight.

[0013] A polishing slurry composition according to one embodiment may further include zirconium in an amount of 0.1 ppm to 7 ppm based on the total weight.

[0014] A polishing slurry composition according to one embodiment may further include hydrogen peroxide.

[0015] 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; polishing particles; and a pH adjuster, and the polishing particles comprise titanium.

[0016] The polishing slurry composition according to the example may include polishing particles containing titanium. In addition, the polishing particles may further include sodium, magnesium, aluminum, calcium, iron, or zirconium.

[0017] In particular, the polishing slurry composition according to the example may contain titanium, sodium, magnesium, aluminum, calcium, iron, or zirconium in an appropriate amount. In particular, the polishing particles may contain colloidal silica containing titanium, sodium, magnesium, aluminum, calcium, iron, or zirconium in an appropriate amount.

[0018] Accordingly, the abrasive particles can have improved strength. That is, the abrasive particles can have improved hardness.

[0019] In addition, the polishing slurry composition according to the example may have improved dispersion stability because it contains titanium, sodium, magnesium, aluminum, calcium, iron, or zirconium in an appropriate amount. In addition, the polishing slurry composition according to the example may have improved long-term storage stability because it contains titanium, sodium, magnesium, aluminum, calcium, iron, or zirconium in an appropriate amount.

[0020] In particular, since the polishing slurry composition according to the example contains titanium, sodium, magnesium, aluminum, calcium, iron, or zirconium in an appropriately low content, it can maintain polishing performance for a long period of time even after being mixed with hydrogen peroxide.

[0021] FIG. 1 schematically illustrates the apparatus configuration for a method of manufacturing the semiconductor device according to one embodiment.

[0022] The advantages and features of the present invention and the methods for achieving them will become clear by referring to the embodiments or examples described below. However, the present invention is not limited to the embodiments or examples disclosed below but may be implemented in various different forms. The embodiments or examples specified below are provided merely 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, and the scope of the rights of the present invention is defined by the scope of the claims.

[0023] In the drawings, the thickness of some components has been enlarged as necessary to clearly represent layers or regions. Additionally, in the drawings, the thickness of some layers and regions has been exaggerated for convenience of explanation. Throughout the specification, the same reference numerals refer to the same components.

[0024] Furthermore, when a part such as a layer, film, region, or plate is described in this specification as being "above," "on," or "on the upper side" of another part, this is interpreted to include not only the case where it is "immediately above" the other part, but also the case where there is another part in between. When a part is described as being "immediately above" another part, it is interpreted to mean that there is no other part in between. Additionally, when a part such as a layer, film, region, or plate is described as being "below," "under," or "below" another part, this is interpreted to include not only the case where it is "immediately below" the other part, but also the case where there is another part in between. When a part is described as being "immediately below" another part, it is interpreted to mean that there is no other part in between.

[0025] Hereinafter, embodiments according to the present invention will be described in detail.

[0026] The polishing slurry composition according to the example may include water, polishing particles, a pH adjuster, and at least one additive.

[0027] The above water may be deionized water. The above water may not substantially contain metal ions.

[0028] The above abrasive particles may include silica. The above abrasive particles may include colloidal silica. The above abrasive particles may be silica particles.

[0029] The above silica particles refer to a composition in the shape of particles in which silica (SiO2) is the main component, and should be understood as a concept that encompasses cases containing trace amounts of heterogeneous components. Here, 'trace amount' may refer to a content of about 0.005% to about 0.03% by weight of the total 100% by weight of the silica particles.

[0030] The average particle size (D50) of the silica particles may be about 5 nm to about 150 nm, for example, about 5 nm to about 100 nm, for example, about 5 nm to about 80 nm, for example, about 10 nm to about 80 nm, for example, about 30 nm to about 50 nm, for example, about 35 nm to about 50 nm, for example, about 40 nm to about 50 nm, for example, about 42 nm to about 48 nm. By including silica particles of such size, not only chemical etching but also physical etching functions of the polishing slurry composition can be adequately secured.

[0031] The above silica particles may have a 10% cumulative mass particle size distribution diameter (D10) in their particle distribution, for example, about 5 nm to about 50 nm, for example, about 5 nm to about 35 nm, for example, about 10 nm to about 35 nm, for example, about 20 nm to about 35 nm, for example, about 23 nm to about 33 nm.

[0032] The above silica particles may have an 80% cumulative mass particle size distribution diameter (D80) in their particle distribution, for example, about 5 nm to about 60 nm, for example, about 10 nm to about 60 nm, for example, about 20 nm to about 60 nm, for example, about 25 nm to about 60 nm, for example, about 35 nm to about 60 nm, for example, about 40 nm to about 55 nm, for example, about 40 nm to about 50 nm.

[0033] The above silica particles may have a 90% cumulative mass particle size distribution diameter (D90) in their particle distribution, for example, about 10 nm to about 90 nm, for example, about 20 nm to about 80 nm, for example, about 30 nm to about 70 nm, for example, about 40 nm to about 60 nm, for example, about 45 nm to about 60 nm.

[0034] The above silica particles may have a particle distribution such that the ratio (D90 / D10) of the 90% cumulative mass particle size distribution diameter (D90) and the 10% cumulative mass particle size distribution diameter (D10) is about 1.90 to about 2.50, for example, about 1.95 to about 2.50, for example, about 2.00 to about 2.50, for example, about 1.90 to about 2.40, for example, about 1.90 to about 2.30, for example, about 1.95 to about 2.30.

[0035] The above silica particles may have a particle distribution such that the ratio (D90 / D80) of the 90% cumulative mass particle size distribution diameter (D90) and the 80% cumulative mass particle size distribution diameter (D80) is greater than about 1.00 and less than about 1.80, for example, about 1.05 to about 1.70, for example, about 1.05 to about 1.60, for example, about 1.05 to about 1.50, for example, about 1.10 to about 1.40.

[0036] The zeta potential of the polishing slurry composition may be +20mV to +45mV or, for example, about +22mV to +40mV. Although the measurement method for the zeta potential of the silica particles in the polishing slurry composition is not particularly limited, for example, it may be measured by introducing about 1 mL of the polishing slurry composition into a measurement cell using a zeta potential measuring device (Malvern, Zeta-sizer Nano ZS). For example, the zeta potential value may be the average value of about 100 measurements. By satisfying the aforementioned range for the zeta potential of the silica particles in the polishing slurry composition, the anti-aggregation effect of the polishing slurry composition and the realization of the desired polishing selectivity ratio may be more advantageous.

[0037] The above abrasive particles may contain titanium. The titanium may be doped into the abrasive particles. The titanium may be chemically bonded to the silica and incorporated into the abrasive particles.

[0038] The above abrasive particles may contain titanium in an amount of about 0.1 ppm to about 13 ppm, about 0.2 ppm to about 10 ppm, about 0.2 ppm to about 10 ppm, about 0.2 ppm to about 8 ppm, about 0.3 ppm to about 7 ppm, about 0.5 ppm to about 5 ppm, about 0.2 ppm to about 5 ppm, about 1 ppm to about 10 ppm, or about 1 ppm to about 5 ppm based on the weight of the solid content.

[0039] Since the abrasive particles contain titanium in the above amount, they can have improved strength and improved dispersion stability. In addition, since the abrasive particles contain titanium in an appropriately low amount, they can maintain abrasive performance even when mixed with hydrogen peroxide and stored for a long period of time.

[0040] The abrasive particles may further contain sodium. The sodium may be doped into the abrasive particles. The sodium may be chemically bonded to the silica and included in the abrasive particles.

[0041] The above abrasive particles may contain sodium in an amount of about 0.1 ppm to about 30 ppm, about 0.1 ppm to about 20 ppm, about 0.1 ppm to about 10 ppm, about 0.1 ppm to about 5 ppm, about 0.2 ppm to about 4 ppm, about 0.2 ppm to about 3 ppm, about 0.2 ppm to about 2 ppm, about 0.5 ppm to about 10 ppm, or about 0.5 ppm to about 5 ppm based on the weight of the solid content.

[0042] Since the abrasive particles contain the sodium in the above amount, they can have improved strength and improved dispersion stability. In addition, since the abrasive particles contain the sodium in an appropriately low amount, they can maintain abrasive performance even when mixed with hydrogen peroxide and stored for a long period of time.

[0043] The abrasive particles may further contain magnesium. The magnesium may be doped into the abrasive particles. The magnesium may be chemically bonded to the silica and included in the abrasive particles.

[0044] The above abrasive particles may contain magnesium in an amount of about 0.01 ppm to about 3 ppm, about 0.01 ppm to about 2 ppm, about 0.01 ppm to about 1 ppm, about 0.01 ppm to about 0.5 ppm, about 0.02 ppm to about 1 ppm, about 0.02 ppm to about 0.7 ppm, about 0.02 ppm to about 0.6 ppm, about 0.05 ppm to about 1 ppm, or about 0.05 ppm to about 0.5 ppm based on the weight of the solid content.

[0045] Since the abrasive particles contain magnesium in the above amount, they can have improved strength and improved dispersion stability. In addition, since the abrasive particles contain magnesium in an appropriately low amount, they can maintain abrasive performance even when mixed with hydrogen peroxide and stored for a long period of time.

[0046] The above abrasive particles may further include aluminum. The aluminum may be doped into the abrasive particles. The aluminum may be chemically bonded to the silica and incorporated into the abrasive particles.

[0047] The above abrasive particles may contain the aluminum in an amount of about 0.1 ppm to about 20 ppm, about 0.1 ppm to about 15 ppm, about 0.1 ppm to about 10 ppm, about 0.1 ppm to about 8 ppm, about 0.2 ppm to about 10 ppm, about 0.5 ppm to about 9 ppm, about 0.5 ppm to about 6 ppm, about 2 ppm to about 10 ppm, or about 2 ppm to about 15 ppm based on the weight of the solid content.

[0048] Since the abrasive particles contain the aluminum in the above amount, they can have improved strength and improved dispersion stability. In addition, since the abrasive particles contain the aluminum in an appropriately low amount, they can maintain abrasive performance even when mixed with hydrogen peroxide and stored for a long period of time.

[0049] The abrasive particles may further contain calcium. The calcium may be doped into the abrasive particles. The calcium may be chemically bonded to the silica and incorporated into the abrasive particles.

[0050] The above abrasive particles may contain calcium in an amount of about 0.01 ppm to about 2 ppm, about 0.01 ppm to about 1.5 ppm, about 0.01 ppm to about 1 ppm, about 0.01 ppm to about 0.8 ppm, about 0.02 ppm to about 1 ppm, about 0.05 ppm to about 0.9 ppm, about 0.05 ppm to about 0.6 ppm, about 0.05 ppm to about 1 ppm, or about 0.02 ppm to about 1.5 ppm based on the weight of the solid content.

[0051] Since the abrasive particles contain calcium in the above amount, they can have improved strength and improved dispersion stability. In addition, since the abrasive particles contain calcium in an appropriately low amount, they can maintain abrasive performance even when mixed with hydrogen peroxide and stored for a long period of time.

[0052] The above abrasive particles may further contain iron. The iron may be doped into the abrasive particles. The iron may be chemically bonded to the silica and incorporated into the abrasive particles.

[0053] The above abrasive particles may contain iron in an amount of about 0.01 ppm to about 5 ppm, about 0.02 ppm to about 4 ppm, about 0.05 ppm to about 3 ppm, about 0.05 ppm to about 2 ppm, about 0.05 ppm to about 1.5 ppm, about 0.5 ppm to about 3 ppm, about 0.5 ppm to about 6 ppm, about 0.5 ppm to about 5 ppm, or about 0.2 ppm to about 1.5 ppm based on the weight of the solid content.

[0054] Since the abrasive particles contain the iron in the above amount, they can have improved strength and improved dispersion stability. In addition, since the abrasive particles contain the iron in an appropriately low amount, they can maintain abrasive performance even when mixed with hydrogen peroxide and stored for a long period of time.

[0055] The above abrasive particles may further contain zinc. The zinc may be doped into the abrasive particles. The zinc may be chemically bonded to the silica and incorporated into the abrasive particles.

[0056] The above abrasive particles may contain zinc in an amount of about 0.001 ppm to about 0.05 ppm, about 0.002 ppm to about 0.04 ppm, about 0.005 ppm to about 0.03 ppm, about 0.005 ppm to about 0.02 ppm, about 0.005 ppm to about 0.015 ppm, about 0.005 ppm to about 0.03 ppm, about 0.005 ppm to about 0.06 ppm, about 0.005 ppm to about 0.05 ppm, or about 0.002 ppm to about 0.015 ppm based on the weight of the solid content.

[0057] Since the abrasive particles contain zinc in the above amount, they can have improved strength and improved dispersion stability. In addition, since the abrasive particles contain zinc in an appropriately low amount, they can maintain abrasive performance even when mixed with hydrogen peroxide and stored for a long period of time.

[0058] The above abrasive particles may further contain zirconium. The zirconium may be doped into the abrasive particles. The zirconium may be chemically bonded to the silica and incorporated into the abrasive particles.

[0059] The above abrasive particles may contain the zirconium in an amount of about 0.1 ppm to about 20 ppm, about 0.2 ppm to about 25 ppm, about 0.5 ppm to about 15 ppm, about 0.5 ppm to about 10 ppm, about 0.5 ppm to about 20 ppm, about 1 ppm to about 15 ppm, about 1 ppm to about 10 ppm, about 0.5 ppm to about 9 ppm, or about 2 ppm to about 8 ppm based on the weight of the solid content.

[0060] Since the abrasive particles contain the zirconium in the above amount, they can have improved strength and improved dispersion stability. In addition, since the abrasive particles contain the zirconium in an appropriately low amount, they can maintain abrasive performance even when mixed with hydrogen peroxide and stored for a long period of time.

[0061] The above abrasive particles may further contain potassium. The potassium may be doped into the abrasive particles. The potassium may be chemically bonded to the silica and incorporated into the abrasive particles.

[0062] The above abrasive particles may contain potassium in an amount of about 30 ppm to about 3000 ppm, about 40 ppm to about 2500 ppm, about 50 ppm to about 1500 ppm, about 50 ppm to about 1000 ppm, about 50 ppm to about 700 ppm, about 50 ppm to about 800 ppm, about 100 ppm to about 1000 ppm, about 50 ppm to about 900 ppm, or about 120 ppm to about 800 ppm based on the weight of the solid content.

[0063] Since the abrasive particles contain potassium in the above amount, they can have improved strength and improved dispersion stability. In addition, since the abrasive particles contain potassium in an appropriately low amount, they can maintain abrasive performance even when mixed with hydrogen peroxide and stored for a long period of time.

[0064] In the above abrasive particles, the content of the total metal excluding silicon may be about 30 ppm to about 3000 ppm, about 40 ppm to about 2500 ppm, about 50 ppm to about 1500 ppm, about 50 ppm to about 1000 ppm, about 50 ppm to about 700 ppm, about 50 ppm to about 800 ppm, about 100 ppm to about 1000 ppm, about 50 ppm to about 900 ppm, or about 120 ppm to about 800 ppm based on the weight of the solid content.

[0065] Since the abrasive particles contain the metal in the above amount, they can have improved strength and improved dispersion stability. In addition, since the abrasive particles contain the metal in an appropriately low amount, they can maintain abrasive performance even when mixed with hydrogen peroxide and stored for a long period of time.

[0066] In the above abrasive particles, the lithium content based on particle weight may be less than 0.1 ppm.

[0067] In the above abrasive particles, the chromium content based on particle weight may be less than 0.1 ppm.

[0068] In the above abrasive particles, the cobalt content based on particle weight may be less than 0.1 ppm.

[0069] In the above abrasive particles, the nickel content based on particle weight may be less than 0.1 ppm.

[0070] In the above abrasive particles, the copper content based on particle weight may be less than 0.1 ppm.

[0071] The above abrasive particles can be manufactured by the following method.

[0072] First, the method for manufacturing the above-mentioned abrasive particles may include the step of preparing a first raw material solution containing an alkoxysilane and the step of preparing a second raw material solution.

[0073] The first raw material solution above may include a component for forming the main framework of the silica particles.

[0074] The above alkoxysilanes are, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetraethylorthosilicate, silicic acid, tetramethylorthosilicate, tetrapropylorthodilicate, triacetoxy(methyl)silane, isobutyl(trimethoxy)silane, tris(trimethylsiloxy)silane, triethoxy(octyl)silane, It may include one selected from the group consisting of trimethoxy(octyl)silane, trimethoxy(octadecyl)silane, triethoxy(octadecyl)silane, tetrakix(trimethylsilyloxy)silane, methyltris(2-methoxyethoxy)silane, trimethoxy[3-methylamino]proptl)silane, and combinations thereof.

[0075] In one embodiment, the alkoxysilane is in an amount of about 5% to about 30% by weight, for example, about 6% to about 30% by weight, for example, about 7% to about 30% by weight, for example, about 8% to about 30% by weight, for example, about 9% to about 30% by weight, for example, about 10% to about 30% by weight, for example, about 11% to about 30% by weight, for example, about 12% to about 30% by weight, for example, about 13% to about 30% by weight, for example, about 5% to about 29% by weight, for example, about 5% to about 28% by weight, for example, about 5% to about 27% by weight, for example, about 5% to about 26% by weight, for example, about It may be included in an amount of 5% to about 25% by weight, for example, about 5% to about 24% by weight, for example, about 5% to about 23% by weight, for example, about 7% to about 28% by weight, for example, about 9% to about 26% by weight, for example, about 11% to about 24% by weight, for example, about 13% to about 22% by weight. If the alkoxysilane is included in an amount that is too small in the total raw material, there is a concern that the efficiency of the particle manufacturing process may be reduced, and if the alkoxysilane is included in an excessive amount in the total raw material, there is a concern that particles of non-uniform size may be produced or that the particle shape may be disadvantageous in terms of defect occurrence.

[0076] The second raw material solution may include an organic solvent, a catalyst, water, and additives. Through such a combination of components, the chemical reaction for forming the silica particles can proceed appropriately. In addition, it may be more advantageous to appropriately control the reaction rate of silica particle generation and to prevent excessive enlargement and aggregation of the particles.

[0077] In one embodiment, the organic solvent may include one selected from the group consisting of methanol, ethanol, propanol (isopropyl alcohol, rubbing alcohol), butanol, pentanol, hexadecanol (cetyl alcohol), and combinations thereof. By using the above type of organic solvent, there may be no reaction with the functional groups generated during the hydrolysis of the first raw material solution, which may be advantageous for producing uniform particles.

[0078] The content of the organic solvent is about 30% to about 90% by weight, for example, about 30% to about 85% by weight, for example, about 30% to about 80% by weight, for example, about 35% to about 90% by weight, for example, about 40% to about 90% by weight, for example, about 45% to about 90% by weight, for example, about 50% to about 90% by weight, for example, about 35% to about 85% by weight, for example, about 40% to about 85% by weight, for example, about 45% to about 80% by weight, for example, about 50% to about 80% by weight, for example, about 55% to about 80% by weight, for example, about 60% to about 90% by weight, for example, based on the total weight of the first raw material solution and the second raw material solution. The amount may be approximately 70% by weight to approximately 90% by weight. If the amount of the organic solvent is excessively small, it may be difficult to sufficiently disperse the first raw material solution, and there is a risk that particles of non-uniform size may be formed. In addition, if the amount of the organic solvent is excessively large, there is a risk that process efficiency may decrease.

[0079] In one embodiment, the catalyst is ammonia (NH3), ammonium nitrate (NH4NO3), ammonium fluoride (NH4F), 4-hydroxybenzehydrazide (HOC6H4CONHNH2), glutamine, urea, ethylenediamine, glycine, pyridine, triethanolamine, 2-methylbutylamine, ethanolamine, cyclopropylpropylamine, triethylamine, propylamine, diethylamine, isopropylamine, 2-cyclopropylethylamine, and 1,2,4-triazole-3-amine. It may include one selected from the group consisting of methylpyrazolamine (1-Methyl-1H-pyrazol-3-amine), aminotetrahydrofuran (3-aminotetrahydrofuran), aminotriazole (3-amino-1,2,4,-Triazole), butylamine, aminothiazole (2-aminothiazole), allylamine, tetramethylenediamine, and combinations thereof.

[0080] The catalyst may be in an amount of about 0.5% to about 5.0% by weight, for example, about 1.0% to about 5.0% by weight, relative to the total weight of the first raw material solution and the second raw material solution. If the amount of the catalyst is excessively small, it may fail to separate the silicon of the alkoxysilane in the first raw material solution from the remaining functional groups, which may result in insufficient silica particles being produced or the particle formation time taking excessively long. Additionally, if the amount of the catalyst is excessively large, the separation of the silicon of the alkoxysilane in the first raw material solution from the remaining functional groups may occur too quickly, resulting in the formation of large particles or the occurrence of gelling during the stabilization process after particle formation.

[0081] The above water may be used in the remainder amount such that the total components, including the aforementioned components of the first raw material liquid and the second raw material liquid, amount to 100% by weight.

[0082] Additionally, the first raw material solution and / or the second raw material solution may include a metal other than silicon. The metal may be included in the first raw material solution and / or the second raw material solution in ionic form. For example, the metal may be included in the first raw material solution and / or the second raw material solution in chloride form.

[0083] The metal may be selected from at least one of the group consisting of titanium, sodium, magnesium, aluminum, calcium, iron, zinc, potassium, or zirconium.

[0084] The metal may be added to the first raw material solution and / or the second raw material solution in an appropriate amount based on the total weight of the alkoxysilane. Accordingly, the abrasive particles may contain the metal in an amount as described above.

[0085] For example, in the first raw material solution and the second raw material solution, the content of the titanium ions can be adjusted to about 0.1 ppm to about 13 ppm, about 0.2 ppm to about 10 ppm, about 0.2 ppm to about 10 ppm, about 0.2 ppm to about 8 ppm, about 0.3 ppm to about 7 ppm, about 0.5 ppm to about 5 ppm, about 0.2 ppm to about 5 ppm, about 1 ppm to about 10 ppm, or about 1 ppm to about 5 ppm based on the weight of the alkoxysilane.

[0086] For example, in the first raw material solution and the second raw material solution, the sodium ion content can be adjusted to about 0.1 ppm to about 30 ppm, about 0.1 ppm to about 20 ppm, about 0.1 ppm to about 10 ppm, about 0.1 ppm to about 5 ppm, about 0.2 ppm to about 4 ppm, about 0.2 ppm to about 3 ppm, about 0.2 ppm to about 2 ppm, about 0.5 ppm to about 10 ppm, or about 0.5 ppm to about 5 ppm based on the weight of the alkoxysilane.

[0087] For example, in the first raw material solution and the second raw material solution, the content of magnesium ions can be adjusted to about 0.01 ppm to about 3 ppm, about 0.01 ppm to about 2 ppm, about 0.01 ppm to about 1 ppm, about 0.01 ppm to about 0.5 ppm, about 0.02 ppm to about 1 ppm, about 0.02 ppm to about 0.7 ppm, about 0.02 ppm to about 0.6 ppm, about 0.05 ppm to about 1 ppm, or about 0.05 ppm to about 0.5 ppm based on the weight of the alkoxysilane.

[0088] For example, in the first raw material solution and the second raw material solution, the content of the aluminum ions may be about 0.1 ppm to about 20 ppm, about 0.1 ppm to about 15 ppm, about 0.1 ppm to about 10 ppm, about 0.1 ppm to about 8 ppm, about 0.2 ppm to about 10 ppm, about 0.5 ppm to about 9 ppm, about 0.5 ppm to about 6 ppm, about 2 ppm to about 10 ppm, or about 2 ppm to about 15 ppm based on the weight of the alkoxysilane.

[0089] For example, in the first raw material solution and the second raw material solution, the calcium ion content may be about 0.01 ppm to about 2 ppm, about 0.01 ppm to about 1.5 ppm, about 0.01 ppm to about 1 ppm, about 0.01 ppm to about 0.8 ppm, about 0.02 ppm to about 1 ppm, about 0.05 ppm to about 0.9 ppm, about 0.05 ppm to about 0.6 ppm, about 0.05 ppm to about 1 ppm, or about 0.02 ppm to about 1.5 ppm based on the weight of the alkoxysilane.

[0090] For example, in the first raw material solution and the second raw material solution, the iron ion content may be about 0.01 ppm to about 5 ppm, about 0.02 ppm to about 4 ppm, about 0.05 ppm to about 3 ppm, about 0.05 ppm to about 2 ppm, about 0.05 ppm to about 1.5 ppm, about 0.5 ppm to about 3 ppm, about 0.5 ppm to about 6 ppm, about 0.5 ppm to about 5 ppm, or about 0.2 ppm to about 1.5 ppm based on the weight of the alkoxysilane.

[0091] For example, in the first raw material solution and the second raw material solution, the content of zinc ions may be about 0.001 ppm to about 0.05 ppm, about 0.002 ppm to about 0.04 ppm, about 0.005 ppm to about 0.03 ppm, about 0.005 ppm to about 0.02 ppm, about 0.005 ppm to about 0.015 ppm, about 0.005 ppm to about 0.03 ppm, about 0.005 ppm to about 0.06 ppm, about 0.005 ppm to about 0.05 ppm, or about 0.002 ppm to about 0.015 ppm based on the weight of the alkoxysilane.

[0092] For example, in the first raw material solution and the second raw material solution, the content of the zirconium ions may be about 0.1 ppm to about 20 ppm, about 0.2 ppm to about 25 ppm, about 0.5 ppm to about 15 ppm, about 0.5 ppm to about 10 ppm, about 0.5 ppm to about 20 ppm, about 1 ppm to about 15 ppm, about 1 ppm to about 10 ppm, about 0.5 ppm to about 9 ppm, or about 2 ppm to about 8 ppm based on the weight of the alkoxysilane.

[0093] For example, in the first raw material solution and the second raw material solution, the potassium ion content may be about 30 ppm to about 3000 ppm, about 40 ppm to about 2500 ppm, about 50 ppm to about 1500 ppm, about 50 ppm to about 1000 ppm, about 50 ppm to about 700 ppm, about 50 ppm to about 800 ppm, about 100 ppm to about 1000 ppm, about 50 ppm to about 900 ppm, or about 120 ppm to about 800 ppm based on the weight of the alkoxysilane. Based on the weight of the solid content, it may be about 0.1 ppm to about 13 ppm, about 0.2 ppm to about 10 ppm, about 0.2 ppm to about 10 ppm, about 0.2 ppm to about 8 ppm, about 0.3 ppm to about 7 ppm, about 0.5 ppm to about 5 ppm, about 0.2 ppm to about 5 ppm, about 1 ppm to about 10 ppm, or about 1 ppm to about 5 ppm.

[0094] Since the content of metal ions contained in the first raw material solution and the second raw material solution is controlled as described above, the abrasive particles can contain the metal in an appropriate amount.

[0095] The method for manufacturing the silica particles described above includes the step of obtaining silica particles by mixing and reacting the first raw material solution and the second raw material solution. In other words, the method for manufacturing the silica particles described above may include a raw material mixing and particle synthesis step. The raw material mixing and particle synthesis step may include a reaction stabilization step. The reaction stabilization step refers to a process in which the particles generated by the reaction of the first raw material solution and the second raw material solution grow sufficiently and stabilize in terms of size and shape.

[0096] The step of obtaining silica particles by mixing and reacting the first raw material solution and the second raw material solution can be performed by mixing the first raw material solution and the second raw material solution and reacting them at a temperature of about 25°C to about 80°C for about 4 hours to about 10 hours. Performing the reaction within such a temperature and time range may be advantageous for the first raw material solution and the second raw material solution to be sufficiently mixed and reacted with each other to obtain particles grown to an appropriate size. If the reaction proceeds at a temperature that is too low, the decomposition rate of the first raw material solution is slow, which may result in a long reaction time or the formation of particles larger than necessary. Additionally, if the reaction proceeds at a temperature that is too high, the decomposition of the first raw material solution may occur excessively, leading to a large amount of particle nucleation and the formation of particles with small and non-uniform sizes. The above reaction time of about 4 hours to about 10 hours includes the reaction stabilization time of the particles produced by the reaction of the first raw material solution and the second raw material solution. If the above reaction time is excessively short, the first raw material solution may not decompose sufficiently, which may lead to a decrease in the yield of the particle production amount and a risk that the particle size may not grow sufficiently.

[0097] In one embodiment, the step of obtaining silica particles by mixing and reacting the first raw material solution and the second raw material solution may include: mixing the first raw material solution in a reactor heated to a first temperature (T1) and the second raw material solution in a reactor heated to a second temperature (T2); and reacting the mixed first raw material solution and the second raw material solution by stirring at a speed greater than 50 rpm.

[0098] The difference (|T1-T2|) between the first temperature (T1) and the second temperature (T2) may be less than about 20°C, for example, greater than or equal to about 0°C, less than about 20°C, for example, between about 0°C and about 15°C, for example, between about 0°C and about 10°C, for example, between about 0°C and about 5°C. By controlling the reactor temperature difference between the first raw material liquid and the second raw material liquid to such a range, it is more advantageous in terms of preventing the formation of large particles, producing silica particles with an appropriate particle size, and increasing the uniformity of particle size.

[0099] In one embodiment, the stirring speed of the mixed first raw material liquid and the second raw material liquid may be, for example, greater than about 50 rpm and less than or equal to about 250 rpm, for example, about 70 rpm to about 250 rpm, for example, about 100 rpm to about 250 rpm, for example, about 150 rpm to about 250 rpm. By reacting the first raw material liquid and the second raw material liquid while stirring within such a speed range, the formation of large particles is prevented, silica particles having an appropriate particle size are produced, and it may be more advantageous in terms of increasing the uniformity of particle size.

[0100] Once the step of obtaining the above silica particles is completed, a silica particle dispersion in an organic solvent is obtained. The silica particle dispersion itself can be applied for various uses.

[0101] In addition, the step of obtaining the silica particles may include a desolvation step of removing the organic solvent of the silica particle dispersion to obtain silica particles optimized for a polishing composition for a semiconductor process; a water exchange step of replacing the silica particle dispersion with a silica particle aqueous dispersion; and a concentration control step of controlling the concentration of silica particles in the silica particle aqueous dispersion.

[0102] In the above desolvation step, the organic solvent and catalyst may be removed after stabilization of the silica particles. In one embodiment, the desolvation step may be performed by applying a method selected from the group consisting of evaporation, vacuum evaporation, membrane separation, filtration, and combinations thereof.

[0103] For example, a filtration method can be applied to the above desolvation step, and more specifically, an ultrafiltration membrane filter can be applied. In one embodiment, the pores of the ultrafiltration membrane filter may be about 30,000 dalton to about 500,000 dalton, for example, about 50,000 dalton to about 500,000 dalton, for example, about 100,000 dalton to about 500,000 dalton.

[0104] The above water exchange step may be a process of preparing a silica particle aqueous dispersion by adding a large amount of water after the above desolvation step to lower the concentration of the organic solvent and increase the proportion of water. The water applied in the above water exchange step may be, for example, ultrapure water.

[0105] The concentration control step may be a step of controlling the particle concentration and particle size of the silica particle aqueous dispersion. In one embodiment, the concentration control step may be performed by applying a method selected from the group consisting of evaporation, vacuum evaporation, membrane separation, filtration, and combinations thereof.

[0106] For example, a filter method can be applied to the concentration control step, and more specifically, an ultrafiltration membrane filter can be applied. In one embodiment, the pores of the ultrafiltration membrane filter may be about 30,000 daltons to about 500,000 daltons, for example, about 50,000 daltons to about 500,000 daltons, for example, about 100,000 daltons to about 500,000 daltons.

[0107] The above desolvation step, the above water exchange step, and the above concentration control step may be repeated two or more times as needed.

[0108] The silica particle aqueous dispersion prepared by the concentration control step may have a solid content of about 20% by weight to about 30% by weight. In addition, the average particle size of the silica particles in the silica particle aqueous dispersion may be about 20nm to about 120nm. By satisfying such solid content and particle size, the silica particles may be more advantageous for application in a polishing composition for semiconductor processes.

[0109] In addition, during the concentration control step, a large amount of deionized water may be introduced into the ultrafiltration membrane filter. Accordingly, ions contained in the silica particle aqueous dispersion may be subjected to exchange treatment. Consequently, the content of metal ions contained in the silica particle aqueous dispersion can be appropriately controlled.

[0110] Subsequently, the silica particles can be surface-treated with an alkoxysilane. The alkoxysilane is slowly introduced into the aqueous dispersion of the silica particles, and the aqueous dispersion of the silica particles is stirred at room temperature for about 12 hours to about 36 hours, so that the silica particles can be surface-treated with the alkoxysilane.

[0111] The above alkoxysilane may include 3-aminopropyltriethoxysilane (APTES).

[0112] The alkoxysilane can be introduced into the aqueous dispersion of the silica particles so that the molar ratio of SiO2 contained in the silica particles and the APTES is about 5:1 to about 20:1.

[0113] The polishing slurry composition according to the embodiment may include at least one additive together with the silica particles. The additive may perform a role in enabling the polishing slurry composition to achieve a technical purpose primarily through chemical action. Specifically, the additive may chemically react with the constituent components of the film to be polished to cause the film to be polished to exhibit a surface state optimized for polishing.

[0114] In one embodiment, the at least one additive may include an organic acid. The role of the organic acid is not particularly limited, but, for example, it may function as a complexing agent to control polishing properties for copper films or to trap metal ions. Additionally, the organic acid may play a role in controlling the hydrogen ion concentration (pH) of the polishing slurry composition. The above organic acids are, for example, acetic acid (CH3COOH), formic acid, benzoic acid, nicotinic acid, picolinic acid, alanine, phenylalanine, valine, leucine, isoleucine, arginine, aspartic acid, citric acid, adipic acid, succinic acid, oxalic acid, malonic acid, glycine, glutamic acid, glutaric acid, phthalic acid, histidine, lysine, glutamine, pyrrolysine, It may include one selected from the group consisting of selenocysteine, threonine, serine, cysteine, methionine, asparagine, tyrosine, diiodotyrosine, tryptophan, proline, oxyproline, ethylenediaminetetraacetic acid (EDTA), nitrotriacetic acid (NTA), iminodiaacetic acid (IDA) and combinations thereof.

[0115] In one embodiment, the content of the organic acid may be about 0.10 parts by weight or more, for example, about 0.20 parts by weight or more, for example, about 0.30 parts by weight or more, for example, about 0.40 parts by weight or more, for example, about 0.50 parts by weight or more, for example, about 0.60 parts by weight or more, for example, about 0.70 parts by weight or more, for example, about 0.80 parts by weight or more, for example, about 5.00 parts by weight or less, for example, about 4.00 parts by weight or less, for example, about 3.00 parts by weight or less, for example, about 2.50 parts by weight or less, for example, about 2.00 parts by weight or less, for example, about 1.50 parts by weight or less, for example, about 1.00 parts by weight or less, based on 100 parts by weight of the silica particles.

[0116] The above at least one additive may include an azole-based compound. The role of the azole-based compound is not particularly limited, but, for example, it may play a role in controlling the surface properties of the copper film. The above azole compounds are, for example, benzotriazole (BTA), 5-methyl-1H-benzotriazole (5-MBTA), 3-amino-1,2,4-triazole (3-Amino-1,2,4-Triazole), 5-phenyl-1H-tetrazole (5-Phenyl-1H-Tetrazole), 3-amino-5-methyl-4H-1,2,4-triazole (3-Amino-5-Methyl-4H-1,2,4-Triazole), 5-aminotetrazole (ATZ), 1,2,4-triazole, 1,2,3-triazole, tetrazole, pentazole, It may include one selected from the group consisting of tolitriazole, imidazole, pyrozole, and combinations thereof.

[0117] In one embodiment, the content of the azole compound may be about 0.10 parts by weight or more, for example, about 0.20 parts by weight or more, for example, about 0.30 parts by weight or more, for example, about 0.40 parts by weight or more, for example, about 0.50 parts by weight or more, for example, about 0.60 parts by weight or more, for example, about 5.00 parts by weight or less, for example, about 4.00 parts by weight or less, for example, about 3.00 parts by weight or less, for example, about 2.50 parts by weight or less, for example, about 2.00 parts by weight or less, for example, about 1.50 parts by weight or less, for example, about 1.00 parts by weight or less, based on 100 parts by weight of the silica particles.

[0118] The above at least one additive may include a sugar alcohol-based compound. The above sugar alcohol may include, for example, one selected from the group consisting of ethylene glycol, glycerol, erythritol, threiol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt, maltitol, lactitol, maltotriitol, maltotetraitol, polyglycitol, and combinations thereof.

[0119] In one embodiment, the content of the sugar alcohol-based compound is about 0.10 parts by weight or more, for example, about 0.20 parts by weight or more, for example, about 0.30 parts by weight or more, for example, about 0.40 parts by weight or more, for example, about 0.50 parts by weight or more, for example, about 0.60 parts by weight or more, for example, about 0.70 parts by weight or more, for example, about 0.80 parts by weight or more, for example, about 0.90 parts by weight or more, for example, about 1.00 parts by weight or more, for example, about 1.10 parts by weight or more, for example, about 1.20 parts by weight or more, for example, about 5.00 parts by weight or less, for example, about 4.00 parts by weight or less, for example, about 3.00 parts by weight or less, for example, about 2.50 parts by weight or less, for example, about 2.00 parts by weight or less, for example, It may be about 1.50 parts by weight or less.

[0120] The above at least one additive may include a hydrogen ion concentration (pH) regulator. The pH regulator may include, for example, one selected from the group consisting of nitric acid, hydrochloric acid, acetic acid, sulfuric acid, potassium hydroxide, sodium hydroxide, ammonia, and combinations thereof.

[0121] In one embodiment, the content of the pH adjuster is about 0.01 parts by weight or more, for example, about 0.02 parts by weight or more, for example, about 0.03 parts by weight or more, for example, about 0.04 parts by weight or more, for example, about 0.05 parts by weight or more, for example, about 0.06 parts by weight or more, for example, about 0.07 parts by weight or more, for example, about 0.08 parts by weight or more, for example, about 0.09 parts by weight or more, for example, about 0.10 parts by weight or more, for example, about 0.20 parts by weight or more, for example, about 0.30 parts by weight or more, for example, about 0.40 parts by weight or more, for example, about 0.50 parts by weight or more, for example, about 0.60 parts by weight or more, for example, about 0.70 parts by weight or more, for example, about 0.80 parts by weight or more, for example, about It may be 5.00 parts by weight or less, for example, about 4.00 parts by weight or less, for example, about 3.00 parts by weight or less, for example, about 2.50 parts by weight or less, for example, about 2.00 parts by weight or less, for example, about 1.50 parts by weight or less.

[0122] The above semiconductor polishing composition may have a solid content of about 3.0 wt% to about 20 wt%, for example, about 3.0 wt% to about 18 wt%, for example, about 3.0 wt% to about 16 wt%, for example, about 3.0 wt% to about 14 wt%, for example, about 3.0 wt% to about 12 wt%, for example, about 3.0 wt% to about 10 wt%. If the solid content is excessively low, there is a concern that the polishing rate for each film of the polishing target may not be sufficiently secured, and if the solid content is excessively high, there is a concern that defects such as scratches may occur during the polishing process due to unnecessary aggregation. The polishing slurry composition comprises the polishing particles, the at least one additive, and the solvent, and satisfies the solid content of the above range, which may be more advantageous for injecting at a uniform flow rate when applied to a polishing process, and may be more advantageous in terms of ensuring uniform dispersibility and storage stability during the distribution and storage of the polishing slurry composition.

[0123] The above polishing slurry composition may have a hydrogen ion concentration (pH) of about 2.0 to about 6.0, for example, about 2.0 to about 5.0, for example, about 3.0 to about 6.0. By satisfying such a hydrogen ion concentration range, the technical effect of the silica particles can be maximized.

[0124] The polishing slurry composition according to the example may further include a polishing aid. The polishing aid may be selected from at least one of the group consisting of sodium chloride, potassium chloride, anhydrous potassium carbonate, sodium sulfate, potassium sulfate, lithium sulfate, sodium pyrophosphate, phosphoric acid, calcium chloride, calcium bromide, magnesium sulfate, barium chloride, barium bromide, magnesium chloride, magnesium bromide, or strontium chloride. The polishing aid may be phosphoric acid. The polishing aid can improve the polishing rate of a silicon nitride film.

[0125] The above-mentioned polishing aid may be included in the polishing slurry composition according to the example in an amount of about 0.01 wt% to about 0.1 wt%, about 0.01 wt% to about 0.2 wt%, about 0.01 wt% to about 0.15 wt%, or about 0.01 wt% to about 0.08 wt% based on the total weight of the composition.

[0126] Since the above-mentioned polishing aid has the above-mentioned characteristics, the polishing slurry composition according to the example can have an improved polishing rate on silicon nitride films, etc.

[0127] In addition, the polishing slurry composition according to the example may include hydrogen peroxide. The hydrogen peroxide may perform the function of an oxidizing agent.

[0128] The polishing slurry composition according to the example may contain the hydrogen peroxide in an amount of about 0.05 wt% to about 1 wt%, about 0.05 wt% to about 0.7 wt%, about 0.05 wt% to about 0.5 wt%, or about 0.05 wt% to about 0.4 wt% based on the total weight.

[0129] The polishing slurry composition according to the example may contain titanium in an amount of about 0.1 ppm to about 5 ppm, 0.1 ppm to about 4 ppm, about 0.1 ppm to about 3 ppm, or about 0.1 ppm to about 2 ppm based on the total weight.

[0130] The polishing slurry composition according to the example may contain aluminum in an amount of about 0.1 ppm to about 6 ppm, 0.1 ppm to about 5 ppm, about 0.1 ppm to about 4 ppm, or about 0.1 ppm to about 3 ppm based on the total weight.

[0131] The polishing slurry composition according to the example may contain zirconium in an amount of about 0.1 ppm to about 7 ppm, 0.1 ppm to about 6 ppm, about 0.1 ppm to about 5 ppm, or about 0.1 ppm to about 4 ppm based on the total weight.

[0132] The polishing slurry composition according to the example may contain sodium in an amount of about 0.05 ppm to about 5 ppm, 0.05 ppm to about 4 ppm, about 0.1 ppm to about 3 ppm, or about 0.1 ppm to about 2 ppm based on the total weight.

[0133] The polishing slurry composition according to the example may contain magnesium in an amount of about 0.05 ppm to about 3 ppm, 0.05 ppm to about 2 ppm, about 0.05 ppm to about 1.5 ppm, or about 0.05 ppm to about 1 ppm based on the total weight.

[0134] The polishing slurry composition according to the example may contain calcium in an amount of about 0.05 ppm to about 3 ppm, 0.05 ppm to about 2 ppm, about 0.05 ppm to about 1.5 ppm, or about 0.05 ppm to about 1 ppm based on the total weight.

[0135] The polishing slurry composition according to the example may contain potassium in an amount of about 10 ppm to about 100 ppm, 10 ppm to about 80 ppm, about 10 ppm to about 70 ppm, or about 10 ppm to about 60 ppm based on the total weight.

[0136] The polishing slurry composition according to the example may contain iron in an amount of about 0.01 ppm to about 1 ppm, 0.01 ppm to about 0.8 ppm, about 0.01 ppm to about 0.7 ppm, or about 0.01 ppm to about 0.8 ppm based on the total weight.

[0137] Since the polishing slurry composition according to the example contains the metal in the above amount, it can have an improved polishing rate.

[0138] In the polishing slurry composition according to the example, the lithium content may be less than 0.1 ppm based on the total weight of the composition.

[0139] In the polishing slurry composition according to the example, the chromium content may be less than 0.1 ppm based on the total weight of the composition.

[0140] In the polishing slurry composition according to the example, the cobalt content may be less than 0.1 ppm based on the total weight of the composition.

[0141] In the polishing slurry composition according to the example, the nickel content may be less than 0.1 ppm based on the total weight of the composition.

[0142] In the polishing slurry composition according to the example, the copper content may be less than 0.1 ppm based on the total weight of the composition.

[0143] The conductivity of the polishing slurry composition according to the example may be about 100 uS / cm to about 300 uS / cm, about 120 uS / cm to about 250 uS / cm, or about 150 uS / cm to about 230 uS / cm.

[0144] The polishing slurry composition according to the example may include polishing particles containing titanium. In addition, the polishing particles may further include sodium, magnesium, aluminum, calcium, iron, or zirconium.

[0145] In particular, the polishing slurry composition according to the example may contain titanium, sodium, magnesium, aluminum, calcium, iron, or zirconium in an appropriate amount. In particular, the polishing particles may contain colloidal silica containing titanium, sodium, magnesium, aluminum, calcium, iron, or zirconium in an appropriate amount.

[0146] Accordingly, the abrasive particles can have improved strength. That is, the abrasive particles can have improved hardness.

[0147] In addition, the polishing slurry composition according to the example may have improved dispersion stability because it contains titanium, sodium, magnesium, aluminum, calcium, iron, or zirconium in an appropriate amount. In addition, the polishing slurry composition according to the example may have improved long-term storage stability because it contains titanium, sodium, magnesium, aluminum, calcium, iron, or zirconium in an appropriate amount.

[0148] In particular, since the polishing slurry composition according to the example contains titanium, sodium, magnesium, aluminum, calcium, iron, or zirconium in an appropriately low content, it can maintain polishing performance for a long period of time even after being mixed with hydrogen peroxide.

[0149] FIG. 1 schematically illustrates the apparatus configuration for a method of manufacturing the semiconductor device according to one embodiment. Referring to FIG. 1, the method of manufacturing the semiconductor device comprises the steps of: arranging the surface to be polished (130) to come into contact with the polishing surface (111) of a polishing pad (110); and injecting a polishing slurry composition (150) onto the polishing surface (111).

[0150] The polishing target (130) may include a semiconductor wafer having a silicon nitride film and a silicon oxide film. Specifically, the surface to be polished may include a surface requiring simultaneous polishing of the silicon nitride film and the silicon oxide film. As the polishing target (130) and the surface to be polished have these characteristics, the polishing slurry composition

[0151] The polishing pad (110) may have a Shore D hardness of about 50 to about 70, for example, about 50 to about 65, for example, about 55 to about 65, measured on the polishing surface (111). A method for measuring the Shore D surface hardness on the polishing surface may be widely applied using methods commonly used in the relevant technical field, but, for example, a sample of the polishing pad cut to a size of 2 cm × 2 cm (thickness: 2 mm) may be prepared, left to stand for 16 hours in an environment with a temperature of 25°C and a humidity of 50 ± 5%, and then measured using a hardness tester (D-type hardness tester). By satisfying the hardness of the polishing surface (111) in this range, the polishing slurry composition (150) can flow at the contact interface between the polishing surface (111) and the polishing target (130), and exhibit a physically appropriate elastic correlation with the polishing pad (110). As a result, the semiconductor device manufactured by the method of manufacturing the semiconductor device may be more advantageous in exhibiting high polishing flatness without defects such as scratches.

[0152] The polishing pad (110) may include grooves or a groove on the polishing surface (111). The grooves or a groove are configured to control the fluidity of the polishing slurry composition (150) injected onto the polishing surface (111). The shape is not particularly limited, but the depth may be, for example, about 300 µm to about 900 µm, for example, about 300 µm to about 850 µm, for example, about 400 µm to about 850 µm, for example, about 450 µm to about 850 µm, for example, about 500 µm to about 800 µm, for example, about 550 µm to about 800 µm, for example, about 600 µm to about 800 µm. In addition, the width of the groove or grooves 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 grooves satisfy such ranges, it may be more advantageous to impart optimized fluidity to the polishing slurry composition.

[0153] The fact that the surface to be polished of the polishing target (130) comes into contact with the polishing surface (111) of the polishing pad (110) can be interpreted to include not only cases where there is direct physical contact between them, but also cases where there is indirect contact between them through the polishing slurry composition.

[0154] The step of injecting the polishing slurry composition (150) onto the polishing surface (111) can be performed specifically by injecting the polishing slurry composition (150) onto the polishing surface (111) through a supply nozzle (140). In one embodiment, the flow rate of the polishing slurry composition (150) injected through the supply nozzle (140) can 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 polishing slurry 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 for improving the polishing performance of the surface to be polished. More specifically, it may be more advantageous for achieving the desired polishing selectivity and simultaneously realizing the effect of preventing defects such as scratches caused by the solid components in the polishing slurry composition.

[0155] The method for manufacturing the semiconductor device described above includes the step of polishing the surface to be polished while rotating the polishing pad (110) and the polishing target (130) relative to each other. Referring to FIG. 1, the polishing pad (110) is mounted on a platen (120) such that the polishing surface (111) is the uppermost surface, and the polishing target (130) can be received in a carrier (160) such that the surface to be polished is the lowermost surface. The polishing pad (110) and the polishing target (130) can each rotate at the same speed and trajectory as the platen (120) and the carrier (160) rotate. Relative rotation of the polishing pad (110) and the polishing target (130) means rotating them while positioned so that the polishing surface and the surface to be polished are 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 directions to each other, or they may be the same direction.

[0156] In one embodiment, the rotational speed of the polishing pad (110) and the polishing target (130) may each be independently about 10 rpm to about 500 rpm, and for example, about 30 rpm to about 200 rpm. When the polishing pad (110) and the polishing target (130) each rotate at a rotational speed within the above range, the frictional behavior of the polishing surface (111) and the surface to be polished due to the centrifugal force is coupled with the polishing slurry composition (150) injected onto the polishing surface (111), so that the surface to be polished may be polished to have a high polishing flatness and may be more advantageous for polishing without defects.

[0157] In one embodiment, the rotational speed of the polishing target (130) may be greater than the rotational speed of the polishing pad (110). By rotating the polishing target (130) at a higher speed than the polishing pad (110), polishing stability is ensured, and at the same time, it may be more advantageous for the polishing surface of the polishing target (130) to be polished without defects.

[0158] In one embodiment, the method for manufacturing the semiconductor device may rotate the polishing pad (110) and the polishing target (130) relative to each other under conditions where the surface to be polished is pressed against the polishing surface (111). The load applied to the surface to be polished against the polishing surface (111) may be, for example, about 0.01 psi to about 20 psi, and for example, about 0.1 psi to about 15 psi.

[0159] The method for manufacturing the semiconductor device described above may further include a step of processing the polished surface (111) through a conditioner (170). The polished surface (111) of the polishing pad (110) is chemically affected as the polishing slurry composition (150) is continuously supplied, and at the same time is physically affected due to physical contact with the surface to be polished of the polishing target (130). If the condition of the polished surface (111) is deformed due to these chemical / physical effects, it may be difficult to maintain uniform polishing performance on the surface to be polished. The conditioner (170) is a means for processing the polished surface (111) during the polishing process, and can contribute to maintaining the polished surface (111) in a uniformly suitable state for polishing throughout the entire polishing process.

[0160] For example, the conditioner (170) can perform the function of roughening the polished surface (111) while rotating at a predetermined speed. The rotational 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.

[0161] The conditioner (170) may rotate while being pressed with a predetermined pressure against the polishing surface (111) of the polishing pad (110). For example, the pressure applied by the conditioner (170) against the polishing surface (111) 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.

[0162] By surface treatment under the aforementioned process conditions through the conditioner (170), the polished surface (111) can maintain an optimal surface condition throughout the entire polishing process, and the effect of extending the polishing life under the application conditions of the polishing slurry composition (150) can be obtained.

[0163] As previously described, the polishing slurry composition includes silica particles as a component, thereby achieving a high polishing rate with a small amount of polishing particles in a polishing process where a high polishing amount of a semiconductor oxide film is required, compared to conventional technology that used a large amount of polishing particles to meet the required level of high polishing amount. This minimizes the occurrence of defects and scratches, while simultaneously securing appropriate attractive forces between the polishing particles and the oxide film, so that the polishing is cleaned thoroughly during the cleaning process after polishing, and effectively results in virtually no residual polishing particles.

[0164] Specific embodiments of the present invention are presented below. However, the embodiments described below are merely for the purpose of specifically illustrating or explaining the present invention, and the scope of the present invention is not to be interpreted as limited by this, and the scope of the present invention is determined by the claims.

[0165]

[0166] Preparation Example

[0167] Abrasive Particle #1: Colloidal Silica #1 (SK Enpulse ST-500 product, solid content 26wt%)

[0168] Abrasive Particle #2: Colloidal Silica #2 (Nouryon, solid content 30 wt%)

[0169] Abrasive aid: Phosphoric acid

[0170] pH buffer: Acetic acid

[0171] Biocide: Benzoisothiazolinone (Benzisothiazolinone, BIT, BNOCHEM, BNOBIT product)

[0172] Corrosion Inhibitor: 5-aminotetrazole

[0173] pH Adjuster: Potassium Hydroxide

[0174] Examples

[0175] About 10 parts by weight of colloidal silica #1, about 0.015 parts by weight of phosphoric acid, about 0.033 parts by weight of acetic acid, about 0.01 parts by weight of benzisothiazolinone, about 0.06 parts by weight of 5-aminotetrazole, and about 90 parts by weight of deionized water were uniformly mixed, and potassium hydroxide was added to prepare a polishing slurry composition #1 with a pH of 4.1.

[0176] Example 4

[0177] Colloidal silica #2 was used instead of colloidal silica #1, and the rest of the process was carried out in the same way.

[0178] Classification Colloidal Silica (parts by weight) Abrasive Aid (parts by weight) pH Buffer (parts by weight) Biocide (parts by weight) Corrosion Inhibitor (parts by weight) Hydrogen Peroxide (parts by weight) Deionized Water (parts by weight) Example 1 #150.0150.0330.010.060.1594.732 Example 2 #150.0250.0330.010.060.1594.732 Example 3 #150.0150.0330.010.030.1594.732 Example 4 #250.0150.0330.010.060.1594.732

[0179] Evaluation example

[0180] Measurement Example 1: Metal Content

[0181] By ICP OES, the metal content contained in the colloidal silica and polishing slurry composition was measured as shown in Tables 2 and 3 below.

[0182] Device: Agilent 5110 SVDV

[0183] Measurement conditions

[0184] RF power: 1.2 kW

[0185] Nebulizer flow: 0.7 L / min

[0186] Plasma flow: 12 L / min

[0187] Aux flow :1 L / min

[0188] Read time : 5 s

[0189] Classification Li(ppm) Na(ppm) Mg(ppm) Al(ppm) K(ppm) Ca(ppm) Ti(ppm) Cr(ppm) Fe(ppm) Co(ppm) Ni(ppm) Cu(ppm) Zn(ppm) Zr(ppm) Total(ppm) Colloidal Silica #10.011.090.325.722700.112.620.111.100.000.010.000.014.66286 Colloidal Silica #20.0030.510.441.7432812.6413.230.132.220.030.000.010.090.453332

[0190] Classification Li(ppm) Na(ppm) Mg(ppm) Al(ppm) K(ppm) Ca(ppm) Ti(ppm) Cr(ppm) Fe(ppm) Co(ppm) Ni(ppm) Cu(ppm) Zn(ppm) Zr(ppm) Total (ppm) Example 1 0.000.300.02 0.9832.100.21 0.55 0.000.08 0.000.000.000.01 0.9835 Example 20.000.35 0.01 0.7334.36 0.12 0.44 0.000.06 0.000.000.02 0.000.9637 Example 30.000.360.010.5832.740.020.320.000.050.000.000.000.000.6135 Example 40.000.520.050.10100.30.200.650.000.050.000.000.010.000.03102

[0191] Measurement Example 2: Measurement of polishing rate. A silicon oxide wafer with a thickness of approximately 20,000 Å, a silicon nitride wafer with a thickness of approximately 2,000 Å, and a copper wafer with a thickness of 15,000 Å were prepared. As shown in FIG. 1, the wafers were placed in a carrier (160) with the surface to be polished facing downward as a polishing target (130). After positioning the carrier (160) so that the surface to be polished and the polishing surface (111) come into contact with a platen (120) on which a polishing pad (110, SK Enpulse Co., Ltd. HD-319B) is mounted so that its polishing surface (111) faces upward, each configuration was operated for 60 seconds with a pressure of 2 psi applied to 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 was performed while applying the polishing slurry compositions of each of the above example and the above comparative example to the polishing surface under conditions of a flow rate of 250 ml / min. At the same time, the polishing surface was processed by driving a conditioner (170, Saesol Diamond Co., Ltd. SKC-CI45) under conditions of a rotation speed of 250 rpm and a pressure of 8 psi. The thickness of the wafer after polishing was measured, and a polishing rate value (Rox) in units of Å / min was calculated using the polishing time and the thickness of the wafer before and after polishing.

[0192] In addition, the polishing slurry compositions prepared in the examples and comparative examples were left at room temperature for 1, 5, 12, 22, and 40 days, and the polishing rate of the copper film was measured in the same manner as above.

[0193] Measurement Example 3: Defect

[0194] The above silicon oxide wafer was prepared. Subsequently, the silicon oxide wafer was polished using the same method as the polishing rate measurement. Subsequently, the optical thickness of the upper surface of the polished silicon oxide wafer was measured over the entire area, and a polishing profile was derived. In the polishing profile, the presence or absence of defects was determined based on the number of peaks exceeding approximately 10 Å.

[0195] O: No defects (peaks exceeding approximately 10 Å)

[0196] X: Defect (peak exceeding approximately 10 Å) present

[0197] Measurement Example 4: Measurement of Zeta Potential and Abrasive Particle Size

[0198] For each of the above examples and comparative examples, the zeta potential and size of the ceria particles contained in the polishing slurry compositions prepared in the examples and comparative examples were measured using a zeta potential meter (Malvern). In addition, the polishing slurry compositions prepared in the examples and comparative examples were left at a temperature of about 60°C for about 7 days, after which the zeta potential and size of the ceria particles were measured.

[0199] Measurement Example 5: Electrical Conductivity

[0200] The above electrical conductivity was measured using an electrical conductivity measuring device (Nano ZS, Malvern Instruments Ltd.).

[0201] As shown in Tables 4 to 6 below, in the polishing slurry compositions according to the examples and comparative examples, the oxide film polishing rate, nitride film polishing rate, defects, electrical conductivity, polishing rate after leaving for a certain period, particle size, and zeta potential were measured.

[0202] Classification Oxide film polishing rate (Å / min) Nitride film polishing rate (Å / min) Copper film polishing rate (Å / min) Defect Example 1 2359208301O Example 2 2312510328O Example 3 2384231588O Example 4 2112214359O

[0203] Classification After 1 day, copper film polishing rate (Å / min) After 5 days, copper film polishing rate (Å / min) After 12 days, copper film polishing rate (Å / min) After 22 days, copper film polishing rate (Å / min) After 40 days, copper film polishing rate (Å / min) Example 1 3 2 2 3 0 2 2 8 7 2 9 8 2 9 5 Example 2 3 2 8 3 1 2 3 1 8 3 0 2 2 9 8 Example 3 5 8 8 5 6 1 5 7 4 5 5 9 5 5 2 Example 4 3 5 9 3 4 2 3 3 1 2 8 5 2 3 8

[0204] Classification pH Conductivity (uS / cm) Particle Size (nm) Zeta Potential (mV) Example 1 4.1 119 34 5.2 9 29.2 Example 2 4.1 1229 45.3 2 29.4 Example 3 4.1 217 6.8 45.3 9 29.8 Example 4 4.0 99 78 40.1 8 22.4

[0205] As described in Tables 4 and 5, the polishing slurry composition according to the examples has an improved polishing rate, selectivity, and low defects, and can have improved long-term storage stability.

Claims

1. Water; Abrasive particles; and It includes a pH adjuster, The above abrasive particles are an abrasive slurry composition containing titanium.

2. The abrasive slurry composition according to claim 1, wherein the abrasive particles further comprise sodium.

3. In claim 2, the abrasive particles are an abrasive slurry composition further comprising calcium.

4. In claim 3, the abrasive particles comprise silica, and The above abrasive particles are an abrasive slurry composition further containing iron.

5. In claim 4, the abrasive particles are an abrasive slurry composition further comprising aluminum.

6. In claim 5, the abrasive particles are an abrasive slurry composition further comprising zirconium.

7. In claim 6, the abrasive particles are an abrasive slurry composition further comprising magnesium.

8. Water; Abrasive particles; and It includes a pH adjuster, A polishing slurry composition containing titanium in an amount of 0.1 ppm to 5 ppm based on total weight.

9. A polishing slurry composition according to claim 8, comprising aluminum in an amount of 0.1 ppm to 5 ppm based on total weight.

10. A polishing slurry composition according to claim 9, comprising zirconium in an amount of 0.1 ppm to 7 ppm based on total weight.

11. A polishing slurry composition according to claim 9, further comprising hydrogen peroxide.

12. Step of preparing the semiconductor substrate; A step of spraying a polishing slit composition onto the semiconductor substrate; and The method includes the step of polishing the semiconductor substrate, The above abrasive slurry composition is water; Abrasive particles; and It includes a pH adjuster, The above-mentioned polishing particles are a method for manufacturing a semiconductor device containing titanium.

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