Slurry composition for chemical-mechanical polishing

Abstract

The present invention relates to a slurry composition for chemical-mechanical polishing, wherein the polishing rate for a low dielectric film is higher than the polishing rate for a silicon nitride film.

Description

Slurry composition for chemical-mechanical polishing

[0001] The present invention relates to a slurry composition for chemical-mechanical polishing.

[0002]

[0003] As semiconductor devices become more diverse and highly integrated, finer pattern formation techniques are being used, and as a result, the surface structure of semiconductor devices becomes more complex, and the interlayer flatness in each process is a very important factor in improving the precision of photolithography. In the manufacture of semiconductor devices, the chemical mechanical polishing (CMP) process is used as this planarization technology. For example, it is widely used as a process for removing an excessive amount of insulating film formed for interlayer insulation, a process for planarizing an insulating film for shallow trench isolation (STI) that provides insulation between chips, and a process for forming metal conductive films such as wiring, contact plugs, and via contacts.

[0004] In the CMP process, the polishing rate, the flatness of the polished surface, and the degree of scratches are important, and are determined by CMP process conditions, the type of slurry, and the type of polishing pad. In particular, it is necessary to prepare a CMP slurry composition suitable for the type of wafer to be polished. In this case, there are cases where selective polishing characteristics are required, such as a high polishing rate for one type of film and a low polishing rate for another type of film.

[0005] Accordingly, there is a need for technological development for a CMP slurry composition capable of controlling the polishing speed depending on the polishing target.

[0006]

[0007] The present invention provides a chemical-mechanical polishing slurry composition that has a high polishing rate for a low-k dielectric film and a low polishing rate when exposed to a silicon nitride film, thereby improving a protective function and suppressing the occurrence of defects after a wafer polishing process.

[0008] However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned can be clearly understood by those skilled in the art from the description below.

[0009]

[0010] One embodiment of the present invention provides a chemical-mechanical polishing slurry composition comprising: an abrasive comprising at least one of cerium oxide and cerium hydroxide; and a polishing selectivity control agent comprising an amine group-containing compound; wherein the polishing rate for a low-k dielectric film is greater than the polishing rate for a silicon nitride film.

[0011] According to one embodiment of the present invention, the zeta potential (ZP) of the abrasive may be 3 mV or more and 60 mV or less.

[0012] According to one embodiment of the present invention, the average size of the abrasive may be 1 nm or more and 60 nm or less.

[0013] According to one embodiment of the present invention, the content of the abrasive may be 0.1 part by weight or more and less than 1 part by weight based on 100 parts by weight of the chemical-mechanical polishing slurry composition.

[0014] According to one embodiment of the present invention, the amine group-containing compound may include at least one of an amine group and a hydroxy group-containing cyclic compound and an amine group-containing polymer.

[0015] According to one embodiment of the present invention, the amine group-containing polymer may include at least polyethylene imine.

[0016] According to one embodiment of the present invention, the molecular weight of the amine group-containing polymer may be 300 g / mol or more and 800 g / mol or less.

[0017] According to one embodiment of the present invention, the content of the polishing selectivity control agent may be 0.01 part by weight or more and 0.1 part by weight or less, based on 100 parts by weight of the chemical-mechanical polishing slurry composition.

[0018] According to one embodiment of the present invention, the weight ratio of the polishing selectivity regulator and the polishing agent may be 1:2 to 1:50.

[0019] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may have a pH of 9 or less.

[0020] According to one embodiment of the present invention, the dielectric constant of the low-k dielectric film may be 4 or less.

[0021] According to one embodiment of the present invention, the low dielectric film may include at least one of polyimide, PTFE, SiCO, SiCOH, SiOCN, SiOF, SiC, and SiCN.

[0022] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may have a ratio of the polishing speed of the low-k dielectric film to the polishing speed of the silicon nitride film of 2 or more and 250 or less.

[0023] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may have a polishing speed of 450 Å / min or less for a silicon nitride film.

[0024] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may have a polishing speed of 700 Å / min or more for a low-k dielectric film.

[0025] According to one embodiment of the present invention, the surface of the abrasive contains silicon, and in the FT-IR spectrum, it has a wavelength of 850 to 950 cm -1Peaks appearing at 1,000 to 1,050 cm -1 may have peaks appearing in .

[0026] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may further include a pH regulator including at least one of a basicity regulator and an acidity regulator.

[0027] According to one embodiment of the present invention, the pKa value of the alkalinity regulator may be 11 or less.

[0028] According to one embodiment of the present invention, the acidity regulator may include at least one of acetic acid, nitric acid, hydrochloric acid, and sulfuric acid.

[0029] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may further include one or more biocides.

[0030]

[0031] A chemical-mechanical polishing slurry composition according to one embodiment of the present invention has high polishing performance for a low-k dielectric film and low polishing performance for a silicon nitride film, thereby realizing excellent selective polishing characteristics.

[0032] In addition, the chemical-mechanical polishing slurry composition according to one embodiment of the present invention has the advantage of being able to easily control the ratio of the polishing speed of a low-k dielectric film to the polishing speed of a silicon nitride film within a specific range.

[0033] In addition, the chemical-mechanical polishing slurry composition according to one embodiment of the present invention can implement an improved removal rate profile as the flowability is improved due to the excellent dispersion of the abrasive within the composition.

[0034] In addition, by using a chemical-mechanical polishing slurry composition according to one embodiment of the present invention, a semiconductor device having superior reliability and characteristics can be manufactured.

[0035] The effects of the present invention are not limited to the effects described above, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and the attached drawings.

[0036]

[0037] Figure 1 shows the FT-IR spectrum of an abrasive according to one embodiment of the present invention.

[0038]

[0039] Throughout this specification, whenever a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0040] Throughout this specification, when it is said that an element is "on" another element, this includes not only cases where the element is in contact with the other element, but also cases where another element exists between the two elements.

[0041] Throughout this specification, the unit “parts by weight” may mean the weight ratio between each component.

[0042] Throughout this specification, terms containing ordinal numbers, such as "first" and "second," are used to distinguish one component from another and are not limited by the ordinal numbers. For example, within the scope of the invention, the first component may also be referred to as the second component, and similarly, the second component may be referred to as the first component.

[0043] Throughout the present specification, the "weight average molecular weight", "molecular weight", etc. of a compound can be calculated using the molecular weight and molecular weight distribution of the compound. Specifically, a sample having a concentration of 1 wt% of the compound is prepared by adding tetrahydrofuran (THF) and the compound to a 1 ml glass bottle, and a standard sample (polystyrene) and the sample sample are filtered through a filter (pore size: 0.45 μm), and then injected into a GPC injector. The elution time of the sample sample is compared with the calibration curve of the standard sample, thereby obtaining the molecular weight and molecular weight distribution of the compound. At this time, Infinity II 1260 (Agilient) can be used as the measuring device, and the flow rate can be set to 1.00 mL / min and the column temperature to 40.0 °C.

[0044]

[0045] Hereinafter, the present specification will be described in more detail.

[0046] One embodiment of the present invention provides a chemical-mechanical polishing slurry composition comprising: an abrasive comprising at least one of cerium oxide and cerium hydroxide; and a polishing selectivity control agent comprising an amine group-containing compound; wherein the polishing rate for a low-k dielectric film is greater than the polishing rate for a silicon nitride film.

[0047] A chemical-mechanical polishing slurry composition according to one embodiment of the present invention has high polishing performance for a low-k dielectric film and low polishing performance for a silicon nitride film, thereby realizing excellent selective polishing characteristics. In addition, the chemical-mechanical polishing slurry composition has the advantage of easily controlling the ratio of the polishing rate of the low-k dielectric film to the polishing rate of the silicon nitride film within a specific range. In addition, the chemical-mechanical polishing slurry composition has excellent dispersion of the abrasive within the composition, thereby improving flowability, and thus can realize an improved removal rate profile. In addition, by using the chemical-mechanical polishing slurry composition, a semiconductor device with superior reliability and characteristics can be manufactured.

[0048] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition (CMP slurry composition) may include at least one of cerium oxide and cerium hydroxide as an abrasive. When the aforementioned type of abrasive is used, the CMP slurry composition can exhibit excellent polishing performance.

[0049] According to one embodiment of the present invention, the zeta potential (ZP) of the abrasive may be 3 mV or more and 60 mV or less. Specifically, the zeta potential of the abrasive may be 5 mV or more and 55 mV or less, 10 mV or more and 50 mV or less, 15 mV or more and 45 mV or less, 20 mV or more and 40 mV or less, 25 mV or more and 35 mV or less, 3 mV or more and 45 mV or less, 5 mV or more and 40 mV or less, 10 mV or more and 30 mV or less, 15 mV or more and 25 mV or less, 30 mV or more and 60 mV or less, 31 mV or more and 50 mV or less, 31 mV or more and 44 mV or less, 35 mV or more and 50 mV or less, 35 mV or more and 40 mV or less, or 40 mV or more and 45 mV or less. At this time, the zeta potential of the abrasive may be a value under the pH conditions of the CMP slurry composition described below. Specifically, the zeta potential of the abrasive may be a value at pH 5 to 9. The abrasive having the zeta potential range described above may have excellent dispersibility within the CMP slurry composition. Through this, the CMP slurry composition may realize excellent polishing performance.

[0050] According to one embodiment of the present invention, the average size of the abrasive may be 1 nm or more and 65 nm or less. Specifically, the average size of the abrasive may be 1 nm or more and 60 nm or less, 5 nm or more and 55 nm or less, 10 nm or more and 50 nm or less, 15 nm or more and 45 nm or less, 20 nm or more and 40 nm or less, 25 nm or more and 35 nm or less, 5 nm or more and 50 nm or less, 15 nm or more and 60 nm or less, 15 nm or more and 30 nm or less, 20 nm or more and 55 nm or less, 25 nm or more and 50 nm or less, or 30 nm or more and 45 nm or less. When the size of the abrasive is within the above-mentioned range, the abrasive can be more homogeneously dispersed in the CMP slurry composition, and the polishing performance of the CMP slurry composition can be improved.

[0051] According to one embodiment of the present invention, based on 100 parts by weight of the chemical-mechanical polishing slurry composition, the content of the abrasive may be 0.1 part by weight or more and less than 1 part by weight. Specifically, the content of the abrasive may be 0.1 part by weight or more and 0.9 part by weight or less, 0.2 part by weight or more and 0.8 part by weight or less, 0.3 part by weight or more and 0.7 part by weight or less, 0.4 part by weight or more and 0.6 part by weight or less, 0.1 part by weight or more and 0.5 part by weight or less, 0.1 part by weight or more and 0.4 part by weight or less, 0.1 part by weight or more and 0.3 part by weight or less, 0.5 part by weight or more and 0.9 part by weight or less, or 0.6 part by weight or more and 0.8 part by weight or less, based on 100 parts by weight of the CMP slurry. By adjusting the content of the abrasive included in the CMP slurry composition within the aforementioned range, it may be easier to control the polishing rate of the CMP slurry composition for a low-k dielectric film to be greater than the polishing rate for a silicon nitride film. Furthermore, when the content of the abrasive is within the aforementioned range, the CMP slurry composition can implement an appropriate polishing rate for a low-k dielectric film while effectively suppressing an increase in the polishing rate for a silicon nitride film.

[0052] According to one embodiment of the present invention, the polishing selectivity regulator may include an amine group-containing compound. When an amine group-containing compound is used as the polishing selectivity regulator, the CMP slurry composition can effectively implement polishing characteristics in which the polishing rate for a low-k dielectric film is higher than the polishing rate for a silicon nitride film. Furthermore, the CMP slurry composition can easily implement a ratio of the polishing rate for a low-k dielectric film to a higher polishing rate for a silicon nitride film.

[0053] According to one embodiment of the present invention, the amine group-containing compound may include at least one of an amine group and a hydroxyl group-containing cyclic compound and an amine group-containing polymer. The polishing selectivity regulator may include a compound containing an amine group and a hydroxyl group as a cyclic compound. The cyclic compound may include a cycloalkyl group or a heterocycloalkyl group in its molecule. In this case, the cycloalkyl group or the heterocycloalkyl group may be a hexagonal ring, and the heterocycloalkyl group may include oxygen as a heteroatom. When a cyclic compound exposing an amine group and a hydroxyl group to the outside is used as a polishing selectivity regulator, a CMP slurry composition can be prepared that can effectively exhibit polishing characteristics in which a polishing rate for a low-k film is higher than a polishing rate for a silicon nitride film compared to a general non-polymerized amine group-containing compound or a non-polymerized hydroxyl group-containing compound.

[0054] In addition, the polishing selectivity regulator may include a polymer compound containing an amine group. The polymer compound containing an amine group may include a polyalkylene imine compound. Specifically, the amine group-containing polymer may include at least polyethylene imine (PEI). When the amine group-containing polymer is used as the polishing selectivity regulator, a CMP slurry composition can be prepared that can effectively exhibit polishing characteristics in which the polishing rate for a low-k dielectric film is higher than the polishing rate for a silicon nitride film, compared to general non-polymerized amine group-containing compounds and non-polymerized hydroxy group-containing compounds. Furthermore, when the polishing selectivity regulator including at least one of an amine group- and hydroxy group-containing cyclic compound and an amine group-containing polymer is used, the CMP slurry composition can more easily increase the ratio of the polishing rate for a low-k dielectric film to the polishing rate for a silicon nitride film.

[0055] According to one embodiment of the present invention, the cyclic compound may include at least one of chitosan, D-glucosamine, and N-acetylglucosamine. A CMP slurry composition comprising the above-described cyclic compound as a polishing selectivity control agent can achieve an appropriate polishing rate for a low-k dielectric film while effectively suppressing an increase in the polishing rate for a silicon nitride film.

[0056] According to one embodiment of the present invention, the molecular weight of the amine group-containing polymer may be 300 g / mol or more and 1,500 g / mol or less. Specifically, the molecular weight of the amine group-containing polymer may be 300 g / mol or more and 800 g / mol or less. When the molecular weight of the amine group-containing polymer is within the above-mentioned range, it may be easier to control the polishing rate of the CMP slurry composition for a low-k dielectric film to be greater than the polishing rate for a silicon nitride film. Furthermore, the CMP slurry composition can easily implement a ratio of the polishing rate of the low-k dielectric film to a higher polishing rate of the silicon nitride film.

[0057] According to one embodiment of the present invention, based on 100 parts by weight of the chemical-mechanical polishing slurry composition, the content of the polishing selectivity regulator may be 0.01 parts by weight or more and 0.2 parts by weight or less, or 0.01 parts by weight or more and 0.15 parts by weight or less. Specifically, the content of the polishing selectivity regulator may be 0.01 parts by weight or more and 0.1 parts by weight or less. More specifically, the content of the polishing selectivity regulator may be 0.03 parts by weight or more and 0.09 parts by weight or less, 0.05 parts by weight or more and 0.08 parts by weight or less, 0.01 parts by weight or more and 0.04 parts by weight or less, 0.03 parts by weight or more and 0.1 parts by weight or less, or 0.05 parts by weight or more and 0.1 parts by weight or less, based on 100 parts by weight of the CMP slurry composition. By controlling the content of the polishing selectivity control agent included in the CMP slurry composition within the above-described range, a CMP slurry composition can be provided that can achieve an appropriate polishing rate for a low-k dielectric film while effectively suppressing an increase in the polishing rate for a silicon nitride film. Furthermore, the CMP slurry composition can easily achieve a ratio of the polishing rate for a low-k dielectric film to a higher polishing rate for a silicon nitride film.

[0058] According to one embodiment of the present invention, the weight ratio of the polishing selectivity regulator and the abrasive may be 1:1.1 to 1:50. Specifically, the weight ratio of the polishing selectivity regulator and the abrasive may be 1:2 to 1:50. More specifically, the weight ratio of the polishing selectivity regulator and the abrasive may be 1:2 to 1:40, 1:2 to 1:30, 1:5 to 1:45, 1:10 to 1:40, 1:15 to 1:35, 1:20 to 1:30, 1:2 to 1:30, 1:2 to 1:25, 1:2 to 1:20, 1:2 to 1:10, 1:2 to 1:5, 1:4 to 1:15, 1:25 to 1:50, or 1:30 to 1:40. When the weight ratio of the polishing selectivity regulator and the abrasive is within the above-mentioned range, the CMP slurry composition can achieve an appropriate polishing rate for a low-k dielectric film while effectively suppressing an increase in the polishing rate for a silicon nitride film. In addition, by controlling the weight ratio of the polishing selectivity regulator and the abrasive within the above-mentioned range, the dispersibility of the CMP slurry composition can be effectively prevented from deteriorating.

[0059] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may have a pH of 9 or less. Specifically, the pH of the CMP slurry composition may be 5 or more and 9 or less, 5 or more and 8 or less, 5 or more and 7 or less, 5 or more and 6 or less, 6 or more and 8 or less, or 7 or more and 8 or less. By adjusting the acidity of the CMP slurry composition within the above-described range, the dispersibility of the polishing agent can be effectively suppressed from deteriorating. In addition, the CMP slurry composition satisfying the above-described acidity range can effectively implement polishing characteristics in which the polishing rate for a low-k dielectric film is higher than the polishing rate for a silicon nitride film.

[0060] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition can increase the ratio of the polishing rate of a low-k dielectric film to the polishing rate of a silicon nitride film as the pH increases. Specifically, the CMP slurry composition can increase the ratio of the polishing rate of a low-k dielectric film to the polishing rate of a silicon nitride film as the pH increases under the condition of pH 5 or more and 8 or less. Accordingly, the CMP slurry composition has the advantage of easily controlling the ratio of the polishing rate of a low-k dielectric film to the polishing rate of a silicon nitride film through a simple method of adjusting the pH.

[0061] According to one embodiment of the present invention, the dielectric constant of the low-k dielectric film may be 4 or less. Specifically, the dielectric constant of the low-k dielectric film may be 1.5 or more and 4 or less.

[0062] The low-k dielectric film may include any low-k dielectric film used in the art without limitation, as long as it satisfies the above dielectric constant. For example, the low-k dielectric film may include at least one of polyimide, PTFE, SiCO, SiCOH, SiOCN, SiOF, SiC, and SiCN.

[0063] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may have a ratio of the polishing speed of the low-k dielectric film to the polishing speed of the silicon nitride film of 2 or more and 250 or less. Specifically, the CMP slurry composition has a ratio of the polishing rate of the silicon nitride film to the polishing rate of the low-k dielectric film of 1:2 to 1:250, 1:5 to 1:230, 1:10 to 1:200, 1:11 to 1:200, 1:45 to 1:200, 1:100 to 1:200, 1:25 to 1:180, 1:40 to 1:150, 1:60 to 1:120, 1:80 to 1:100, 1:2 to 1:100, 1:10 to 1:100, 1:20 to 1:85, 1:30 to 1:60, 1:100 to 1:250, 1:120 to 1:230, or 1:150 to It can be 1:200. The CMP slurry composition in which the ratio of the polishing speed of the low-k dielectric film to the polishing speed of the silicon nitride film satisfies the above-mentioned range can effectively suppress the increase in the polishing speed of the silicon nitride film while simultaneously implementing excellent polishing properties for the low-k dielectric film.

[0064] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may have a polishing rate of 450 Å / min or less for a silicon nitride film. Specifically, the CMP slurry composition may have a polishing rate of 400 Å / min or less, 350 Å / min or less, 300 Å / min or less, 250 Å / min or less, 100 Å / min or less, 50 Å / min or less, or 30 Å / min or less for a silicon nitride film. In addition, the CMP slurry composition may have a polishing rate of 5 Å / min or more, 10 Å / min or more, 20 Å / min or more, 50 Å / min or more, 100 Å / min or more, 150 Å / min or more, 200 Å / min or more, or 300 Å / min or more for a silicon nitride film. The CMP slurry composition having a polishing speed of a silicon nitride film satisfying the above-mentioned range can effectively exhibit reduced polishing characteristics for a silicon nitride film.

[0065] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may have a polishing rate of 700 Å / min or more for a low-k dielectric film. Specifically, the polishing rate of the CMP slurry composition for a low-k dielectric film may be 700 Å / min or more and 6,000 Å / min or less, 1,000 Å / min or more and 6,000 Å / min or less, or 1,200 Å / min or more and 3,000 Å / min or less. The CMP slurry composition having a polishing rate of a low-k dielectric film satisfying the above-mentioned range can effectively exhibit excellent polishing properties for a low-k dielectric film.

[0066] Figure 1 shows the FT-IR spectrum of an abrasive according to one embodiment of the present invention.

[0067] According to one embodiment of the present invention, the surface of the abrasive contains silicon, and in the FT-IR spectrum, it has a wavelength of 850 to 950 cm -1 Peaks appearing at 1,000 to 1,050 cm -1It may have a peak appearing in . The silicon included on the surface of the abrasive may be derived from the dispersion stabilizer described below.

[0068] Referring to Figure 1, the abrasive has a 910 cm-cm FT-IR spectrum indicating a “Si-O-Ce” bond. -1 The peak corresponding to 1017 cm, representing the “Si-O-Si” bond -1 can exhibit a peak corresponding to that. That is, the abrasive whose surface is modified with a dispersion stabilizer can exhibit the aforementioned peak in the FT-IR spectrum.

[0069] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may further include a dispersion stabilizer. By adding a dispersion stabilizer to the CMP slurry composition, the dispersibility and dispersion stability of the abrasive can be effectively improved. Specifically, the abrasive can have its surface modified with the dispersion stabilizer, thereby improving the dispersibility and dispersion stability within the CMP slurry composition.

[0070] According to one embodiment of the present invention, the dispersion stabilizer may include a compound represented by the following chemical formula 1.

[0071] [Chemical Formula 1]

[0072]

[0073] In the above chemical formula 1, R1 to R3 are each independently a straight-chain or branched-chain alkoxy group having 1 to 5 carbon atoms, and R4 is an alkylene having 2 to 5 carbon atoms. When a dispersion stabilizer including a compound represented by the above chemical formula 1 is used, the dispersibility and dispersion stability of the abrasive can be effectively improved. For example, the compound represented by the above chemical formula 1 can include at least one of APTES ((3-Aminopropyl)triethoxysilane) and APTMS ((3-Aminopropyl)trimethoxysilane).

[0074] According to one embodiment of the present invention, the content of the dispersion stabilizer may be 0.01 parts by weight or more and 0.1 parts by weight or less, based on 100 parts by weight of the chemical-mechanical polishing slurry composition. When the content of the dispersion stabilizer is within the above-mentioned range, the surface of the abrasive can be effectively modified, thereby improving dispersibility.

[0075] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may further include a pH regulator including at least one of a basicity regulator and an acidity regulator. By including the pH regulator, the CMP slurry composition may have the acidity range described above. The content of the pH regulator may be 0.0005 parts by weight or more and 2 parts by weight or less, based on 100 parts by weight of the CMP slurry composition. In order to adjust the acidity of the CMP slurry composition to a desired range, the content of the pH regulator may be adjusted within the above-described range.

[0076] According to one embodiment of the present invention, the pKa value of the basicity regulator may be 11 or less. Specifically, the pKa value of the basicity regulator may be 5 or more and 11 or less. By using the basicity regulator having a pKa value satisfying the above-mentioned range, the pH of the CMP slurry composition can be easily controlled to a desired value. The basicity regulator may include, for example, at least one of imidazole (pKa value: 6.93), diethanolamine (pKa value: 8.88), monoethanolamine (pKa value: 9.5), and triethanolamine (pKa value: 10.65). However, the type of the basicity regulator is not limited thereto, and a substance satisfying the above-mentioned pKa value can be used as the basicity regulator.

[0077] According to one embodiment of the present invention, the acidity regulator may include at least one of acetic acid, nitric acid, hydrochloric acid, and sulfuric acid. By using the acidity regulator, the pH of the CMP slurry composition can be easily controlled to a desired value.

[0078] According to one embodiment of the present invention, the chemical-mechanical polishing slurry composition may further include one or more biocides. The biocides are used to prevent microbial contamination, and for example, polyhexamethylene guanidine (PHMG) or isothiazolinone-based compounds may be used. As the isothiazolinone-based compounds, at least one selected from the group consisting of methylisothiazolinone (MIT), chloromethyl isothiazolinone (CMIT), and 1,2-benzisothiazol-3(2H)-one ((1,2-benzisothiazol-3(2H)-one: Benzisothiazolinone, BIT) may be used.

[0079] According to one embodiment of the present invention, the content of the biocide may be 0.0001 parts by weight or more and 0.1 parts by weight or less, based on 100 parts by weight of the chemical-mechanical polishing slurry composition. When the content of the biocide included in the CMP slurry composition is within the above-mentioned range, an excellent sterilizing effect can be implemented, thereby preventing the generation of microorganisms and effectively suppressing changes in CMP performance.

[0080]

[0081] Hereinafter, the present invention will be described in detail using examples. However, the examples according to the present invention may be modified in various ways, and the scope of the present invention is not limited to the examples described below. The examples in this specification are provided to more fully explain the present invention to those of ordinary skill in the art.

[0082]

[0083] Experimental example

[0084] Abrasive size analysis

[0085] The average size of the abrasives used was analyzed using DLS (Litesizer 500; Anton Paar).

[0086]

[0087] pH measurement

[0088] The acidity of the CMP slurry composition was measured using Metrohm 704 (Metrohm).

[0089]

[0090] Polishing speed measurement

[0091] A 12-inch blanket of SiOCH, a low-k dielectric film, and a 12-inch blanket of silicon nitride film (PE-Nit) were prepared as wafers to be polished.

[0092] Polishing was performed using AP-300 (CTS) as a polishing equipment (Polisher) under the evaluation conditions shown in Table 1 below, and the polishing speed was calculated using the following mathematical equation 1. The thickness of the wafer was measured using ST-5000 (K-Mac).

[0093]

[0094] RPMPlaten93Head87CMP slurry compositionFlow rate200 ml / minPressure(psi)W12.5W22W32W42W52PadIC1010

[0095]

[0096] [Mathematical Formula 1]

[0097] Polishing rate = (wafer thickness before CMP rotation - wafer thickness after CMP rotation) / CMP process time (min)

[0098]

[0099] Zeta potential measurement

[0100] The zeta potential of the abrasive was measured using DLS (Litesizer 500; Anton Paar) according to the conditions in Table 2 below.

[0101]

[0102] Measurement principle Electrophoretic light scattering (ELS) / cmPALS Measurement range > + / -1000 mV Size range 3.8 nm to 100 μm (diameter) Minimum sample concentration 0.1 mg / mL (lysozyme) Maximum sample concentration 70 % w / v (sample dependent) Maximum sample conductivity 200 mS / cm

[0103]

[0104] Example 1

[0105] Ceria having an average size of 46 nm was prepared as an abrasive, polyethylene imine (PEI) having a molecular weight of 300 g / mol was prepared as an abrasive selectivity regulator, and nitric acid was prepared as a pH regulator. Thereafter, the abrasive, the abrasive selectivity regulator, and the pH regulator were added to deionized water to prepare a CMP slurry composition. At this time, based on 100 parts by weight of the CMP slurry, the content of the abrasive was 0.3 parts by weight, the content of the abrasive selectivity regulator was 0.01 parts by weight, and the content of the pH regulator was 0.01 parts by weight.

[0106] Thereafter, using the manufactured CMP slurry composition, a CMP process was performed on a low-k dielectric film (SiOCH) and a silicon nitride film, and the polishing rate for the CMP process is shown in Table 4 below. In addition, the zeta potential (ZP) value of the abrasive included in the CMP slurry composition and the pH of the CMP slurry composition were measured using the above-described method, and the results are shown in Table 4 below.

[0107]

[0108] Examples 2 to 7

[0109] Example 2

[0110] Ceria with an average size of 30 nm was prepared as an abrasive, PEI with a molecular weight of 800 g / mol was prepared as an abrasive selectivity regulator, and nitric acid was prepared as a pH regulator. Thereafter, the abrasive, the abrasive selectivity regulator, and the pH regulator were added to deionized water to prepare a CMP slurry composition. At this time, based on 100 parts by weight of the CMP slurry, the content of the abrasive was 0.2 parts by weight, the content of the abrasive selectivity regulator was 0.01 parts by weight, and the content of the pH regulator was 0.01 parts by weight.

[0111]

[0112] Examples 3 to 7

[0113] A CMP slurry composition was prepared in the same manner as in Example 2, except that the content of the polishing selectivity regulator and the content of the pH regulator were adjusted as shown in Table 3 below.

[0114]

[0115] In the same manner as in Example 1, a CMP process was performed on a low-k dielectric film (SiOCH) and a silicon nitride film, and the polishing rate for the CMP process is shown in Table 4 below. In addition, the zeta potential (ZP) value of the abrasive included in the CMP slurry composition and the pH of the CMP slurry composition were measured and shown in Table 4 below.

[0116]

[0117] (1) Abrasive (2) (1) / (2) (3) Content Type Size (nm) Content Molecular weight (g / mol) Content Example 1 Ceria 460.3 3000.01 300.01 Example 2 Ceria 300.28000.01 200.01 Example 3 Ceria 300.28000.03 6.7 0.02 Example 4 Ceria 300.28000.05 40.04 Example 5 Ceria 300.28000.08 2.5 0.07 Example 6 Ceria 300.28000.10 20.09 Example 7 Ceria 300.28000.15 1.3 0.14

[0118]

[0119] In the above Table 3, (2) refers to a polishing selectivity regulator, and (3) refers to a pH regulator. In addition, the content of the polishing agent, the content of the polishing selectivity regulator, and the content of the pH regulator are contents (parts by weight) based on 100 parts by weight of the CMP slurry composition.

[0120]

[0121] pHZP(mV)(1) SiOCH(Å / min)(2) Si3N4(Å / min)(1) / (2)Example 16387,16460812Example 26423,39026013Example 36423,05713922Example 46422,9196446Example 56422,5745448Example 66422,2294550Example 76426523022

[0122]

[0123] Referring to Tables 3 and 4 above, it was confirmed that the CMP slurry compositions manufactured in Examples 1 to 7 had a higher polishing rate for a low-k dielectric film than for a silicon nitride film. In addition, it was confirmed that in the case of Examples 1 to 7, excellent polishing performance was achieved for a low-k dielectric film, while suppressed polishing performance was exhibited for a silicon nitride film. In addition, it was confirmed that the polishing rate of the CMP slurry composition for a low-k dielectric film and a silicon nitride film was controlled by adjusting the content of the polishing selectivity modifier.

[0124]

[0125] Examples 8 to 12

[0126] Example 8

[0127] Ceria having an average size of 15 nm was prepared as an abrasive, PEI having a molecular weight of 800 g / mol was prepared as an abrasive selectivity regulator, and nitric acid was prepared as a pH regulator. Thereafter, the abrasive, the abrasive selectivity regulator, and the pH regulator were added to deionized water to prepare a CMP slurry composition. At this time, based on 100 parts by weight of the CMP slurry, the content of the abrasive was 0.2 parts by weight, the content of the abrasive selectivity regulator was 0.05 parts by weight, and the content of the pH regulator was 0.04 parts by weight.

[0128]

[0129] Examples 9 to 12

[0130] A CMP slurry composition was prepared in the same manner as in Example 8, except that abrasives having different average sizes were used as shown in Table 5 below.

[0131]

[0132] In the same manner as in Example 1, a CMP process was performed on a low-k dielectric film (SiOCH) and a silicon nitride film, and the polishing rate for the CMP process is shown in Table 6 below. In addition, the zeta potential (ZP) value of the abrasive included in the CMP slurry composition and the pH of the CMP slurry composition were measured and shown in Table 6 below.

[0133]

[0134] (1) Abrasive (2) (1) / (2) (3) Content Type Size (nm) Content Molecular weight (g / mol) Content Example 8 Ceria 150.28000.0540.04 Example 9 Ceria 300.28000.0540.04 Example 10 Ceria 440.28000.0540.04 Example 11 Ceria 600.28000.0540.04 Example 12 Ceria 630.28000.0540.04

[0135]

[0136] In the above Table 5, (2) refers to a polishing selectivity regulator, and (3) refers to a pH regulator. In addition, the content of the polishing agent, the content of the polishing selectivity regulator, and the content of the pH regulator are contents (parts by weight) based on 100 parts by weight of the CMP slurry composition.

[0137]

[0138] pHZP(mV)(1) SiOCH(Å / min)(2) Si3N4(Å / min)(1) / (2)Example 86441,8002572Example 96422,9196446Example 106383,26410232Example 116315,77538515Example 126314,75243211

[0139]

[0140] Referring to Tables 5 and 6 above, it was confirmed that the CMP slurry compositions manufactured in Examples 8 to 12 had a higher polishing rate for a low-k dielectric film than for a silicon nitride film. In addition, it was confirmed that in the case of Examples 8 to 12, excellent polishing performance was achieved for a low-k dielectric film, while suppressed polishing performance was exhibited for a silicon nitride film. In addition, it was confirmed that the polishing rate of the CMP slurry composition for a low-k dielectric film and a silicon nitride film was controlled by adjusting the average size of the abrasive.

[0141]

[0142] Examples 13 to 16

[0143] Example 13

[0144] Ceria with an average size of 30 nm was prepared as an abrasive, PEI with a molecular weight of 800 g / mol was prepared as an abrasive selectivity regulator, and nitric acid was prepared as a pH regulator. Thereafter, the abrasive, the abrasive selectivity regulator, and the pH regulator were added to deionized water to prepare a CMP slurry composition. At this time, based on 100 parts by weight of the CMP slurry, the content of the abrasive was 0.1 parts by weight, the content of the abrasive selectivity regulator was 0.05 parts by weight, and the content of the pH regulator was 0.04 parts by weight.

[0145]

[0146] Examples 14 to 16

[0147] A CMP slurry composition was prepared in the same manner as in Example 13, except that the content of the abrasive was adjusted as shown in Table 7 below.

[0148]

[0149] In the same manner as in Example 1, a CMP process was performed on a low-k dielectric film (SiOCH) and a silicon nitride film, and the polishing rate for the CMP process is shown in Table 8 below. In addition, the zeta potential (ZP) value of the abrasive included in the CMP slurry composition and the pH of the CMP slurry composition were measured and shown in Table 8 below.

[0150]

[0151] (1) Abrasive (2) (1) / (2) (3) Content Type Size (nm) Content Molecular weight (g / mol) Content Example 13 Ceria 300.18000.05 20.04 Example 14 Ceria 300.28000.05 40.04 Example 15 Ceria 300.58000.05 100.04 Example 16 Ceria 3018000.05 200.04

[0152]

[0153] In the above Table 7, (2) refers to a polishing selectivity regulator, and (3) refers to a pH regulator. In addition, the content of the polishing agent, the content of the polishing selectivity regulator, and the content of the pH regulator are contents (parts by weight) based on 100 parts by weight of the CMP slurry composition.

[0154]

[0155] pHZP(mV)(1) SiOCH(Å / min)(2) Si3N4(Å / min)(1) / (2)Example 136421,9253555Example 146422,9196446Example 156425,9789861Example 1664210,02912768

[0156]

[0157] Referring to Tables 7 and 8 above, it was confirmed that the CMP slurry compositions manufactured in Examples 13 to 16 had a higher polishing rate for a low-k dielectric film than for a silicon nitride film. In addition, it was confirmed that Examples 13 to 16 exhibited excellent polishing performance for a low-k dielectric film, while exhibiting suppressed polishing performance for a silicon nitride film. In addition, it was confirmed that the polishing rate of the CMP slurry composition for a low-k dielectric film and a silicon nitride film was controlled by adjusting the content of the abrasive.

[0158]

[0159] Examples 17 to 22

[0160] Example 17

[0161] Ceria having an average size of 26 nm was prepared as an abrasive, PEI having a molecular weight of 800 g / mol was prepared as an abrasive selectivity regulator, nitric acid was prepared as a pH regulator, and APTMS was prepared as a dispersion stabilizer. Thereafter, the abrasive, the abrasive selectivity regulator, the pH regulator, and the dispersion stabilizer were added to deionized water to prepare a CMP slurry composition. At this time, based on 100 parts by weight of the CMP slurry, the content of the abrasive was 0.2 parts by weight, the content of the abrasive selectivity regulator was 0.01 parts by weight, the content of the pH regulator was 0.01 parts by weight, and the content of the dispersion stabilizer was 0.03 parts by weight.

[0162]

[0163] Examples 18 to 22

[0164] A CMP slurry composition was prepared in the same manner as in Example 17, except that the content of the polishing selectivity regulator and the content of the pH regulator were adjusted as shown in Table 9 below.

[0165]

[0166] In the same manner as in Example 1, a CMP process was performed on a low-k dielectric film (SiOCH) and a silicon nitride film, and the polishing rate for the CMP process is shown in Table 10 below. In addition, the zeta potential (ZP) value of the abrasive included in the CMP slurry composition and the pH of the CMP slurry composition were measured, and are shown in Table 10 below.

[0167]

[0168] (1) Abrasive (2) (1) / (2) (3) Content (4) Content Type Content Molecular weight (g / mol) Content Example 17 Ceria 0.28000.01 200.01 0.03 Example 18 Ceria 0.28000.03 6.7 0.03 0.03 Example 19 Ceria 0.28000.05 40.05 0.03 Example 20 Ceria 0.28000.08 2.5 0.07 0.03 Example 21 Ceria 0.28000.12 0.10.03 Example 22 Ceria 0.28000.15 1.3 0.12 0.03

[0169]

[0170] In the above Table 9, (2) refers to a polishing selectivity regulator, (3) refers to a pH regulator, and (4) refers to a dispersion stabilizer. In addition, the content of the polishing agent, the content of the polishing selectivity regulator, the content of the pH regulator, and the content of the dispersion stabilizer are contents (parts by weight) based on 100 parts by weight of the CMP slurry composition.

[0171]

[0172] pHZP(mV)(1) SiOCH(Å / min)(2) Si3N4(Å / min)(1) / (2)Example 178403,85011035Example 188403,4504282Example 198402,64026102Example 208401,83010183Example 218401,2848161Example 228407383246

[0173]

[0174] Referring to Tables 9 and 10 above, it was confirmed that the CMP slurry compositions manufactured in Examples 17 to 22 had a higher polishing rate for a low-k dielectric film than for a silicon nitride film. In addition, it was confirmed that Examples 17 to 22 exhibited excellent polishing performance for a low-k dielectric film, while exhibiting suppressed polishing performance for a silicon nitride film. In addition, it was confirmed that Examples 17 to 22 could achieve a higher ratio of the polishing rate of a low-k dielectric film to the polishing rate of a silicon nitride film as the pH of the CMP slurry composition increased, compared to Examples 2 to 7 described above.

[0175]

[0176] Examples 23 to 25

[0177] Example 23

[0178] Ceria having an average size of 28 nm was prepared as an abrasive, PEI having a molecular weight of 300 g / mol was prepared as an abrasive selectivity regulator, and nitric acid was prepared as a pH regulator. Thereafter, the abrasive, the abrasive selectivity regulator, and the pH regulator were added to deionized water to prepare a CMP slurry composition. At this time, based on 100 parts by weight of the CMP slurry, the content of the abrasive was 0.2 parts by weight, the content of the abrasive selectivity regulator was 0.1 parts by weight, and the content of the pH regulator was 0.01 parts by weight.

[0179]

[0180] Examples 24 to 25

[0181] A CMP slurry composition was prepared in the same manner as in Example 23, except that the molecular weight of the polishing selectivity regulator and the content of the pH regulator were adjusted as shown in Table 11 below.

[0182]

[0183] In the same manner as in Example 1, a CMP process was performed on a low-k dielectric film (SiOCH) and a silicon nitride film, and the polishing rate for the CMP process is shown in Table 12 below. In addition, the zeta potential (ZP) value of the abrasive included in the CMP slurry composition and the pH of the CMP slurry composition were measured and shown in Table 12 below.

[0184]

[0185] (1) Abrasive (2) (1) / (2) (3) Content Type Size (nm) Content Molecular weight (g / mol) Content Example 23 Ceria 280.2 3000.120.01 Example 24 Ceria 280.2 8000.120.12 Example 25 Ceria 280.21, 2000.120.10

[0186]

[0187] In the above Table 11, (2) refers to a polishing selectivity regulator, and (3) refers to a pH regulator. In addition, the content of the polishing agent, the content of the polishing selectivity regulator, and the content of the pH regulator are contents (parts by weight) based on 100 parts by weight of the CMP slurry composition.

[0188]

[0189] pHZP(mV)(1) SiOCH(Å / min)(2) Si3N4(Å / min)(1) / (2)Example 236412,3584552Example 246413,53824147Example 256416588

[0190]

[0191] Referring to Tables 11 and 12 above, it was confirmed that the CMP slurry compositions manufactured in Examples 23 to 25 had a higher polishing rate for a low-k dielectric film than for a silicon nitride film. In addition, in the case of Examples 23 to 25, it was confirmed that excellent polishing performance was achieved for a low-k dielectric film, while suppressed polishing performance was exhibited for a silicon nitride film. In addition, it was confirmed that the polishing rate of the CMP slurry composition for a low-k dielectric film and a silicon nitride film was controlled by adjusting the molecular weight of the polishing selectivity modifier.

[0192]

[0193] Comparative Examples 1 and 2

[0194] Comparative Example 1

[0195] Ceria having an average size of 14 nm was prepared as an abrasive, and hydroxyethyl cellulose (HEC) having a molecular weight of 300 g / mol was prepared as a polishing selectivity regulator. Thereafter, the abrasive and the polishing selectivity regulator were added to deionized water to prepare a CMP slurry composition. At this time, the content of the abrasive was 0.3 parts by weight and the content of the polishing selectivity regulator was 0.01 parts by weight based on 100 parts by weight of the CMP slurry.

[0196]

[0197] Comparative Example 2

[0198] Silica with an average size of 90 nm was prepared as an abrasive, and PEI with a molecular weight of 300 g / mol was prepared as an abrasive selectivity regulator. Thereafter, the abrasive and the abrasive selectivity regulator were added to deionized water to prepare a CMP slurry composition. At this time, the content of the abrasive was 0.3 parts by weight and the content of the abrasive selectivity regulator was 0.02 parts by weight based on 100 parts by weight of the CMP slurry.

[0199]

[0200] In the same manner as in Example 1, a CMP process was performed on a low-k dielectric film (SiOCH) and a silicon nitride film, and the polishing rate for the CMP process is shown in Table 14 below. In addition, the zeta potential (ZP) value of the abrasive included in the CMP slurry composition and the pH of the CMP slurry composition were measured and shown in Table 14 below.

[0201]

[0202] (1) Abrasive (2) (1) / (2) Type Size (nm) Content Molecular weight (g / mol) Content Comparison Example 1 Ceria 140.3 HEC / 3000.0130 Comparison Example 2 Silica 900.3 PEI / 3000.0215

[0203]

[0204] In the above Table 13, (2) refers to a polishing selectivity regulator. In addition, the content of the polishing agent and the content of the polishing selectivity regulator are contents (parts by weight) based on 100 parts by weight of the CMP slurry composition.

[0205]

[0206] pHZP(mV)(1) SiOCH(Å / min)(2) Si3N4(Å / min)(1) / (2)Comparative example 16502,3526044Comparative example 26-131005000.2

[0207]

[0208] Referring to Tables 13 and 14 above, in Comparative Example 1, which used HEC as a polishing selectivity regulator, it was confirmed that the ratio of the polishing rate of the low-k dielectric film to the polishing rate of the silicon nitride film was lower than in the aforementioned examples. In addition, it was confirmed that Comparative Example 2, which used silica as an abrasive, did not provide a CMP slurry composition in which the polishing rate for the low-k dielectric film was higher than the polishing rate for the silicon nitride film.

[0209]

[0210] Therefore, it can be seen that the CMP slurry composition according to one embodiment of the present invention can effectively implement polishing characteristics in which the polishing rate for a low-k dielectric film is greater than the polishing rate for a silicon nitride film.

Claims

1. An abrasive comprising at least one of cerium oxide and cerium hydroxide; and A polishing selectivity regulator comprising an amine group-containing compound; A chemical-mechanical polishing slurry composition having a polishing rate for a low-k dielectric film greater than a polishing rate for a silicon nitride film.

2. In paragraph 1, A chemical-mechanical polishing slurry composition, wherein the zeta potential (ZP) of the above-mentioned abrasive is 3 mV or more and 60 mV or less.

3. In paragraph 1, A chemical-mechanical polishing slurry composition, wherein the average size of the abrasive is 1 nm or more and 60 nm or less.

4. In paragraph 1, A chemical-mechanical polishing slurry composition, wherein the content of the abrasive is 0.1 part by weight or more and less than 1 part by weight based on 100 parts by weight of the chemical-mechanical polishing slurry composition.

5. In paragraph 1, The above amine group-containing compound is, A chemical-mechanical polishing slurry composition comprising at least one of an amine group-containing and a hydroxyl group-containing cyclic compound and an amine group-containing polymer.

6. In paragraph 5, A chemical-mechanical polishing slurry composition wherein the above amine group-containing polymer comprises at least polyethylene imine.

7. In paragraph 5, A chemical-mechanical polishing slurry composition, wherein the molecular weight of the above amine group-containing polymer is 300 g / mol or more and 800 g / mol or less.

8. In paragraph 1, A chemical-mechanical polishing slurry composition, wherein the content of the polishing selectivity regulator is 0.01 part by weight or more and 0.1 part by weight or less, based on 100 parts by weight of the chemical-mechanical polishing slurry composition.

9. In paragraph 1, A chemical-mechanical polishing slurry composition, wherein the weight ratio of the polishing selectivity regulator and the abrasive is 1:2 to 1:

50.

10. In paragraph 1, A chemical-mechanical polishing slurry composition having a pH of 9 or less.

11. In paragraph 1, A chemical-mechanical polishing slurry composition, wherein the dielectric constant of the above low-k dielectric film is 4 or less.

12. In paragraph 1, A chemical-mechanical polishing slurry composition wherein the low-k dielectric film comprises at least one of polyimide, PTFE, SiCO, SiCOH, SiOCN, SiOF, SiC and SiCN.

13. In paragraph 1, The above chemical-mechanical polishing slurry composition comprises: A chemical-mechanical polishing slurry composition having a ratio of a polishing rate of a low-k dielectric film to a polishing rate of a silicon nitride film of 2 or more and 250 or less.

14. In paragraph 1, The above chemical-mechanical polishing slurry composition comprises: A chemical-mechanical polishing slurry composition having a polishing speed of 450 Å / min or less for a silicon nitride film.

15. In paragraph 1, The above chemical-mechanical polishing slurry composition comprises: A chemical-mechanical polishing slurry composition having a polishing speed of 700 Å / min or more for a low-k dielectric film.

16. In paragraph 1, The surface of the above abrasive contains silicon, FT-IR spectrum at 850–950 cm -1 Peaks appearing at 1,000 to 1,050 cm -1 A chemical-mechanical polishing slurry composition having a peak appearing in .

17. In paragraph 1, A chemical-mechanical polishing slurry composition further comprising a pH adjusting agent comprising at least one of a base adjusting agent and an acid adjusting agent.

18. In paragraph 17, A chemical-mechanical polishing slurry composition wherein the pKa value of the above alkalinity regulator is 11 or less.

19. In Article 17, A chemical-mechanical polishing slurry composition wherein the acidity regulator comprises at least one of acetic acid, nitric acid, hydrochloric acid and sulfuric acid.

20. In paragraph 1, A chemical-mechanical polishing slurry composition further comprising one or more biocides.

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