Composition for semiconductor process, method for producing the same, and method for producing semiconductor device

Abstract

The present invention relates to a composition for semiconductor processing, a method for manufacturing the same, and a method for manufacturing a semiconductor device. The present invention relates to a composition for semiconductor processing, which is suitable for a polishing process for a semiconductor wafer, more specifically, a semiconductor process involving a polishing process for a semiconductor wafer, wherein the composition for semiconductor processing comprises polishing particles, wherein at pH 6, the polishing particles have a zeta potential of 50 mV to 10 mV, and a zeta potential change rate represented by the following formula (1) is 6 mV / pH to 30 mV / pH, wherein the formula (1) is: zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|, wherein p6 is pH 6, p5 is pH 5, Z6 is the zeta potential at pH 6, and Z5 is the zeta potential at pH 5.

Description

Technical Field

[0001] The present invention relates to a composition applicable to semiconductor manufacturing and processing technology and a method for manufacturing the same, and more particularly to a composition applicable to a polishing process in semiconductor manufacturing and processing and a method for manufacturing the same. Background Art

[0002] Chemical Mechanical Polishing (CMP) is a technique that polishes a sample surface to a target level by rubbing a polishing pad against the surface of the object being polished while injecting a polishing slurry into the interface between the polishing pad and the object being polished.

[0003] With the application of modern chemical mechanical polishing in the manufacture of large-scale semiconductor integrated circuits, it is used as an essential technology for planarizing the surface of interlayer insulating films of devices such as transistors and multilayer wiring, and forming tungsten or copper wiring.

[0004] As the integration density of semiconductor devices increases year by year and chip size continues to shrink, the surface structure of semiconductor devices becomes more complex, and the step difference between interlayer films becomes larger. Therefore, the chemical mechanical polishing process applicable to the manufacturing process of semiconductor devices requires high-resolution lithography (lithography) and atomic-level planarization technology.

[0005] This CMP process is a process for planarizing a film by simultaneously utilizing physical friction and chemical reaction, and significantly different polishing results can be calculated depending on slight differences in process components and / or process liquids used therefor.

[0006] Therefore, the precision required for the manufacture and design of such process components and / or process liquids is being increased to a higher level. Summary of the Invention

[0007] Problems to be solved by the invention

[0008] An object of the present invention is to provide a composition for semiconductor processing, a method for producing the same, and a method for producing a semiconductor device using the same.

[0009] Another object of the present invention is to provide a composition for semiconductor processing that can achieve excellent polishing performance, minimize defects, and achieve a flat polishing result by being applied to a semiconductor process involving a polishing process of a semiconductor wafer.

[0010] Another object of the present invention is to provide a method for producing a composition for semiconductor processing having excellent dispersibility by minimizing pH shock of polishing particles to prevent agglomeration between particles.

[0011] Another object of the present invention is to provide a method for manufacturing a semiconductor device, wherein the defective rate is minimized by applying the semiconductor process composition to polishing a semiconductor wafer.

[0012] Means used to solve problems

[0013] To achieve the above-mentioned object, a composition for semiconductor processing according to one embodiment of the present invention includes polishing particles. Under the condition of pH 6, the zeta potential of the polishing particles is -50 mV to -10 mV, and the zeta potential change rate represented by the following formula 1 can be 6 mV / pH to 30 mV / pH. Formula 1: Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|, wherein p6 is pH 6, p5 is pH 5, Z6 is the zeta potential at the pH 6 condition, and Z5 is the zeta potential at the pH 5 condition.

[0014] According to another embodiment of the present invention, a method for manufacturing a composition for semiconductor processing may include the following steps: adding an acidic solution to polishing particles having a pH of 6 and a zeta potential of -50 mV to -10 mV to adjust the pH to 2 to pH 4; and stirring the pH-adjusted polishing particles and adding an organic component and an organic acid to the polishing particles.

[0015] According to another embodiment of the present invention, a method for manufacturing a semiconductor device includes the following steps: preparing a platform on which a polishing pad having a polishing surface is mounted, preparing a carrier for accommodating a polishing object, rotating the platform and the carrier with the polishing surface of the polishing pad and the polished surface of the polishing object in contact with each other, and supplying a semiconductor process composition onto the polishing surface; the semiconductor process composition may have a zeta potential change rate expressed by the following formula (1) of 6 mV / pH to 30 mV / pH:

[0016] Formula 1:

[0017] Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|

[0018] In the formula 1, p6 is pH 6, p5 is pH 5, Z6 is the zeta potential at pH 6, and Z5 is the zeta potential at pH 5.

[0019] According to another embodiment of the present invention, a composition for semiconductor processing includes polishing particles. At pH 6, the polishing particles have a zeta potential of -50 mV to -10 mV, a zeta potential change rate represented by the following formula (1) is 14 mV / pH to 24 mV / pH, and a zeta potential change rate represented by the following formula (4) is 9.5 mV / pH to 20 mV / pH.

[0020] Formula 1:

[0021] Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|

[0022] Form 4:

[0023] Zeta potential change rate (mV / pH) = |(Z6-Z2) / (p6-p2)|

[0024] In the first and fourth formulas, p6 is pH 6, p5 is pH 5, p2 is pH 2, Z6 is the zeta potential at pH 6, Z5 is the zeta potential at pH 5, and Z2 is the zeta potential at pH 2.

[0025] According to another embodiment of the present invention, a method for manufacturing a semiconductor process composition includes the steps of: adding an acidic solution to polishing particles having a pH of 6 and a zeta potential of -50 mV to -10 mV to adjust the pH to 2 to 4; stirring the pH-adjusted polishing particles; and adding an organic component and an organic acid to the polishing particles; wherein the zeta potential change rate of the polishing particles represented by the following formula (1) is 14 mV / pH to 24 mV / pH, and the zeta potential change rate represented by the following formula (4) is 9.5 mV / pH to 20 mV / pH.

[0026] Formula 1:

[0027] Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|

[0028] Form 4:

[0029] Zeta potential change rate (mV / pH) = |(Z6-Z2) / (p6-p2)|

[0030] In the first and fourth formulas, p6 is pH 6, p5 is pH 5, p2 is pH 2, Z6 is the zeta potential at pH 6, Z5 is the zeta potential at pH 5, and Z2 is the zeta potential at pH 2.

[0031] According to another embodiment of the present invention, a method for manufacturing a semiconductor device includes the following steps: preparing a platform on which a polishing pad having a polishing surface is mounted, preparing a carrier for accommodating a polishing object, rotating the platform and the carrier with the polishing surface of the polishing pad and the polished surface of the polishing object in contact with each other, and supplying a semiconductor process composition onto the polishing surface; the semiconductor process composition includes polishing particles and at least one additive; at pH 6, the zeta potential of the polishing particles is between -50 mV and -10 mV, the zeta potential change rate of the polishing particles is expressed by the following formula (1) and is between 14 mV / pH and 24 mV / pH, and the zeta potential change rate expressed by the following formula (4) is between 9.5 mV / pH and 20 mV / pH,

[0032] Formula 1:

[0033] Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|

[0034] Form 4:

[0035] Zeta potential change rate (mV / pH) = |(Z6-Z2) / (p6-p2)|

[0036] In the first and fourth formulas, p6 is pH 6, p5 is pH 5, p2 is pH 2, Z6 is the zeta potential at pH 6, Z5 is the zeta potential at pH 5, and Z2 is the zeta potential at pH 2.

[0037] According to another embodiment of the present invention, a composition for semiconductor processing includes polishing particles. At pH 6, the polishing particles have a zeta potential of -50 mV to -10 mV, and at pH 5, the polishing particles have a zeta potential of -5 mV to -6 mV. The zeta potential change rate represented by the following formula (1) is 14 mV / pH to 24 mV / pH, the zeta potential change rate represented by the following formula (4) is 9.5 mV / pH to 20 mV / pH, and the zeta potential change rate represented by the following formula (3) is 8 mV / pH to 20 mV / pH.

[0038] Formula 1:

[0039] Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|

[0040] Form 4:

[0041] Zeta potential change rate (mV / pH) = |(Z6-Z2) / (p6-p2)|

[0042] Form 3:

[0043] Zeta potential change rate (mV / pH) = |(Z6-Z1) / (p6-p1)|

[0044] In the first, fourth and third formulas, p6 is pH 6, p5 is pH 5, p2 is pH 2, p1 is pH 1, Z6 is the zeta potential at pH 6, Z5 is the zeta potential at pH 5, Z2 is the zeta potential at pH 2, and Z1 is the zeta potential at pH 1.

[0045] According to another embodiment of the present invention, a method for producing a composition for semiconductor processing includes the steps of: adding an acidic solution to polishing particles having a zeta potential of -50 mV to -10 mV at pH 6 and a zeta potential of -5 mV to -6 mV at pH 5 to adjust the pH to 2 to 4; stirring the pH-adjusted polishing particles; and adding an organic component and an organic acid to the polishing particles; wherein the zeta potential change rate represented by the following formula (1) is 14 mV / pH to 24 mV / pH, the zeta potential change rate represented by the following formula (4) is 9.5 mV / pH to 20 mV / pH, and the zeta potential change rate represented by the following formula (3) is 8 mV / pH to 20 mV / pH.

[0046] Form 1:

[0047] Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|

[0048] Form 4:

[0049] Zeta potential change rate (mV / pH) = |(Z6-Z2) / (p6-p2)|

[0050] Form 3:

[0051] Zeta potential change rate (mV / pH) = |(Z6-Z1) / (p6-p1)|

[0052] In the first, fourth and third formulas, p6 is pH 6, p5 is pH 5, p2 is pH 2, p1 is pH 1, Z6 is the zeta potential at pH 6, Z5 is the zeta potential at pH 5, Z2 is the zeta potential at pH 2, and Z1 is the zeta potential at pH 1.

[0053] According to another embodiment of the present invention, a method for manufacturing a semiconductor device includes the following steps: preparing a platform on which a polishing pad having a polishing surface is mounted, preparing a carrier for accommodating a polishing object, rotating the platform and the carrier with the polishing surface of the polishing pad and the polished surface of the polishing object in contact with each other, and supplying a semiconductor process composition onto the polishing surface; the semiconductor process composition includes polishing particles and at least one additive; the polishing particles have a zeta potential of -50 mV to -10 mV at pH 6 and a zeta potential of -5 mV to -6 mV at pH 5; the polishing particles have a zeta potential change rate expressed by the following formula (1) of 14 mV / pH to 24 mV / pH, a zeta potential change rate expressed by the following formula (4) of 9.5 mV / pH to 20 mV / pH, and a zeta potential change rate expressed by the following formula (3) of 8 mV / pH to 20 mV / pH;

[0054] Form 1:

[0055] Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|

[0056] Form 4:

[0057] Zeta potential change rate (mV / pH) = |(Z6-Z2) / (p6-p2)|

[0058] Form 3:

[0059] Zeta potential change rate (mV / pH) = |(Z6-Z1) / (p6-p1)|

[0060] In the first, fourth and third formulas, p6 is pH 6, p5 is pH 5, p2 is pH 2, p1 is pH 1, Z6 is the zeta potential at pH 6, Z5 is the zeta potential at pH 5, Z2 is the zeta potential at pH 2, and Z1 is the zeta potential at pH 1.

[0061] Effects of the Invention

[0062] The present invention is applied to a semiconductor process involving a polishing process of a semiconductor wafer, thereby achieving excellent polishing performance, minimizing defects, and achieving a flat polishing result.

[0063] Furthermore, when a method for manufacturing a semiconductor device using a composition for semiconductor processing having excellent dispersibility by minimizing pH shock of polishing particles to prevent agglomeration of particles is applied, semiconductor devices with a minimized defect rate can be manufactured. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] Figure 1 The configuration of a semiconductor device is schematically shown.

[0065] Figure 2 The configuration of the method for manufacturing the semiconductor device is schematically shown.

[0066] Figure 3 The present invention relates to a change in zeta potential according to a change in pH of polishing particles according to an embodiment of the present invention.

[0067] Figure 4 This shows the stabilized state of the polishing particles.

[0068] Figure 5 This shows the unstable state of the polishing particles.

[0069] Figure 6 The relationship between the zeta potential of the polishing particles and the zeta potential of the semiconductor wafer is schematically shown.

[0070] Figure 7 The relationship between the zeta potential of the polishing particles and the zeta potential of the semiconductor wafer is schematically shown.

[0071] Description of Reference Numerals

[0072] 10: Silicon substrate

[0073] 20: SiO2 oxide film

[0074] 30: Metal barrier film

[0075] 40: Tungsten film

[0076] 110: Polishing pad

[0077] 120: Platform

[0078] 130: Polishing Object

[0079] 140: Supply nozzle

[0080] 150: Compositions for semiconductor processes

[0081] 160: Carrier

[0082] 170: Dresser

[0083] 200: Zeta potential changes of polishing particles dispersed in weak acidic solution

[0084] 210: Polishing particles dispersed in weak acid solution

[0085] 220: Polishing particles dispersed in a strong acid solution

[0086] 230: Surface modified polishing particles dispersed in a strong acid solution

[0087] 300: Zeta potential changes of polishing particles dispersed in a strong alkaline solution

[0088] 310: Polishing particles dispersed in a strong alkaline solution

[0089] 320: Polishing particles dispersed in a strong acid solution

[0090] 330: Surface modified polishing particles dispersed in a strong acid solution

[0091] 400: Polished particles with a surface treatment to give a positive (+) zeta potential value

[0092] 410: Polishing particles with a surface treatment to give a negative (-) zeta potential value DETAILED DESCRIPTION

[0093] The advantages, features, and implementation methods of the present invention will be more clearly understood based on the following embodiments. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various forms. This embodiment is only intended to make the disclosure of the present invention more complete and to fully provide the scope of the present invention to those skilled in the art. The present invention is defined by the appended claims.

[0094] In this specification, unless otherwise specified, “including,” “comprising,” or “having” means that other components may also be included.

[0095] In order to clearly express the various layers and regions in the figures, the thickness is magnified and shown. In addition, in the drawings, for the convenience of explanation, the thickness of some layers and regions is exaggerated. Throughout the specification, the same reference numerals represent the same components.

[0096] In addition, in this specification, when a part of a layer, film, region, plate, etc. is referred to as being "on" or "above" another part, this includes not only the case where it is directly "above" the other part, but also the case where there is another part in between. Conversely, when a part is referred to as being directly "on" another part, it means that there is no other part in between. At the same time, when a part of a layer, film, region, plate, etc. is referred to as being "below" or "under" another part, this includes not only the case where it is directly "under" the other part, but also the case where there is another part in between. Conversely, when a part is referred to as being directly "under" another part, it means that there is no other part in between.

[0097] In the present invention, polishing particles are defined as inorganic particles dispersed in a solvent such as water, and the pH of the polishing particles refers to the pH in a state of being dispersed in a solvent such as water.

[0098] According to one embodiment of the present invention, a semiconductor process composition includes polishing particles. Under a pH of 6, the zeta potential of the polishing particles is -50 mV to -10 mV, and the zeta potential change rate expressed by the following formula (1) can be 6 mV / pH to 30 mV / pH.

[0099] Formula 1:

[0100] Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|

[0101] In the formula 1, p6 is pH 6, p5 is pH 5, Z6 is the zeta potential at pH 6, and Z5 is the zeta potential at pH 5.

[0102] Since the composition for semiconductor processing includes polishing particles having a zeta potential change rate as expressed in Formula 1, agglomeration of the polishing particles in the composition is prevented, thereby preventing defects from occurring during the polishing process. Furthermore, excellent polishing performance can be achieved by being applied to semiconductor processes for polishing tungsten films and metal barrier films.

[0103] Using the semiconductor process composition of the present invention, a semiconductor wafer such as a semiconductor wafer to be polished is polished. Figure 1 As described Figure 1 As shown, a SiO2 oxide film 20 as an interlayer insulating film is formed on a silicon substrate 10 and the SiO2 oxide film 20 is etched to form a contact hole.

[0104] Subsequently, a metal barrier film 30 such as Ti / TiN (adhesion layer / diffusion prevention layer) is formed on the entire surface of the substrate including the contact hole, and a tungsten film 40 is deposited thereon to completely fill the contact hole. The tungsten film 40 and the metal barrier film 30 on the SiO2 oxide film 20 are then polished using a semiconductor process composition in a polishing process, thereby forming a tungsten plug.

[0105] In the manufacturing process of the semiconductor device as described above, the semiconductor process composition generally contains polishing particles and other additives, wherein the polishing particles are used for mechanical polishing of the target film, and the other additives are used to improve or supplement the performance of the semiconductor process composition.

[0106] In the semiconductor process composition, when the value of the first formula satisfies the above range, the polishing particles can exhibit a high level of dispersibility, thereby providing a polishing composition having a uniform particle size distribution.

[0107] Specifically, in the semiconductor process composition of the present invention, the zeta potential of the polishing particles can be -50 mV to -10 mV under a pH of 6. Under the aforementioned pH of 6, when polishing particles with a zeta potential of -50 mV to -10 mV are used to produce a polishing composition, when weakly acidic polishing particles are used to produce the polishing composition, a polishing composition with excellent dispersibility can be produced without an additional aging process. That is, as described later, the polishing particles can be surface-treated with an organic component. To surface-treat the polishing particles as described above, the pH is adjusted so that the polishing particles in a weakly acidic state become acidic and can be mixed with the organic component. When the mixed organic component binds to the surface of the polishing particles, the polishing particles can be surface-treated. During the surface treatment process, even if the pH changes, causing the polishing particles in a weakly acidic state to become acidic, no pH shock will occur due to the pH change, and therefore no agglomeration between the particles will occur.

[0108] Conventionally, polishing particles included in semiconductor process compositions have been dispersed in a strongly alkaline solution. During the manufacture of the semiconductor process composition, these alkaline polishing particles are mixed and stirred with an acidic solution to adjust the pH to a strongly acidic state. However, this mixing and stirring with the acidic solution causes a sudden pH change in the polishing particles, resulting in a pH shock and agglomeration of the particles.

[0109] The acidic solution is specifically an organic acid. For example, the organic acid may be selected from nitric acid, acetic acid, formic acid, benzoic acid, nicotinic acid, picolinic acid, alanine, phenylalanine, valine, leucine, isoleucine, arginine, aspartic acid, citric acid, adipic acid, succinic acid, oxalic acid, glycine, glutamic acid, glutaric acid, phthalic acid ... The organic acid may be selected from the group consisting of nitric acid, histidine, threonine, serine, cysteine, methionine, asparagine, tyrosine, diiodotyrosine, tryptophan, proline, oxyproline, ethylenediaminetetraacetic acid (EDTA), nitrotriacetic acid (NTA), iminodiacetic acid (IDA), and combinations thereof. In one embodiment, the organic acid may be nitric acid or acetic acid, but is not limited to the above examples. Any organic acid may be used without limitation as long as the polishing particles remain stably dispersed in the solution and the pH can be adjusted to a strongly acidic state.

[0110] Specifically, Figure 3 The present invention relates to a change in zeta potential according to a change in pH of polishing particles according to an embodiment of the present invention. Figure 4 Shows the polishing particles in a stabilized state. Figure 5 It shows the agglomeration phenomenon between polishing particles in an unstable state.

[0111] Figure 3 Regarding the change in zeta potential according to pH of the polishing particles, the zeta potential value of the polishing particles changes from a negative value to a positive value as the pH changes, and the zeta potential value can be further changed according to the surface modification of the polishing particles.

[0112] More specifically, when observing the zeta potential change 200 of polishing particles dispersed in a weakly acidic solution, polishing particles 210 initially dispersed in the weakly acidic solution can exhibit a negative zeta potential value. However, upon mixing with an acidic solution and changing the pH to a strongly acidic one, the zeta potential of polishing particles 220 dispersed in the strongly acidic solution can become positive. Furthermore, the zeta potential value of surface-modified polishing particles 230 dispersed in the strongly acidic solution can be further altered by surface modification.

[0113] Furthermore, when observing the change in zeta potential 300 of polishing particles dispersed in a strongly alkaline solution, polishing particles 310 initially dispersed in the strongly alkaline solution can exhibit a negative zeta potential value. However, during the manufacture of the polishing composition, the zeta potential of polishing particles 320 dispersed in the strongly acidic solution can become positive due to the pH becoming strongly acidic by mixing with an acidic solution. Furthermore, the zeta potential value of surface-modified polishing particles 330 dispersed in the strongly acidic solution, formed through surface modification, can be further altered.

[0114] At this time, when the polishing particles 310 dispersed in the strong alkaline solution are mixed with the acidic solution, a longer reaction time and stabilization of the polishing particles may be required due to pH shock.

[0115] The stabilized state of the polishing particles means that Figure 4 The particles are shown to maintain a certain distance between them due to a repulsive force, while the unstable state between the polishing particles means an aggregated phenomenon.

[0116] When polishing particles dispersed in a strong alkaline solution are mixed with an acidic solution, a pH shock occurs due to a sudden change in pH, which may cause the following: Figure 5 That is, due to the pH shock occurring in the polishing particles, an aging process is required for stabilizing the polishing particles, and thus an additional process is required for manufacturing the semiconductor process composition, and the total process time may increase.

[0117] On the contrary, when polishing particles in a weakly acidic environment are used as in the present invention, even when the composition for semiconductor processing is mixed with an acidic solution during the manufacturing process, the pH change is small, and thus no pH shock occurs in the polishing particles, so that the stabilized state between the polishing particles can be maintained. Figure 4 As shown, when the polishing composition is manufactured in a state where the polishing particles are maintained in a stabilized state, an additional aging process for the polishing particles can be omitted.

[0118] The polishing particles of the present invention are characterized by having a uniform size within a certain range by maintaining a stable state between the polishing particles during the manufacture of a semiconductor process composition. Specifically, using an Accusizer Fx Nano (PSSA), when a semiconductor process composition diluted to an initial concentration of 4000 particles / mL, a minimum size of 0.56 μm, and a maximum size of 20 μm is injected at 15 mL / min and LPC measurement is performed. The number of particles larger than 5 μm can range from about 100 to about 700, about 100 to about 500, about 100 to about 450, or about 100 to about 400. The number of particles larger than 3 μm can range from about 100 to about 1100, about 200 to about 1000, about 300 to about 900, or about 400 to about 900. The number of particles larger than 1 μm may be from about 1,000 to about 3,400, from about 1,200 to about 3,000, from about 1,300 to about 2,800, or from about 1,500 to about 2,500. As shown in the LPC measurement results, the semiconductor process composition of the present invention includes polishing particles having a small diameter, and thus, when used in a polishing process, can prevent defects from being generated on the surface of a semiconductor wafer.

[0119] As described above, the polishing particles of the present invention are characterized in that pH changes have no influence on stabilization and that the zeta potential change rate represented by the following formula 1 is 6 mV / pH to 30 mV / pH.

[0120] Formula 1:

[0121] Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|

[0122] In the formula 1, p6 is pH 6, p5 is pH 5, Z6 is the zeta potential at pH 6, and Z5 is the zeta potential at pH 5.

[0123] The zeta potential change rates according to Formula 1 are 6 mV / pH to 30 mV / pH, 14 mV / pH to 24 mV / pH, 14 mV / pH to 19 mV / pH, and 14.5 mV / pH to 18.5 mV / pH. When polishing compositions are manufactured using polishing particles having zeta potential change rates within these ranges, pH changes are minimal when mixed with an acidic solution, preventing pH shock within the polishing particles. This maintains a stable state between the polishing particles, thereby improving the production efficiency of the polishing composition. Furthermore, since the polishing particles maintain a stable state, agglomeration is prevented, thereby preventing defects during the polishing process.

[0124] The zeta potential change rate is the rate of change from a weakly acidic pH state. When the polishing particles used to prepare the polishing composition are dispersed in an initial weakly acidic solution and mixed with an acidic solution, the zeta potential change rate can be from about 14 mV / pH to about 30 mV / pH when the pH changes from 6 to 5.

[0125] Furthermore, when the pH of the polishing particles of the present invention changes from 5 to 4, the zeta potential change rate may be from about 10 mV / pH to about 55 mV / pH, from about 15 mV / pH to about 48 mV / pH, or from about 16 mV / pH to about 44 mV / pH. When the pH of the polishing particles of the present invention changes from 4 to 3, the zeta potential change rate may be from about 0 mV / pH to about 10 mV / pH, from about 0.5 mV / pH to about 6 mV / pH, or from about 0.5 mV / pH to about 5 mV / pH. When the pH of the polishing particles of the present invention changes from 3 to 2, the zeta potential change rate may be from about -5 mV / pH to about 10 mV / pH, from about -3 mV / pH to about 8 mV / pH, or from about 1 mV / pH to about 7 mV / pH. When the pH of the polishing particles of the present invention changes from 2 to 1, the zeta potential change rate can be from about -5 mV / pH to about 10 mV / pH, from about -3 mV / pH to about 8 mV / pH, or from about -2 mV / pH to about 6 mV / pH. When these zeta potential change rates are met, the polishing particles in the semiconductor processing composition do not agglomerate but remain in a stabilized state. Therefore, when used in a polishing process, the polishing particles not only provide excellent polishing performance but also prevent defects during the polishing process.

[0126] The polishing particles of the present invention are characterized in that the zeta potential change rate represented by the following formula 2 is 14 mV / pH to 40 mV / pH,

[0127] Form 2:

[0128] Zeta potential change rate (mV / pH) = |(Z6-Z4) / (p6-p4)|

[0129] Wherein, the p6 is pH 6, the p4 is pH 4, the Z6 is the ZETA potential under the pH 6 condition, and the Z4 is the ZETA potential under the pH 4 condition.

[0130] The zeta potential change rate according to the second formula can be about 14mV / pH to about 40mV / pH, about 20mV / pH to 38mV / pH, or about 22mV / pH to about 35mV / pH. As described above, the polishing particles of the present invention are provided in a weakly acidic state to manufacture a semiconductor process composition. In the weakly acidic state, when the pH is changed by supplying an organic acid, the zeta potential of the polishing particles also changes. Figure 3 The pH of the polishing particles 210 dispersed in the weak acidic solution is 6, and when the semiconductor process composition is manufactured, the pH can be changed to 4. Due to the pH change as described above, the zeta potential value of the polishing particles changes, and whether a pH shock occurs is determined based on the degree of change in the zeta potential value, such as Figure 3 As shown, satisfying the range of Formula 2 indicates that the polishing particles do not experience an additional pH shock due to pH changes. Furthermore, by satisfying the aforementioned range, the polishing particles in the semiconductor processing composition do not agglomerate but remain in a stabilized state. Therefore, when used in a polishing process, the composition not only provides excellent polishing performance but also prevents defects during the polishing process.

[0131] As described above, the polishing particles of the present invention are characterized in that the zeta potential change rate represented by the following formula 3 is 8 mV / pH to 20 mV / pH:

[0132] Form 3:

[0133] Zeta potential change rate (mV / pH) = |(Z6-Z1) / (p6-p1)|

[0134] Wherein, the p6 is pH 6, the p1 is pH 1, the Z6 is the ZETA potential under the pH 6 condition, and the Z1 is the ZETA potential under the pH 1 condition.

[0135] The zeta potential change rate according to equation 3 can be from about 8 mV / pH to about 20 mV / pH, from about 8 mV / pH to 18 mV / pH, or from about 8 mV / pH to about 16 mV / pH. Equation 3 relates to the zeta potential change rate as the state of the polishing particles changes from weakly acidic to strongly acidic. When the above range is met, both the polishing particles in the weakly acidic state and the polishing particles in the strongly acidic state have excellent dispersibility. When the degree of change in the zeta potential values ​​of the polishing particles in the weakly acidic state and the polishing particles in the strongly acidic state fall within the above range, the polishing particles have excellent dispersibility in the semiconductor process composition, and agglomeration between the particles does not occur. As described above, the polishing particles remain in a stable state, exhibiting a uniform size within a certain range.

[0136] As described above, the polishing particles of the present invention are characterized in that the zeta potential change rate represented by the following formula (4) is 9.5 mV / pH to 20 mV / pH:

[0137] Form 4:

[0138] Zeta potential change rate (mV / pH) = |(Z6-Z2) / (p6-p2)|

[0139] Wherein, the p6 is pH 6, the p2 is pH 2, the Z6 is the ZETA potential under the pH 6 condition, and the Z2 is the ZETA potential under the pH 2 condition.

[0140] The zeta potential change rate according to Formula 4 can be from about 9.5 mV / pH to about 20 mV / pH, from about 9.5 mV / pH to 19 mV / pH, or from about 9.5 mV / pH to about 18 mV / pH. In order to manufacture a polishing composition using weakly acidic polishing particles, when manufacturing strongly acidic polishing particles, the zeta potential change within the range of Formula 4 does not cause shocks due to pH changes, eliminating the need for additional steps to prevent particle agglomeration. This simplifies the manufacturing process and improves production efficiency. Furthermore, when a semiconductor process composition containing the polishing particles is used in a polishing process, the polishing rate of the target film is excellent and defects can be prevented.

[0141] Furthermore, as described above, the polishing particles of the present invention can exhibit a zeta potential change of approximately 31 mV to approximately 75 mV, approximately 35 mV to approximately 68 mV, or approximately 35 mV to approximately 65 mV, depending on the pH change during the process, such as from pH 6 to pH 4. As described above, when the polishing particles of the present invention are used to prepare a semiconductor process composition, the pH is changed from a weakly acidic pH of 6 to a weakly acidic pH of 4. The zeta potential changes depending on the extent of the pH change, and this change can occur within the above-mentioned range. This means that the zeta potential change can prevent the occurrence of pH shocks caused by pH changes in the polishing particles during the process for manufacturing the semiconductor process composition. Within this range, even when the zeta potential changes due to pH changes, the polishing particles do not experience shocks. Consequently, when provided as a semiconductor process composition, the polishing particles exhibit excellent dispersibility. Therefore, when used in a polishing process, the polishing particles can not only provide excellent polishing performance but also prevent defects during the polishing process.

[0142] Specifically, when used in chemical mechanical polishing of semiconductor wafers, the composition not only achieves excellent results in terms of polishing flatness but also minimizes the occurrence of defects. The composition can be used in the polishing process of semiconductor wafers, thereby significantly improving the polishing performance of tungsten films and metal barrier films.

[0143] That is, the composition for semiconductor processing of the present invention can achieve a target level of polishing performance while preventing the occurrence of defects on a semiconductor wafer including a tungsten film and a metal barrier film.

[0144] The polishing particles according to one embodiment of the present invention may include particles that have been surface-treated such that the polishing particles in the semiconductor processing composition exhibit a positive (+) zeta potential. Specifically, the polishing particles are surface-treated such that, when the pH is 4, the zeta potential has a positive (+) zeta potential, wherein the zeta potential is from about 10 mV to about 50 mV, preferably from about 15 mV to about 45 mV, and more preferably from about 20 mV to about 40 mV.

[0145] The polishing particles contained in the semiconductor process composition of the present invention described above are characterized in that they are surface-treated to have a positive (+) zeta potential value, and this characteristic can prevent the occurrence of defects.

[0146] like Figure 6 As shown, a semiconductor processing composition containing polishing particles 400 that have been surface-treated to have a positive (+) zeta potential exhibits excellent adsorption efficiency with semiconductor wafers, thereby improving polishing performance. Specifically, the zeta potential of the semiconductor wafer surface has a negative (-) value. As described above, since the semiconductor wafer surface exhibits a negative zeta potential, the use of polishing particles with a positive zeta potential can improve the adsorption efficiency between the semiconductor wafer and the polishing particles through electrostatic attraction. This improved adsorption efficiency facilitates chemical bonding and mechanical abrasion, making it easier to remove the target film.

[0147] In addition, although polishing particles that have been surface-treated to have a positive zeta potential value can easily bond to a semiconductor wafer having a negative zeta potential value through electrostatic attraction, the bond as described above can be easily separated by squeezing and rotating the semiconductor wafer and the polishing pad.

[0148] On the contrary, Figure 7 As shown, the semiconductor process composition containing polishing particles 410 that have been surface-treated to have a negative (-) zeta potential can electrostatically repel a semiconductor wafer having a negative zeta potential. Figure 7The polishing particles shown may not be adsorbed to the semiconductor wafer and thus may not be susceptible to mechanical abrasion or removal of the target film.

[0149] More specifically, the polishing particles can include inorganic particles, and the inorganic particles can include particles surface-treated with at least one organic component.

[0150] In one embodiment, the at least one organic component used for surface treatment of inorganic particles can be one selected from the group consisting of, for example, aminosilane, alkoxysilane, ethoxysilane, epoxysilane, and combinations thereof. The organic component may be an aminosilane, and the aminosilane may more specifically be selected from the group consisting of 3-aminopropyltriethoxysilane (APTES), 3-aminopropyltrimethoxysilane (APTMS), 3-glycidoxypropyltrimethoxysilane (GPTMS), 3-glycidoxypropylmethyldimethoxysilane (GPDMS), 3-aminopropylmethyldiethoxysilane (APDES), 3-mercaptopropyltrimethoxysilane (MrPTMS), 3-mercaptopropyltrimethyldimethoxysilane (MrPDMS), 3-methacryloxypropyltrimethoxysilane (MPTMS), 3-methacryloxypropylmethyldimethoxysilane (MPDMS), and combinations thereof.

[0151] In one embodiment, the inorganic particles include silicon dioxide (SiO2), and the at least one organic component suitable for surface treatment of the inorganic particles may include aminosilane or epoxysilane. The polishing particles dispersed in the acidic solution are characterized by having a positive zeta potential. As a result, the surface is easily adsorbed to the surface of a semiconductor wafer exhibiting a negative zeta potential, and mechanical wear is facilitated, thereby improving the polishing rate of the target film.

[0152] For surface treatment with an organic component, the polishing particles of the present invention contain from about 0.01 to about 1 part by weight of the organic component and from about 0.01 to about 1 part by weight of an organic acid, preferably from about 0.05 to about 0.8 part by weight of the organic component and from about 0.05 to about 0.8 part by weight of the organic acid, and more preferably from about 0.1 to about 0.8 part by weight of the organic component and from about 0.05 to about 0.5 part by weight of the organic acid, per 100 parts by weight of the polishing particles. When these contents are within the above ranges, dispersibility is improved when the pH of the polishing particles is adjusted, and the polishing particles can exhibit a positive zeta potential, thereby improving polishing performance and preventing defects when used in a semiconductor device manufacturing process after being manufactured into a semiconductor process composition.

[0153] In another embodiment, the polishing particles may include organic-inorganic composite particles. For example, the organic-inorganic composite particles may be particles having a core-shell structure consisting of a core comprising a polymer resin and a shell comprising an inorganic component disposed on the surface of the core.

[0154] The core of the organic-inorganic composite particle may include a polymer resin such as polymethylmethacrylate (PMMA) resin or polystyrene (PS) resin. The inorganic component of the shell may include silica (SiO2), cerium dioxide (CeO2), aluminum oxide (Al2O3), titanium dioxide (TiO2), zirconium oxide (ZrO2), germanium oxide (GeO2), etc.

[0155] The average particle size (D50) of the polishing particles can be, for example, about 5 nm to about 150 nm, about 5 nm to about 100 nm, about 5 nm to about 80 nm, about 10 nm to about 80 nm, about 30 nm to about 50 nm, about 30 nm to about 45 nm, or about 34 nm to about 44 nm. Using polishing particles of such a size can further facilitate the semiconductor process composition satisfying the condition of Formula 1.

[0156] For example, in the particle distribution of the polishing particles, a 10% cumulative mass particle size distribution diameter (D10) may be 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.

[0157] For example, in the particle distribution of the polishing particles, a 90% cumulative mass particle size distribution diameter (D90) may be about 40 nm to about 150 nm, for example, about 40 nm to about 100 nm, for example, about 45 nm to about 80 nm, for example, about 45 nm to about 65 nm, for example, 50 nm to about 60 nm.

[0158] For example, in the particle distribution of the polishing particles, a 10% cumulative mass particle size distribution diameter (D10) may be about 23 nm to about 33 nm, a 50% cumulative mass particle size distribution diameter (D50) may be about 34 nm to about 44 nm, and a 90% cumulative mass particle size distribution diameter (D90) may be about 50 nm to about 60 nm.

[0159] The polishing particles may have a particle size distribution that satisfies the conditions of 1.10 ≤ D90 / D50 ≤ 1.80, for example, 1.50 ≤ D90 / D10 ≤ 2.70, or for example, 1.00 ≤ D50 / D10 ≤ 2.00. Using polishing particles having such a particle size distribution can further facilitate the semiconductor process composition satisfying the values ​​of Formula 1 within a predetermined range, and can further facilitate calculation of corresponding excellent polishing results.

[0160] The method for determining the particle size distribution of the polishing particles is not particularly limited and can be derived using any common equipment in the art for particle size analysis of nanometer (nm)-scale particles and powders.

[0161] In addition to the polishing particles described above, the semiconductor process composition may further include at least one additive. The at least one additive is mainly capable of adjusting the surface state of the polishing object to be suitable for polishing through a chemical reaction.

[0162] For example, the at least one additive may include an organic acid. The organic acid can function as a complexing agent that captures metal ions such as tungsten ions. The complexing agent chelates metal oxides oxidized by the oxidizing agent. Specifically, the complexing agent inhibits the oxidized metal oxides from re-adsorbing onto the polished layer, i.e., the metal film layer, through a chelation reaction with the metal oxide. This increases the polishing rate of the metal film and reduces surface defects. For example, the organic acid may include an amino acid selected from the group consisting of acetic acid, formic acid, benzoic acid, nicotinic acid, picolinic acid, alanine, phenylalanine, valine, leucine, isoleucine, arginine, aspartic acid, citric acid, adipic acid, succinic acid, oxalic acid, glycine, glutamic acid, glutaric acid, phthalic acid, thiazolinone, thiazolinone, thiazolinone, glutamic acid, glutaric acid ... The organic acid may be selected from the group consisting of amino acids, histidine, threonine, serine, cysteine, methionine, asparagine, tyrosine, diiodotyrosine, tryptophan, proline, oxyproline, ethylenediaminetetraacetic acid (EDTA), nitrotriacetic acid (NTA), iminodiacetic acid (IDA), and combinations thereof. In one implementation, the organic acid may include glycine.

[0163] For example, the at least one additive may include a polyol. The polyol can inhibit the adsorption of polishing particles on the polished surface or defects (such as scratches) and improve the dispersibility in the semiconductor process composition. For example, the polyol may include one selected from the group consisting of polyvinyl alcohol, cellulose, sorbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, glycerol monomethyl ether, glycerol dimethyl ether, glycerol diethyl ether, glycerol triethyl ether and combinations thereof. In one implementation example, the polyol may include sorbitol.

[0164] The at least one additive may be a fluorine-based surfactant. The inclusion of the fluorine-based surfactant effectively prevents excessive adsorption of the polishing particles onto the surface of the object being polished before and / or during the polishing process. Furthermore, the inclusion of fluorine prevents the growth of bacteria and fungi in the semiconductor process composition, thereby improving long-term storage stability.

[0165] Specifically, the surfactant of the present invention can be selected from BNO Chem's BNO-BS-BOH, Chemours tm The company's FS-30, FS-31, FS-34, ET-3015, ET-3150, ET-3050, Capstone FS-3100 and a group consisting of a mixture thereof, but there is no particular limitation as long as the substance plays a role in preventing excessive adsorption of carbon residues on the surface of the semiconductor substrate during the polishing process.

[0166] The surfactant of the present invention is a nonionic surfactant. The surfactant comprising a nonionic fluorine-based polymer compound can be used alone or in combination with other nonionic surfactants.

[0167] The nonionic surfactant may be selected from the group consisting of polyethylene glycol, polypropylene glycol, polyethylene-propylene copolymer, polyalkyloxide, polyoxyethylene oxide (PEO), polyethylene oxide, and polypropylene oxide; and the fluorine-based surfactant may be 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. The present invention relates to a group consisting of a polyoxyethylene fluorosurfactant and a polyoxyethylene fluorosurfactant.

[0168] The at least one additive may further include a pH adjuster. The pH adjuster may include one selected from the group consisting of, for example, hydrochloric acid (HCl), phosphoric acid (H3PO4), sulfuric acid (H2SO4), nitric acid (HNO3), ammonium hydroxide (NH4OH), potassium hydroxide (KOH), sodium hydroxide (NaOH), and combinations thereof. When the at least one additive includes a pH adjuster, the pH adjuster may be included in an amount of about 0.01 wt% to about 5 wt% relative to the weight of the total semiconductor process composition.

[0169] The semiconductor process composition may include a residual amount of a solvent in addition to the above components. For example, the solvent may be water (H2O), and specifically, ultrapure water may be used.

[0170] The semiconductor process composition may include about 1 to 10 weight percent of polishing particles, about 0.5 to 5 weight percent of a polyol, about 0.01 to 1 weight percent of an organic acid, and the balance solvent. Preferably, the composition may include about 1 to 8 weight percent of polishing particles, about 0.5 to 4 weight percent of a polyol, about 0.01 to 0.8 weight percent of an organic acid, and the balance solvent. More preferably, the composition may include about 1 to 5 weight percent of polishing particles, about 1 to 4 weight percent of a polyol, about 0.05 to 0.8 weight percent of an organic acid, and the balance solvent. When the composition is within the above range, the polishing particles can be prevented from adsorbing to the polished surface, preventing the occurrence of defects, and can be more conducive to achieving a polishing speed, dispersion stability of the semiconductor process composition, and excellent flatness of the polished surface.

[0171] The solid content of the semiconductor process composition can be from about 5% to about 20% by weight. If the solid content is too low, there is a concern that the polishing rate of the silicon oxide film cannot be sufficiently ensured, while if it is too high, there is a concern that defects may occur due to agglomeration of polishing particles, etc. That is, when the semiconductor process composition includes the components and the solvent and satisfies the solid content within the above range, it can be advantageous to inject the semiconductor process composition at a uniform flow rate when it is used in the polishing process. In addition, it can be advantageous to ensure uniform dispersion and storage stability during the circulation and storage of the semiconductor process composition.

[0172] In another embodiment of the present invention, a method for manufacturing a semiconductor process composition includes the following steps: adding an acidic solution to polishing particles having a pH of 6 and a zeta potential of -50 mV to -10 mV to adjust the pH to 2 to 4; and stirring the pH-adjusted polishing particles and adding an organic component and an organic acid to the polishing particles. The zeta potential change rate of the polishing particles, as expressed by the following formula (1), can be 6 mV / pH to 30 mV / pH:

[0173] Formula 1:

[0174] Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|

[0175] In the formula 1, p6 is pH 6, p5 is pH 5, Z6 is the zeta potential at pH 6, and Z5 is the zeta potential at pH 5.

[0176] As described above, the semiconductor processing composition of the present invention is manufactured using polishing particles dispersed in a weakly acidic solution. Under weakly acidic conditions of pH 6, the zeta potential of the polishing particles can range from approximately -50 mV to approximately -10 mV, approximately -40 mV to approximately -12 mV, approximately -35 mV to approximately -19 mV, or approximately -20.5 mV to approximately -30 mV. Polishing particles having zeta potential values ​​within these ranges prevent pH shock even when the pH changes due to mixing with an acidic solution, thereby enabling the manufacture of a polishing composition in a stabilized state.

[0177] Specifically, the zeta potential change rate according to Formula 1 can be 6 mV / pH to 30 mV / pH, 14 mV / pH to 24 mV / pH, 14 mV / pH to 19 mV / pH, and 14.5 mV / pH to 18.5 mV / pH. As described above, the value of Formula 1 falling within the range of the present invention means that the stabilized state between the polishing particles is maintained even after mixing with an acidic solution. Furthermore, when the value falls within the above range, pH changes are minimal during the polishing composition manufacturing process even when mixed with an acidic solution. Therefore, pH shock does not occur in the polishing particles, and a stabilized state can be maintained between the polishing particles, thereby improving the manufacturing efficiency of the polishing composition. Furthermore, since the stabilized state is maintained between the polishing particles, agglomeration does not occur, thereby preventing the occurrence of defects during the polishing process.

[0178] While the polishing particles are being stirred, an organic acid is added to reduce the pH to a strong acidity of pH 2 to pH 4. Subsequently, a stirring process is performed, and an organic component and an organic acid are added to bind the organic component to the surface of the polishing particles.

[0179] To maintain a stable state between the polishing particles and allow the organic component to bind to the particle surfaces, the stirring process is performed at a speed of 1500 to 2000 rpm, preferably 1600 to 1900 rpm, and more preferably 1600 to 1800 rpm. When the stirring process is performed at a high speed within this range, the zeta potential of the polishing particles maintains a stable state between the particles, and the organic component can easily bind to the particle surfaces. Furthermore, since this stable state is maintained between the polishing particles, excellent dispersion characteristics can be achieved.

[0180] The polishing particles bound to the amine-based surface binding agent are separated by an ion exchange membrane, and the polishing particles bound to the separated amine-based surface binding agent can be used to manufacture a composition for semiconductor processing.

[0181] The polishing particles can be mixed with at least one additive to produce a semiconductor process composition. The at least one additive can adjust the surface state of the polishing object to be suitable for polishing mainly through chemical reaction.

[0182] As described above, the at least one additive may include an organic acid, a polyol, a fluorine-based surfactant, and a solvent. In addition, the additive may further include a pH adjuster, an azole compound, a phosphoric acid-based compound, and the like.

[0183] Regarding the description of the additives, the matters described above can be comprehensively interpreted and applied to the method for producing the composition for semiconductor processing in the same manner.

[0184] In another embodiment of the present invention, a method for manufacturing a semiconductor device includes the following steps: preparing a platform on which a polishing pad having a polishing surface is mounted, preparing a carrier for accommodating a polishing object, rotating the platform and the carrier with the polishing surface of the polishing pad and the polished surface of the polishing object in contact with each other, and supplying a semiconductor process composition onto the polishing surface; the semiconductor process composition includes polishing particles and at least one additive; the polishing particles have a zeta potential change rate expressed by the following formula (1) of 6 mV / pH to 30 mV / pH:

[0185] Formula 1:

[0186] Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|

[0187] In the formula 1, p6 is pH 6, p5 is pH 5, Z6 is the zeta potential at pH 6, and Z5 is the zeta potential at pH 5.

[0188] Matters related to the composition for semiconductor processes and Formula 1 are the same as those described with respect to the composition for semiconductor processes.

[0189] Figure 2 The structure of the manufacturing method of the semiconductor device according to one embodiment is schematically shown. Figure 2 The method for manufacturing a semiconductor device may include: preparing a platform 120 on which a polishing pad 110 having a polishing surface is mounted; and preparing a carrier 160 for accommodating a polishing object 130 .

[0190] In the method for manufacturing the semiconductor device, the polishing object 130 may be a material having Figure 1Specifically, a SiO2 oxide film is formed on a silicon substrate as an interlayer insulating film, and the SiO2 oxide film is etched to form contact holes.

[0191] Subsequently, a metal barrier film such as Ti / TiN (adhesion layer / diffusion prevention layer) is formed on the entire surface of the substrate including the contact hole, and a tungsten (W) film is deposited thereon to completely fill the contact hole. The tungsten film and the metal barrier film on the SiO2 oxide film are then polished using a semiconductor process composition to form a tungsten plug.

[0192] The semiconductor process composition of the present invention is applied to the polishing process to polish the tungsten film and the metal barrier film on the SiO2 oxide film to form a tungsten plug, which has excellent polishing performance for the tungsten film and the metal barrier film and can minimize the occurrence of defects.

[0193] Reference Figure 1 and Figure 2 The polishing object 130 may be a semiconductor wafer having a tungsten film 40 and a metal barrier film 30, and the semiconductor wafer may include: a silicon substrate 10; a SiO2 oxide film 20; a metal barrier film 30 such as Ti / TiN (adhesion layer / diffusion prevention layer) on the SiO2 oxide film; and a tungsten film 40 on the metal barrier film. A SiO 2 oxide film 20 is formed to a thickness of 1000 Å, and the SiO 2 oxide film 20 is etched to form a contact hole.

[0194] Reference Figure 2 The method for manufacturing a semiconductor device may include the following steps: rotating the platform 120 and the carrier 160 while the polishing surface of the polishing pad 110 and the polished surface of the polishing object 130 are arranged to be in contact with each other.

[0195] The polishing pad 110 is mounted on the platform 120 with its polishing surface as the uppermost surface, and the polishing object 130 is accommodated on the carrier 160 with its polished surface as the lowermost surface, thereby enabling the polishing surface and the polished surface to be in contact with each other. The polishing surface and the polished surface being in contact with each other can be interpreted as including not only direct physical contact but also indirect contact through the polishing particles in the semiconductor processing composition.

[0196] As the platform 120 rotates, the polishing pad 110 also rotates at substantially the same trajectory and speed, and as the carrier 160 rotates, the polishing object 130 also rotates at substantially the same trajectory and speed. The platform 120 and the carrier 160 can rotate in the same direction or in different directions.

[0197] In one embodiment of the present invention, the rotational speeds of the platform 120 and the carrier 160 can each be approximately 10 rpm to approximately 500 rpm, for example, approximately 30 rpm to approximately 200 rpm. When the platform 120 and the carrier 160 rotate at speeds within these ranges, the friction between the polishing surface and the polished surface caused by the centrifugal force interacts with the semiconductor processing composition supplied to the polishing surface, thereby achieving an effect of ensuring the polishing flatness of the polished surface.

[0198] In one embodiment of the present invention, the carrier 160 may rotate at a higher speed than the platform 120. By rotating the carrier 160 at a higher speed than the platform 120, the polishing surface of the polishing object 130 can be polished without defects while ensuring polishing stability.

[0199] In one embodiment of the present invention, the semiconductor device manufacturing method rotates the platform 120 and the carrier 160, wherein the rotation is performed while the carrier 160 applies pressure to the polishing surface. By applying pressure to the polishing surface under predetermined pressure conditions by the carrier 160, excellent polishing performance can be achieved both when the polished surface of the polishing object 130 is polished in direct contact with the polishing surface of the polishing pad 110, and when the semiconductor process composition 150 is used as a medium for indirect contact polishing. For example, the load applied by the carrier 160 to the polishing surface can be from about 0.01 psi to about 20 psi, or, for example, from about 0.1 psi to about 15 psi.

[0200] Reference Figure 2 The method for manufacturing a semiconductor device may further include supplying a semiconductor process composition 150 to the polishing surface. More specifically, the semiconductor process composition 150 is supplied to the polishing surface through a supply nozzle 140 .

[0201] In one embodiment of the present invention, the flow rate of the semiconductor process composition 150 sprayed through the supply nozzle 140 can be from about 10 mL / min to about 1000 mL / min, for example, from about 10 mL / min to about 800 mL / min, or for example, from about 50 mL / min to about 500 mL / min. When the semiconductor process composition 150 is supplied to the polishing surface at a flow rate within this range, the friction between the polishing surface and the polished surface, through which the composition 150 acts as a medium, can further improve the polishing performance of the polished surface. More specifically, based on the structure of the semiconductor wafer, the polishing result of the polished surface including the tungsten film and the metal barrier film is excellent in polishing performance and can prevent the occurrence of defects.

[0202] The semiconductor process composition may include polishing particles and at least one additive. The polishing particles and the at least one additive are the same as those described for the semiconductor process composition. Specifically, all of the specific examples and technical advantages associated with the polishing particles and the at least one additive described above for the semiconductor process composition can be comprehensively applied to the semiconductor process composition used in the semiconductor device manufacturing method, and can achieve beneficial interactions with other components of the semiconductor device manufacturing method, such as the structure and driving of the platform and carrier.

[0203] Reference Figure 2 In one embodiment, the semiconductor device manufacturing method may further include processing the polishing surface of the polishing pad 110 using a conditioner 170. As the semiconductor process composition 150 is continuously supplied, the polishing surface of the polishing pad 110 is chemically affected and, at the same time, physically affected by physical contact with the polished surface of the polishing object 130. If the state of the polishing surface is deformed by these chemical / physical effects, it may be difficult to uniformly maintain the polishing performance of the polished surface. Processing the polishing surface using the conditioner 170 can help the polishing surface consistently maintain a state suitable for polishing.

[0204] For example, the dresser 170 can perform a function of roughening the polishing surface while rotating at a predetermined speed. The rotation speed of the dresser 170 can 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, greater than about 200 rpm and less than about 400 rpm.

[0205] The dresser 170 can rotate while applying a predetermined pressure to the polishing surface of the polishing pad 110. For example, the dresser 170 can apply a pressure of about 1 psi to about 20 psi to the polishing surface, 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.

[0206] The dresser 170 performs surface treatment under the above-mentioned process conditions, so that the polishing surface can maintain an optimal surface state throughout the entire polishing process, and under the condition of applying the semiconductor process composition 150, the polishing life can be extended.

[0207] The following are specific embodiments of the present invention. However, the following embodiments are only used to illustrate or describe the present invention in detail, and the scope of the present invention is not limited thereby. The scope of the present invention is determined by the claims.

[0208] Production Example 1

[0209] Preparation of polishing particles (Example 1)

[0210] Weakly acidic colloidal silica is produced by using water glass as a precursor and KOH as a catalyst. Specifically, KOH is added to the water glass and adjusted to an alkaline condition of pH 10. Under the alkaline conditions, SiO is formed and seed crystals are formed, which then grow into particles. Subsequently, a small amount of nitric acid is added and unnecessary metal ions are removed by deionization of an ion exchange resin to produce weakly acidic colloidal silica. The weakly acidic colloidal silica has a pH of 6, a zeta potential of -24 mV, and an average particle size (D50) of 41 nm.

[0211] While the weakly acidic colloidal silica was stirred at 1700 rpm, acetic acid and 3-aminopropyltriethoxysilane (APTES) as an aminosilane were slowly added at a rate of 100 mL / min to produce weakly acidic surface-modified colloidal silica having a pH of 3.8.

[0212] Examples 2 to 3

[0213] Based on Preparation Example 1, weakly acidic surface-modified colloidal silica was prepared, wherein the injection amounts of the weakly acidic colloidal silica, aminosilane, and acetic acid are shown in Table 1 below.

[0214] Comparative Example 1

[0215] Strongly alkaline colloidal silica with a pH of 9 and a zeta potential of -52 mV was prepared. Nitric acid was added to the strongly alkaline colloidal silica at 1700 rpm to produce strongly acidic colloidal silica with a pH of 2.3. Acetic acid was rapidly injected at a rate of 50 mL / sec.

[0216] Surface-modified colloidal silica was produced by slowly adding 3-aminopropyltriethoxysilane (APTES) as an aminosilane and nitric acid to the strongly acidic colloidal silica while stirring the colloidal silica at 1700 rpm.

[0217] Comparative Example 2

[0218] The same method as in Comparative Example 1 was carried out except that the injection rate was kept at 1 mL / sec when acetic acid was added to the strongly alkaline colloidal silica.

[0219] Comparative Example 3

[0220] Colloidal silica was prepared by dispersing it in a neutral solution having a zeta potential of -12 mV at pH 6. Nitric acid was added to the neutral colloidal silica while stirring it at high speed to produce strongly acidic colloidal silica having a pH of 2.3.

[0221] The strongly acidic colloidal silica was stirred at high speed, and 3-aminopropyltriethoxysilane (APTES) as an aminosilane and nitric acid were slowly added to the strongly acidic colloidal silica while being stirred at high speed to produce surface-modified colloidal silica.

[0222] Comparative Example 4

[0223] Colloidal silica was prepared by dispersing it in a strongly alkaline solution having a pH of 9 and a zeta potential of -52 mV. The colloidal silica was stirred at 1700 rpm and nitric acid was added to prepare strongly acidic colloidal silica having a pH of 2.3.

[0224] Surface-modified colloidal silica was produced by slowly adding 3-aminopropyltriethoxysilane (APTES) as an aminosilane and nitric acid to the strongly acidic colloidal silica while stirring the colloidal silica at 1700 rpm.

[0225] The zeta potential values ​​according to the contents of the constituent components and pH used to produce the surface-modified colloidal silica of the examples and comparative examples are shown in Table 1. From the measured zeta potential values, the value according to the following formula 1 was also derived.

[0226] Form 1:

[0227] Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)|

[0228] In the formula 1, p6 is pH 6, p5 is pH 5, Z6 is the zeta potential at pH 6, and Z5 is the zeta potential at pH 5.

[0229] Using the same method as the above-mentioned formula 1, the values ​​of the following formulas 2 to 4 are also derived.

[0230] Form 2:

[0231] Zeta potential change rate = |(Z6-Z4) / (p6-p4)|

[0232] Wherein, the p6 is pH 6, the p4 is pH 4, the Z6 is the ZETA potential under the pH 6 condition, and the Z4 is the ZETA potential under the pH 4 condition.

[0233] Form 3:

[0234] Zeta potential change rate = |(Z6-Z1) / (p6-p1)|

[0235] Wherein, the p6 is pH 6, the p1 is pH 1, the Z6 is the ZETA potential under the pH 6 condition, and the Z1 is the ZETA potential under the pH 1 condition.

[0236] Form 4:

[0237] Zeta potential change rate = |(Z6-Z2) / (p6-p2)|

[0238] Wherein, the p6 is pH 6, the p2 is pH 2, the Z6 is the ZETA potential under the pH 6 condition, and the Z2 is the ZETA potential under the pH 2 condition.

[0239] The following zeta potential change rate is calculated in the same manner as in the above formula 1. Specifically, the change rate from 1 to 2 is calculated as (zeta potential at pH 1 - zeta potential at pH 2) / (pH 2 - pH 1). Other values ​​are calculated in the same manner.

[0240] [Table 1]

[0241]

[0242] (Unit weight parts, aminosilane and acetic acid are weight parts relative to 100 weight parts of colloidal silica)

[0243] *Examples 1 to 3 show the change in zeta potential when the pH value changes from 6 to 4, and Comparative Examples 1 to 3 show the change in zeta potential when the pH value changes from 6 to 2.

[0244] Production Example 2

[0245] Production of compositions for semiconductor processing

[0246] Polishing particles produced in Examples 1 to Comparative Examples 4 were used, and glycine (A3-10, Yunwoo Chemical Co., Ltd.), sorbitol (GC-30, Yunwoo Chemical Co., Ltd.), and a fluorine-based surfactant (FS-30, Chemours) were mixed with the polishing particles. Specifically, a semiconductor process composition was prepared by mixing 3 wt% of the polishing particles, 0.1 wt% of glycine, 2 wt% of a sorbitol solution, 0.0025 wt% of a fluorine-based surfactant, and the remainder of ultrapure water.

[0247] Experimental methods

[0248] (1) Measuring LPC

[0249] Prepare 100 mL of each sample and age it for 2 hours to remove foam. Before measuring the sample, rinse the entire equipment line with ultrapure water. Measure the diluted sample at least five times using the following equipment and conditions, and calculate the average.

[0250] Equipment Name: Accusizer Fx Nano (PSSA)

[0251] Flow rate: 15 mL / min

[0252] Number of channels: 32

[0253] Light Extinction collection time: 60 seconds

[0254] Initial concentration: 4000 cells / mL

[0255] Minimum size: 0.56μm

[0256] Maximum size: 20μm

[0257] (2) Measurement Defect

[0258] Reference Figure 1A wafer is prepared, which includes a SiO2 oxide film as an interlayer insulating film on a silicon substrate 10, includes a contact hole formed by etching the interlayer insulating film, and includes a metal barrier film 30 such as Ti / TiN (adhesion layer / diffusion prevention layer) on the entire surface of the substrate including the contact hole, and includes a tungsten film formed on the upper portion in such a manner that the contact hole is completely filled. Figure 2 As shown, a pattern wafer 130 was used as the polishing target, and the polished surface was placed in a carrier 160 with the carrier facing downward. The carrier 160 was positioned so that the polished surface and the polishing surface were in contact with each other on a platform 120 mounted with a polishing pad 110 facing upward. The polishing surface was then operated for 60 seconds with the carrier 160 applying a pressure of 3.0 psi, the carrier 160 rotating at 93 rpm, and the platform 120 rotating at 87 rpm. The semiconductor process composition of each of the examples and comparative examples was applied to the polishing surface at a flow rate of 300 ml / min. After polishing, a cleaning process was performed for 60 seconds while spraying a cleaning solution at a brush rotation speed of 500 rpm and a spray rate of 2000 cc / min. The pattern wafers that had completed the cleaning process were sealed in a wafer cassette and the total number of defects measured using SKC's own AIT-XP+ equipment. The polishing rate is calculated by measuring the thickness after polishing under the above polishing conditions.

[0259] [Table 2]

[0260]

[0261] Table 2 shows that when the polishing compositions of Examples 1 to 3 of the present invention were used in the polishing process, the number of defects that occurred was significantly different from that of the comparative examples. Specifically, 243 defects were observed in Example 1, 181 defects in Example 2, and 269 defects in Example 3. In contrast, 1785 defects were observed in Comparative Example 1, 2783 defects in Comparative Example 2, 3482 defects in Comparative Example 3, and 5529 defects in Comparative Example 4.

[0262] As described above, the number of defects shows significant differences, allowing comparison through LPC analysis results. In Example 1, there were 284 particles larger than 5 μm and 630 particles larger than 3 μm. In Example 2, there were 143 particles larger than 5 μm and 423 particles larger than 3 μm. In Example 3, there were 344 particles larger than 5 μm and 821 particles larger than 3 μm. In Comparative Example 1, there were 724 particles larger than 5 μm and 2423 particles larger than 3 μm. In Comparative Example 2, there were 435 particles larger than 5 μm and 1872 particles larger than 3 μm. In Comparative Example 3, there were 921 particles larger than 5 μm and 3114 particles larger than 3 μm. In Comparative Example 4, there were 587 particles larger than 5 μm and 1142 particles larger than 3 μm, showing significant differences in particle size.

[0263] In addition, according to the measurement results of the polishing rate of the oxide film, Example 1 is Example 2 is Example 3 is In the case of Comparative Examples 1 to 4, and Thus, it was confirmed that no major differences were shown.

[0264] This means that the semiconductor process composition containing the polishing particles of the present invention has equivalent or better polishing performance than the polishing particles contained in conventional semiconductor process compositions and can reduce the occurrence of defects.

[0265] The preferred embodiments of the present invention are described in detail above, but the scope of the present invention is not limited thereto. Various modifications and improvements made by those skilled in the art using the basic concept of the present invention are also within the scope of the rights of the present invention as defined in the appended claims.

Claims

1. A composition for semiconductor processing, wherein: Contains polishing particles, Under the condition of pH 6, the zeta potential of the polishing particle is -50 mV to -10 mV, and under the condition of pH 5, the zeta potential of the polishing particle is -5 mV to -6 mV, and the zeta potential change rate represented by the following formula 1 is 14 mV / pH to 24 mV / pH, the zeta potential change rate represented by the following formula 4 is 9.5 mV / pH to 20 mV / pH, and the zeta potential change rate represented by the following formula 3 is 8 mV / pH to 20 mV / pH. Form 1: Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)| Form 4: Zeta potential change rate (mV / pH) = |(Z6-Z2) / (p6-p2)| Form 3: Zeta potential change rate (mV / pH) = |(Z6-Z1) / (p6-p1)| In the first, fourth and third formulas, p6 is pH 6, p5 is pH 5, p2 is pH 2, and p1 is pH 1. The Z6 is the zeta potential at the pH 6 condition, the Z5 is the zeta potential at the pH 5 condition, the Z2 is the zeta potential at the pH 2 condition, and the Z1 is the zeta potential at the pH 1 condition.

2. The semiconductor process composition according to claim 1, wherein At a pH of pH 2 to pH 4, the polishing particles are surface treated to have a positive zeta potential value.

3. The semiconductor process composition according to claim 2, wherein The zeta potential of the polishing particles is 10 mV to 50 mV.

4. The semiconductor process composition according to claim 1, wherein The polishing particles include one selected from the group consisting of silica, ceria, alumina, zirconia, and combinations thereof.

5. The semiconductor process composition according to claim 1, wherein The semiconductor process composition further comprises at least one additive selected from the group consisting of organic acids, polyols, surfactants, and combinations thereof.

6. A method for producing a composition for semiconductor processing, wherein: The steps include: By adding an acidic solution to polishing particles having a zeta potential of -50 mV to -10 mV at pH 6 and a zeta potential of -5 mV to -6 mV at pH 5, adjusting to pH 2 to pH 4, and stirring the pH-adjusted polishing particles and adding an organic component and an organic acid to the polishing particles; The polishing particles have a zeta potential change rate of 14 mV / pH to 24 mV / pH as expressed by the following formula 1, a zeta potential change rate of 9.5 mV / pH to 20 mV / pH as expressed by the following formula 4, and a zeta potential change rate of 8 mV / pH to 20 mV / pH as expressed by the following formula 3. Form 1: Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)| Form 4: Zeta potential change rate (mV / pH) = |(Z6-Z2) / (p6-p2)| Form 3: Zeta potential change rate (mV / pH) = |(Z6-Z1) / (p6-p1)| In the first, fourth and third formulas, p6 is pH 6, p5 is pH 5, p2 is pH 2, and p1 is pH 1. The Z6 is the zeta potential at the pH 6 condition, the Z5 is the zeta potential at the pH 5 condition, the Z2 is the zeta potential at the pH 2 condition, and the Z1 is the zeta potential at the pH 1 condition.

7. The method for producing a composition for semiconductor processing according to claim 6, wherein: The polishing particles are stirred at a rotation speed of 1500 rpm to 2000 rpm.

8. The method for producing a composition for semiconductor processing according to claim 6, wherein: The organic component is selected from the group consisting of aminosilane, alkoxysilane, epoxysilane and combinations thereof.

9. The method for producing a composition for semiconductor processing according to claim 6, wherein: The organic acid is selected from the group consisting of nitric acid, acetic acid, formic acid, benzoic acid, nicotinic acid, picolinic acid, alanine, phenylalanine, valine, leucine, isoleucine, arginine, aspartic acid, citric acid, adipic acid, succinic acid, oxalic acid, glycine, glutamic acid, glutaric acid, phthalic acid, histidine, threonine, serine, cysteine, methionine, asparagine, tyrosine, diiodotyrosine, tryptophan, proline, hydroxyproline, ethylenediaminetetraacetic acid, nitrotriacetic acid, iminodiacetic acid, and combinations thereof.

10. A method for manufacturing a semiconductor device, wherein: The steps include: Prepare a platform on which a polishing pad having a polishing surface is mounted, preparing a carrier containing a polishing object, In a state where the polishing surface of the polishing pad and the polished surface of the polishing object are arranged in contact with each other, rotating the platform and the carrier, and supplying a semiconductor processing composition onto the polishing surface; The semiconductor process composition comprises polishing particles and at least one additive; Under the condition of pH 6, the zeta potential of the polishing particle is -50 mV to -10 mV. Under the condition of pH 5, the zeta potential of the polishing particle is -5 mV to -6 mV. The zeta potential change rate of the polishing particle expressed by the following formula 1 is 14 mV / pH to 24 mV / pH, the zeta potential change rate expressed by the following formula 4 is 9.5 mV / pH to 20 mV / pH, and the zeta potential change rate expressed by the following formula 3 is 8 mV / pH to 20 mV / pH. Form 1: Zeta potential change rate (mV / pH) = |(Z6-Z5) / (p6-p5)| Form 4: Zeta potential change rate (mV / pH) = |(Z6-Z2) / (p6-p2)| Form 3: Zeta potential change rate (mV / pH) = |(Z6-Z1) / (p6-p1)| In the first, fourth and third formulas, p6 is pH 6, p5 is pH 5, p2 is pH 2, and p1 is pH 1. The Z6 is the zeta potential at the pH 6 condition, the Z5 is the zeta potential at the pH 5 condition, the Z2 is the zeta potential at the pH 2 condition, and the Z1 is the zeta potential at the pH 1 condition.

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