CN107922819B - Chemical mechanical polishing slurry composition for organic film, method for preparing the same, and method for polishing organic film using the same - Google Patents
Chemical mechanical polishing slurry composition for organic film, method for preparing the same, and method for polishing organic film using the same Download PDFInfo
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- CN107922819B CN107922819B CN201680047980.8A CN201680047980A CN107922819B CN 107922819 B CN107922819 B CN 107922819B CN 201680047980 A CN201680047980 A CN 201680047980A CN 107922819 B CN107922819 B CN 107922819B
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- organic film
- chemical mechanical
- mechanical polishing
- polishing slurry
- slurry composition
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- 238000005498 polishing Methods 0.000 title claims abstract description 178
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
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Abstract
The invention relates to a chemical mechanical polishing slurry composition for an organic film, a preparation method thereof and a method for polishing the organic film by using the chemical mechanical polishing slurry composition. The chemical mechanical polishing slurry for organic film of the present invention has a Δ θ represented by equation (1) of about 5 ° to 90 °wWhich is a change in water contact angle, and is measured after immersing a wafer to be polished, coated with an organic film, in a chemical mechanical polishing slurry for 10 hours. Equation (1): water contact angle change delta thetaw＝|θ1‑θ2|。
Description
Technical Field
The invention relates to a chemical mechanical polishing slurry composition for an organic film, a preparation method thereof and a method for polishing the organic film by using the same. More particularly, the present invention relates to a chemical mechanical polishing slurry composition suitable for polishing an organic film formed on a surface of a polishing target such as a semiconductor wafer, a method for preparing the same, and a method for polishing an organic film using the same.
Background
With the high integration of semiconductor devices, there is an increasing need to form finer patterns and multi-layer circuits. Therefore, there is a technique of using an inorganic film formed on a semiconductor and a hydrocarbon organic film which can be exclusively etched as auxiliary materials. For example, a method is proposed in which an inorganic film is formed on a patterned silicon wafer, followed by a gap-filling process in which a through-hole (via-hole) formed in the inorganic film is filled with an organic film material. After the gap-fill (gap-fill) process, a planarization process is performed to remove an excessive organic film by CMP (chemical mechanical polishing).
However, most of the chemical mechanical polishing slurries are generally used for polishing copper wires or inorganic films such as silicon oxide films or silicon nitride films, but are not suitable for polishing organic films. The organic film is softer than the inorganic film. Therefore, when the organic film is polished using the chemical mechanical polishing slurry for the inorganic film, the mechanical action of the abrasive particles is dispersed, thereby severely limiting the polishing of the organic film. When the amount or size of the abrasive particles is increased to increase the polishing rate, there may be a problem of dishing, a phenomenon in which the inorganic film is also polished together with the organic film.
In order to overcome these problems, korean patent application No. 2007-0057009 discloses a method of using polymer particles having functional groups on the surface thereof as abrasive particles for chemical mechanical polishing slurry instead of inorganic particles. However, this method has a problem in that such a chemical mechanical polishing slurry comprising polymer particles as abrasive particles cannot provide a sufficient polishing rate when used for polishing an organic film having a high film density or a high hardness.
Since organic films have different film qualities depending on their compositions, it is necessary to provide a chemical mechanical polishing slurry having an optimum composition for an organic film as a polishing target. Unlike inorganic films, organic films are formed by reactions between various compounds, and it is difficult to predict the polishing characteristics of organic films from the composition of chemical mechanical polishing slurries. Therefore, chemical mechanical polishing slurries for organic films are being developed by: preparing a slurry having a specific composition, polishing a wafer coated with an organic film to be polished with the slurry, and observing the film thickness and film characteristics to monitor whether the composition of the slurry is proper. However, this method has problems of increasing production time and production cost and being inefficient.
Disclosure of Invention
Technical problem
One embodiment of the present invention provides a chemical mechanical polishing slurry composition for an organic film, which has an excellent effect in polishing the organic film.
It is another object of the present invention to provide a method of manufacturing a chemical mechanical polishing slurry composition for organic films, which can provide optimized polishing characteristics for organic films to be polished in less time and cost.
It is another object of the present invention to provide a method for polishing an organic film using a chemical mechanical polishing slurry composition for an organic film, which has an excellent polishing effect on the organic film.
Solution scheme
According to one aspect of the present invention, a chemical mechanical polishing slurry composition for organic films is provided, comprising an oxidizing agent and a solvent. The chemical mechanical polishing slurry composition has a water contact angle change Δ θ calculated by equation (1) of 5 ° to 90 °, specifically 5 ° to 70 °, more specifically 10 ° to 50 °wMeasured after immersing a wafer to be polished coated with an organic film in a chemical mechanical polishing slurry composition for 10 hours:
equation (1):
water contact angle change (delta theta)w)＝│θ1-θ2│，
In equation (1), θ1Represents a water contact angle of an organic film measured by dropping deionized water (DIWATER) onto a surface of the organic film before immersing a wafer coated with the organic film in the chemical mechanical polishing slurry composition, and θ2Represents the water contact angle of the organic film measured by dropping deionized water (DIWATER) onto the surface of the organic film after immersing the wafer in the chemical mechanical polishing slurry composition for 10 hours.
The oxidant may comprise a material selected from Fe3+、Ce4+、Ce3+、Cu2+And Ag+And optionally, further comprises hydrogen peroxide. Specifically, the oxidant may include Fe3+、Cu2+、Ce3+Or Ce4+Or may comprise Ce4+、Ce3+、Cu2+And Ag+A mixture of at least one metal ion of (a) with hydrogen peroxide.
The oxidizing agent may include a metal salt including Ce and hydrogen peroxide in a weight ratio of 1:1.5 to 1: 3.
The oxidizing agent may be present in the chemical mechanical polishing slurry composition in an amount of 0.001 wt% to 5 wt% by weight.
The chemical mechanical polishing slurry composition may further comprise an abrasive including at least one selected from the group consisting of silicon oxide, aluminum oxide, cerium oxide, titanium oxide, and zirconium oxide. Here, the abrasive may be present in the chemical mechanical polishing slurry composition in an amount of 0.01 to 5 wt%.
The chemical mechanical polishing slurry composition may have a cyclohexane (cyclohexane) contact angle variation Δ θ calculated by equation (2) of 1 ° to 50 °, specifically 1 ° to 20 °, more specifically 1 ° to 10 °nMeasured after immersing a wafer to be polished coated with an organic film in a chemical mechanical polishing slurry composition for 10 hours:
equation (2): contact angle variation (Δ θ)n)＝│θ3–θ4│，
In equation (2), θ3Represents a contact angle of an organic film measured by dropping cyclohexane (cyclohexane) onto a surface of the organic film before immersing a wafer coated with the organic film in the chemical mechanical polishing slurry composition, and θ4Represents a contact angle of the organic film measured by dropping cyclohexane (cyclohexane) onto the surface of the organic film after immersing the wafer in the chemical mechanical polishing slurry composition for 10 hours.
The organic film as a grinding target may have a carbon content of 50 to 95 wt%.
The chemical mechanical polishing slurry composition can have a polishing rate of 500 to 10,000, specifically 1,000 to 8000, more specifically 1,500 to 5,000 angstroms per minute relative to the organic film.
According to another aspect of the present invention, there is provided a method for preparing a chemical mechanical polishing slurry composition for organic films, the method comprising: mixing an oxidizing agent with a solvent, wherein the mixing of the oxidizing agent with the solvent is performed such that the chemical mechanical polishing slurry composition has a water contact angle variation Δ θ of 5 ° to 90 ° calculated by equation (1)wnMeasured after immersing the wafer to be polished coated with the organic film in the slurry composition for 10 hours.
According to still another aspect of the present invention, there is provided a method of polishing an organic film, the method including: the organic film is polished using the chemical mechanical polishing slurry composition for organic film as described above.
Advantageous effects
The chemical mechanical polishing slurry composition for organic films of the present invention has an excellent polishing rate for organic films and provides optimized polishing characteristics for various organic films.
According to the method of manufacturing a chemical mechanical polishing slurry composition for an organic film of the present invention, a chemical mechanical polishing slurry composition for an organic film can be manufactured, optimizing the polishing characteristics of the organic film.
Drawings
Fig. 1(a) and 1(b) are diagrams of a method of polishing an organic film according to an embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
Chemical mechanical polishing slurry composition for organic film
First, a chemical mechanical polishing slurry composition for organic films according to the present invention will be described.
The chemical mechanical polishing slurry composition for organic film according to the present invention comprises a solvent and an oxidizing agent, and has a water contact angle variation Δ θ calculated by equation (1) of 5 ° to 90 °wMeasured after immersing the wafer to be polished coated with the organic film in the chemical mechanical polishing slurry composition for 10 hours.
For example, the chemical mechanical polishing slurry composition for organic membranes may have a chemical mechanical polishing slurry composition calculated by equation (1) of 5 °,6 °, 7 °, 8 °, 9 °, 10 °, 11 °, 12 °, 13 °, 14 °, 15 °, 16 °, 17 °, 18 °, 19 °, 20 °, 21 °, 22 °, 23 °, 24 °, 25 °, 26 °, 27 °, 28 °, 29 °, 30 °, 31 °, 32 °, 33 °, 34 °, 35 °, 36 °, 37 °, 38 °, 39 °, 40 °, 41 °, 42 °, 43 °, 44 °, 45 °, 46 °, 47 °, 48 °, 49 °,50 °, 51 °, 52 °, 53 °, 54 °, 55 °, 56 °, 57 °, 58 °, 59 °, 60 °, 61 °, 62 °, 63 °, 64 °, 65 °, 66 °, 67 °, 68 °, 69 °, 70 °, 71 °, 72 °, 73 °, 74 °, 75 °, 76 °, etc, Change in water contact angle Δ θ of 77 °, 78 °, 79 °, 80 °, 81 °, 82 °, 83 °, 84 °, 85 °, 86 °, 87 °, 88 °, 89 °, or 90 °wMeasured after immersing the wafer to be polished coated with the organic film in the slurry composition for 10 hours. Further, there may be a change in water contact angle Δ θ that is greater than or equal to one of the above values and less than or equal to one of the above valuesw. In particular, the method of manufacturing a semiconductor device,may have a change in water contact angle Δ θ of 5 ° to 70 °, more specifically 10 ° to 50 °w：
Equation (1):
water contact angle change (delta theta)w)＝│θ1-θ2│，
In equation (1), θ1Represents a WATER contact angle of an organic film measured by dropping deionized WATER (DI WATER) onto a surface of the organic film before immersing a wafer coated with the organic film in the chemical mechanical polishing slurry composition, and θ2Represents the WATER contact angle of the organic film measured by dropping deionized WATER (DI WATER) onto the surface of the organic film after immersing the wafer in the chemical mechanical polishing slurry composition for 10 hours.
As described above, since the organic film has a complicated structure formed by chemical reactions between various components, it is difficult to predict the polishing characteristics of the organic film. After conducting extensive studies, the inventors found that the polishing characteristics of an organic film are related to the change in water contact angle, which is found by measuring the water contact angle of the organic film as a polishing target before and after immersing a wafer coated with the organic film in a chemical mechanical polishing slurry composition.
In particular, when the variation of the water contact angle is found to be in the range of 5 ° to 90 °, for example, 5 ° to 70 ° or 10 ° to 50 °, by measuring the water contact angle of the polishing target before and after immersing the polishing target in the chemical mechanical polishing slurry composition, excellent polishing performance is exhibited with respect to the organic film as the polishing target. If the water contact angle changes less than 5 ° or greater than 90 °, there is a relatively low polishing rate for the organic film.
The wafer coated with an organic film used in measuring the water contact angle can be prepared by coating an organic film on a silicon oxide wafer.
The Silicon oxide wafer may be, but is not limited to, a wafer in which a2,000 to 12,000 angstrom thick Silicon oxide film is uniformly formed on a standard Silicon wafer (Silicon) having a diameter of 200 mm or 300 mm such that a relative standard deviation of a thickness of the Silicon oxide film is within 10%.
The wafer coated with the organic film may be prepared by coating the organic film composition on a silicon oxide wafer (silicon oxide). Here, the coating of the organic film may be performed by a process having a plurality of steps using different revolutions per minute, but is not limited thereto. For example, the coating of the organic film may be performed by a three-step spin coating (spinning) process under the following conditions:
step 1: 1000rpm, 2 seconds.
Step 2: 1500rpm, 20 seconds.
And step 3: 1000rpm, 2 seconds.
The spin coating process can be performed using a MS-A200 standard spin coater, commonly available from Sanchi corporation. The organic film composition is coated on a wafer, followed by baking (baking) on a hot plate (hot plate) to cure the organic film. For example, a2 minute bake (baking) is performed in air on a hot plate at about 400 ℃. After baking (baking), cooling was performed at room temperature for 10 minutes, whereby an organic film was formed. Through the above process, an organic film having an average thickness of 2,000 to 3,000 angstroms can be uniformly formed such that a relative standard deviation of the thickness of the film is within 5%.
The average thickness of the organic film and the relative standard deviation of the thickness of the organic film can be found by measuring the thickness of the organic film at 30 points equally spaced along the diameter of the wafer surface coated with the organic film. Here, the thickness of the organic film at each point is measured, for example, using a standard Spectral Reflectometer (Spectral Reflectometer) available from K-MAC corporation, and the values measured by the optical interference method are calibrated based on a scanning electron microscope SEM image of the cut surface of the wafer so that the error between the measured values can be within 5% of the measured values.
The water contact angle can be measured on the entire wafer coated with the organic film prepared as described above or on a sample obtained by cutting the wafer into sizes of 2 cm and 2 cm or more in length and width without causing damage to the organic film. It is understood that the measurement of the water contact angle is performed on the surface of the wafer on which the organic film is coated.
The oxidizing agent facilitates polishing of the organic film by oxidizing the surface of the organic film, and can improve the degree of planarization by leveling the surface of the organic film.
The oxidant may comprise Fe3+、Ce4+、Ce3+、Cu2+And Ag+At least one of (a). For example, the oxidizing agent may include Fe in terms of polishing rate3+、Cu2+、Ce3+And Ce4+At least one of (a). Specifically, the oxidizing agent may be a metal salt containing metal ions as described above, and may include, for example, at least one of cerium ammonium nitrate (ceric ammonium nitrate), cerium sulfate (ceric sulfate), copper chloride (cupric chloride), copper nitride (cupric nitride), iron nitride (ferri nitride), iron chloride (ferri chloride), cerium nitrate (cerous nitrate), and silver nitrate (silver nitrate).
The oxidizing agent may further include hydrogen peroxide in addition to the metal ion. When the oxidizing agent further includes hydrogen peroxide, the oxidizing ability is increased, thereby further increasing the polishing rate. For example, the oxidizing agent may include, but is not limited to, Ce4 +、Ce3+、 Cu2+And Ag+A mixture of at least one metal ion of (a) with hydrogen peroxide.
The oxidizing agent can be present in the chemical mechanical polishing slurry composition in an amount of 0.001 wt.%, 0.005 wt.%, 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, or 5 wt.%. Further, the oxidizing agent may be present in an amount greater than or equal to one of the above values and less than or equal to one of the above values. For example, the oxidizing agent may be present in the chemical mechanical polishing slurry composition in an amount of 0.001 wt% to 5 wt%, such as 0.01 wt% to 3 wt%, or 0.05 wt% to 3 wt%. Within this range, proper etching properties can be maintained with respect to the organic film.
The oxidizing agent may include a metal salt including Ce and hydrogen peroxide in a weight ratio of 1:1.5 to 1: 3.
The solvent may be used to reduce friction when the organic film is abraded with an abrasive, and may include, for example, water, deionized water, organic amines, organic alcohols, organic alcohol amines, organic ethers, organic ketones, and the like. The solvent may be present in the balance in the cmp slurry composition.
The chemical mechanical polishing slurry composition for organic film according to the present invention may further comprise an abrasive. Here, the abrasive may be a metal oxide abrasive. The abrasive may abrade the organic film at a high abrasion rate, and may include, for example, at least one selected from the group consisting of silicon oxide, aluminum oxide, cerium oxide, titanium oxide, and zirconium oxide. Specifically, the abrasive may include at least one of silicon oxide capable of providing better dispersion stability and cerium oxide capable of providing a higher grinding rate.
The abrasive can be spherical particles and have an average particle size of 10 nanometers to 150 nanometers, such as 30 nanometers to 70 nanometers. Within this range, the abrasive can provide a sufficient polishing rate with respect to an organic film as a polishing target without generating scratches, and can improve flatness.
The abrasive can be present in the chemical mechanical polishing slurry composition in an amount of 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%. In addition, the chemical mechanical polishing slurry composition can have the abrasive present in an amount greater than or equal to one of the above values and less than or equal to one of the above values. Specifically, the abrasive can be present in the chemical mechanical polishing slurry composition in an amount of 0.01 wt% to 5 wt%, such as 0.01 wt% to 3 wt%. Within this range, the abrasive can provide a sufficient polishing rate with respect to an organic film as a polishing target without generating scratches, and can exhibit good dispersion stability. Specifically, by increasing the average particle diameter of the abrasive and decreasing the amount of the abrasive in the slurry composition, it is possible to have an increased polishing rate with respect to an organic film and a low polishing rate with respect to an inorganic film.
In the chemical mechanical polishing slurry composition according to the present invention, the abrasive may be mixed with the oxidizing agent in a weight ratio of 100:1 to 1:500, specifically 10:1 to 1: 100.
In some embodiments, the chemical mechanical polishing slurry composition can be acidic. In the embodiments, the chemical mechanical polishing slurry composition can increase the polishing amount per unit time relative to the organic film, improve the flatness of the polished surface, and increase the polishing selectivity to the inorganic film. Specifically, the chemical mechanical polishing slurry composition can have a pH of 7 or less than 7, such as 6 or less than 6, more specifically 1 to 5. For example, the chemical mechanical polishing slurry composition may be adjusted to a pH within the range as described above by a pH adjusting agent. The pH adjusting agent may include, but is not limited to: inorganic acids such as at least one of nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid; and organic acids, such as organic acids having a pKa of 5 or less than 5, such as at least one of acetic acid and citric acid.
The chemical mechanical polishing slurry composition may further comprise an additive. The additive is used for supplementing the property of the chemical mechanical polishing slurry composition and can be a polishing accelerator. When the polishing accelerator is included, the polishing selectivity to the inorganic film can be improved by suppressing the polishing rate relative to the inorganic film. The milling accelerator may include an organic acid, such as at least one of malic acid, citric acid, formic acid, glutaric acid, oxalic acid, phthalic acid, succinic acid, tartaric acid, maleic acid, and malonic acid. The polishing accelerator may be present in the chemical mechanical polishing slurry composition in an amount of 0.01 wt% to 1 wt%. Within this range, the slurry accelerator does not adversely affect the polishing rate, dispersion stability of the slurry, and surface properties of the organic carbon film.
The chemical mechanical polishing slurry composition for organic film may have a chemical mechanical polishing slurry composition of 1 °, 2 °, 3 °,4 °,5 °,6 °, 7 °, 8 °, 9 °, 10 °, 11 °, 1 as calculated by equation (2)A change in cyclohexane contact angle of 2 °, 13 °, 14 °, 15 °, 16 °, 17 °, 18 °, 19 °, 20 °, 21 °, 22 °, 23 °, 24 °, 25 °, 26 °, 27 °, 28 °, 29 °, 30 °, 31 °, 32 °, 33 °, 34 °, 35 °, 36 °, 37 °, 38 °, 39 °, 40 °, 41 °, 42 °, 43 °, 44 °, 45 °, 46 °, 47 °, 48 °, 49 °, or 50 ° of Δ θnMeasured after immersing the wafer to be polished coated with the organic film in the chemical mechanical polishing slurry composition for 10 hours. Further, there can be a cyclohexane contact angle change Δ θ that is greater than or equal to one of the above values and less than or equal to one of the above valuesn. For example, there can be a cyclohexane contact angle change Δ θ of 1 ° to 50 °, specifically 1 ° to 20 °, more specifically 1 ° to 10 °n：
Equation (2):
contact angle variation (Δ θ)n)＝│θ3–θ4│，
In equation (2), θ3Represents a contact angle of an organic film measured by dropping cyclohexane (cyclohexane) onto a surface of the organic film before immersing a wafer coated with the organic film in the chemical mechanical polishing slurry composition, and θ4Represents a contact angle of the organic film measured by dropping cyclohexane (cyclohexane) onto the surface of the organic film after immersing the wafer in the chemical mechanical polishing slurry composition for 10 hours. Here, the wafer used in measuring the contact angle is the same as the wafer used in measuring the water contact angle.
The chemical mechanical polishing slurry composition may have a polishing rate of 500 to 10,000 a/min, specifically 1000 to 8000 a/min, more specifically 1500 to 5000 a/min, relative to an organic film, and thus has an excellent polishing rate.
Method for preparing chemical mechanical polishing slurry composition for organic film
A method for preparing a chemical mechanical polishing slurry composition for an organic film according to the present invention may comprise mixing an oxidizing agent with a solvent, wherein the method is performedMixing the oxidant and the solvent so that a change in water contact angle Δ θ calculated by equation (1)wIn the range of 5 DEG to 90 DEG, measured after immersing the wafer to be polished coated with the organic film in the chemical mechanical polishing slurry composition for 10 hours.
Mixing the oxidizing agent with the solvent may further comprise mixing an abrasive.
Mixing the oxidizing agent with the solvent may further include mixing an additive, such as a milling accelerator.
Since the details of the examples and amounts of the oxidizing agent, the solvent, the abrasive and the additive are the same as those described above, they will not be described again.
Organic film
Hereinafter, the organic film as the polishing target according to the present invention will be described in detail.
"substituted" in "substituted or unsubstituted" as used herein means that at least one hydrogen atom in a functional group is substituted by: a hydroxyl group, a halogen atom, a sulfinyl group, a thiol group, a cyano group, an amine group, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, a C6 to C30 aryl group, a C7 to C30 aralkyl group, a C1 to C20 heteroalkyl group, a C2 to C30 heterocycloalkyl group, a C2 to C30 heterocycloalkenyl group, a C2 to C30 heteroaryl group, a C2 to C30 heteroaralkyl group, a C1 to C20 alkylamino group, a C1 to C30 alkoxy group, a C6 to C30 aryloxy group, a C1 to C20 aldehyde group, a C1 to C40 alkyl ether group, a C7 to C20 aralkylene ether group, a C1 to C30 haloalkyl group, a P-containing functional group, a B-containing functional group, or a combination thereof.
Herein, the "P-containing functional group" may be represented by formula a, and the "B-containing functional group" may be represented by formula B.
< formula A >
*-(O)n-(CH2)m-P(＝O)(Ra)(Rb)
< formula B >
*-B(Rc)(Rd)
<Formula A>And<formula B>In which n is 0 or 1; m is an integer of 0 to 10; and R isa、Rb、RcAnd RdEach independently is hydrogen, hydroxy, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C1 to C20 haloalkyl, substituted or unsubstituted C1 to C20 alkylsulfonate, substituted or unsubstituted C1 to C20 alkylsulfonyl, substituted or unsubstituted C2 to C20 alkylamide, substituted or unsubstituted C3 to C20 alkylsulfonate, substituted or unsubstituted C2 to C20 cyanoalkyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aralkyl, or substituted or unsubstituted C6 to C30 aryloxy, or RaAnd RbOr RcAnd RdAre linked to each other to form a substituted or unsubstituted C3 to C20 cycloalkyl or a substituted or unsubstituted C3 to C20 heterocycloalkyl, being the point of attachment.
Specifically, the "functional group containing P" is a functional group containing P and O, for example, -O-P (═ O) (OH)2、 -P(＝O)(OCH2CH3)2and-P (═ O) (C)2H4C6H5)(OCH2CH3) And "functional group containing B" is a functional group containing B and O, e.g., -B (OH)2、-B(H)(CH3) and-B (CH)2CH3)2。
In some embodiments, the organic film can have a carbon content of 50 to 95 wt%, specifically 65 to 95 wt%, or 70 to 92 wt%. For example, the organic film can have a carbon content of 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, or 95 wt%. Within this range, the organic film may have a high polishing rate without being subjected to scratching when polished with an abrasive, and may exhibit high flatness on the polished surface.
In some embodiments, the organic film can have a film density of 0.5 to 2.5 grams per cubic centimeter, specifically 1.0 to 2.0 grams per cubic centimeter, or 1.2 to 1.6 grams per cubic centimeter. For example, the organic film can have a film density of 0.5, 0.6, 1.7, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.2, 2.3, 2.4, or 2.5 grams/cc. Within this range, the organic film may have a high polishing rate without being subjected to scratching when polished with an abrasive, and may exhibit high flatness on the polished surface.
In some embodiments, the organic film may have a hardness of 0.4GPa or greater than 0.4GPa, specifically 1.0GPa or greater than 1.0GPa, or 1.3GPa or greater than 1.3 GPa. For example, the organic film may have a hardness of 1.0GPa to 1.5GPa, such as 0.4GPa, 0.5GPa, 0.6GPa, 0.7GPa, 0.8GPa, 0.9GPa, 1.0GPa, 1.1GPa, 1.2GPa, 1.3GPa, 1.4GPa, or 1.5 GPa. Within this range, the organic film may have a high polishing rate without being subjected to scratching when polished with an abrasive, and may exhibit high flatness on the polished surface.
Further, the organic film according to the present invention may have an acid value of substantially 0mg KOH/g. In this context, the term "substantially" means that the acid value includes not only 0mg KOH/g, but also 0mg KOH/g within an acceptable margin of error. When the organic film has an acid value of substantially 0mg KOH/g, the polishing rate to the organic film can be further increased.
Specifically, the organic film according to the present invention may be formed of an organic film composition including a compound containing a substituted or unsubstituted aromatic group. More specifically, the organic film according to the present invention may be formed by: an organic film composition including a compound containing a substituted or unsubstituted aromatic group is coated on an inorganic film, and then baked (baking) at a high temperature, for example, at a temperature of 200 to 400 ℃.
The organic film formed from the organic film composition comprising a compound containing a substituted or unsubstituted aromatic group does not undergo decomposition of the aromatic group after baking, and therefore has a high carbon content. The aromatic group may be a carbon 6 to carbon 100 aromatic group, such as carbon 6 to carbon 50, having a single ring structure or a two or more ring fused (polycyclic) structure. For example, the aromatic group may include compounds represented by formula 1-1 to formula 1-26.
< formula 1-1>
< formulas 1 and 2>
< formulas 1 to 3>
< formulas 1 to 4>
< formulas 1 to 5>
< formulas 1 to 6>
< formulas 1 to 7>
< formulas 1 to 8>
< formulas 1 to 9>
< formulas 1 to 10>
< formulas 1 to 11>
< formulas 1 to 12>
< formulas 1 to 13>
< formulas 1 to 14>
< formulas 1 to 15>
< formulas 1 to 16>
< formulas 1 to 17>
< formulas 1 to 18>
< formulas 1 to 19>
< formulas 1 to 20>
< formulas 1 to 21>
< formulas 1 to 22>
< formulas 1 to 23>
< formulas 1 to 24>
< formulas 1 to 25>
< formulas 1 to 26>
(in formula 1-1 to formula 1-26, Z1To Z18Each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 cycloalkenylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroaryl group, - (C ═ O) -, -NRe-、-CRfRg-, oxygen (O), sulfur (S), or a combination thereof, and Re、RfAnd RgEach independently hydrogen, substituted or unsubstituted C1 to C10 alkyl groups, halogen atoms, substituted or unsubstituted C6 to C20 arylene groups, substituted or unsubstituted C2 to C20 arylene groups, or combinations thereof.
Next, an example of the organic film composition including a compound containing a substituted or unsubstituted aromatic group will be described in more detail.
In a first embodiment, the organic film composition may include one material including a unit represented by formula 2 as a compound containing a substituted or unsubstituted aromatic group.
< formula 2>
In the formula 2, a satisfies 1 ≤ a < 190;
R1is hydrogen, hydroxy, halogen atom, allyl, sulfinylA thiol group, a cyano group, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C30 to C30 heterocycloalkyl group, a substituted or unsubstituted C30 to C30 cycloalkenyl group, a substituted or unsubstituted C30 to C30 aryl group, a substituted or unsubstituted C30 to C30 aralkyl group, a substituted or unsubstituted C30 to C30 heterocycloalkyl group, a substituted or unsubstituted C30 to C30 heteroaryl group, a substituted or unsubstituted C30 to C30 heteroaralkyl group, a substituted or unsubstituted C30 to C30 alkylamine group, a substituted or unsubstituted C30 to C30 alkoxy group, A substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C40 alkyl ether group, a substituted or unsubstituted C7 to C20 aralkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a P-containing functional group, a B-containing functional group, or a combination thereof;
R2is hydrogen, substituted or unsubstituted amino, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C20 aryloxy, -NRhRi(RhAnd RiEach independently is a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C10 aryl group), a hydroxyl group, a halogen atom, an allyl group, a sulfinyl group, a thiol group, a cyano group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkenyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C3929 to C2 aryl group, or a substituted or unsubstituted C3929 to C4684 heterocycloalkenyl groupC30 heteroaralkyl, substituted or unsubstituted C1 to C20 alkylamino, substituted or unsubstituted C1 to C30 heteroalkoxy, substituted or unsubstituted C1 to C20 aldehyde groups, substituted or unsubstituted C1 to C40 alkyl ether groups, substituted or unsubstituted C7 to C20 aralkylene ether groups, substituted or unsubstituted C1 to C30 haloalkyl, P-containing functional groups, B-containing functional groups, or combinations thereof; and is
R3Is one selected from substituted or unsubstituted materials represented by the following formulae:
-CH2-
for example, R2May be a substituted or unsubstituted C1 to C10 alkoxy group.
The material including the unit represented by formula 2 may increase the carbon content, film density, and hardness of the organic film after baking the organic film composition. A more detailed process is disclosed in korean patent No. 10-0866015.
The organic film composition according to the first embodiment may further include at least one of a crosslinking component, an acid catalyst, and an organic solvent, in addition to the material including the unit represented by formula 2. Specifically, the composition according to the first embodiment may include 1 to 20% by weight of the material including the unit represented by formula 2, 0.1 to 5% by weight of the crosslinking component, 0.001 to 0.05% by weight of the acid catalyst, and 75 to 98.8% by weight of the organic solvent.
The crosslinking component may include at least one of a melamine resin (e.g., N-methoxymethyl-melamine resin or N-butoxymethyl-melamine resin), a methylated or butylated urea resin, an amine-based resin, an acetylene urea derivative represented by formula 3, a diepoxide compound represented by formula 4, and a melamine derivative represented by formula 5.
< formula 3>
< formula 4>
< formula 5>
The acidic catalyst may include at least one of p-toluenesulfonic acid monohydrate, pyridinium p-toluenesulfonate, 2,4,4, 6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids.
The organic solvent may be any organic solvent capable of sufficiently dissolving a compound containing a substituted or unsubstituted aromatic group, without limitation. For example, the organic solvent may include propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, and the like.
The organic film may be produced by coating the organic film composition according to the first embodiment to a thickness of 500 to 4,000 angstroms, specifically 2,000 to 3,000 angstroms, followed by baking at a temperature of 200 to 400 ℃ for 10 seconds to 10 minutes, but is not limited thereto.
In a second embodiment, the organic film composition may include a material represented by formula 6 as a compound containing a substituted or unsubstituted aromatic group.
< formula 6>
<Formula 6>In, R4To R9And X1To X6Each independently of the others hydrogen, hydroxy, halogen, allyl, sulfinyl, thiol, cyano, or a salt thereof,Substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C30 to C30 alkenyl, substituted or unsubstituted C30 to C30 alkynyl, substituted or unsubstituted C30 to C30 cycloalkyl, substituted or unsubstituted C30 to C30 heterocycloalkyl, substituted or unsubstituted C30 to C30 cycloalkenyl, substituted or unsubstituted C30 to C30 aryl, substituted or unsubstituted C30 to C30 aralkyl, substituted or unsubstituted C30 to C30 heterocycloalkenyl, substituted or unsubstituted C30 to C30 heteroaryl, substituted or unsubstituted C30 to C30 heteroaralkyl, substituted or unsubstituted C30 to C30 alkylamino, substituted or unsubstituted C30 to C30 alkoxy, or substituted or unsubstituted C30 to C30 alkoxy, substituted or unsubstituted C30 to C30 alkoxy, A substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C40 alkyl ether group, a substituted or unsubstituted C7 to C20 aralkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a P-containing functional group, a B-containing functional group, or a combination thereof; and n is1To n6Each independently ranging from 0 to 2 and satisfying 2 ≦ n1+n2+n3+n4+n5+n6≤6。
For example, R4To R9Each may independently be a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a P-containing functional group, or a B-containing functional group.
For example, X1To X6Each independently can be hydrogen, hydroxyl, substituted or unsubstituted C1 to C20 alkylamino, amino, a P-containing functional group, or a B-containing functional group.
The organic film composition according to the second embodiment is substantially the same as the organic film composition according to the first embodiment except that the organic film composition according to the second embodiment includes a material represented by formula 6 instead of the material including the unit represented by formula 2 as the compound containing a substituted or unsubstituted aromatic group. Therefore, only the material represented by formula 6 will be described in detail below.
The aromatic compound represented by formula 6 may have a weight average molecular weight of 500 g/mol to 4000 g/mol. Within this range, the organic film composition can form an excellent thin film or organic film having an appropriate thickness.
The material represented by formula 6 may be prepared by a typical method known in the art. For example, it can be prepared by reacting acetyl chloride, benzoyl chloride, naphthaloyl chloride or cyclohexanecarbonyl chloride with coronene, followed by reduction of the resulting material, but is not limited thereto. A more detailed process is disclosed in korean patent No. 10-1311942.
The material represented by formula 6 may increase the carbon content, film density, and hardness of the organic film after baking the organic film composition. The organic film composition including the material represented by < formula 6> includes an aromatic ring exhibiting strong absorption at a short wavelength (e.g., 193 nm or 248 nm), and thus cross-linking occurs at a high temperature even without using a specific catalyst, thereby preventing contamination due to the catalyst. The material represented by formula 6 may be a mixture of two or more compounds including substituents at different positions.
In the third embodiment, the organic film composition may include, as the compound containing a substituted or unsubstituted aromatic group, an aromatic group-containing polymer selected from the following compounds (i), (ii), and (iii).
(i) A compound comprising a unit represented by formula 7.
(ii) A mixture of a compound comprising a unit represented by formula 7 and a compound comprising a unit represented by formula 8.
(iii) A compound comprising a unit represented by formula 9.
< formula 7>
< formula 8>
< formula 9>
(in the formulae 7 to 9, b, c, d and e are each independently 1 to 750;
2≤c+d<1500；
R10is one selected from substituted or unsubstituted materials represented by the following formulae:
(R is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C3 to C20 cycloalkenyl group);
R11is hydrogen, hydroxyl, a halogen atom, sulfinyl, thiol, cyano, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C30 to C30 aralkyl group, a substituted or unsubstituted C30 to C30 heterocycloalkenyl group, a substituted or unsubstituted C30 to C30 heteroaryl group, a substituted or unsubstituted C30 to C30 heteroaralkyl group, a substituted or unsubstituted C30 to C30 alkyl group, a substituted or unsubstituted C30 alkoxy group or a substituted or unsubstituted C30 to C30 alkoxy group, Substituted or unsubstituted C6 to C30 aryloxy groups, substituted or unsubstituted C1 to C20 aldehyde groups, substituted or unsubstituted C1 to C40 alkyl ether groups, substituted or unsubstituted C7 to C20 aralkylene groupsAn ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a P-containing functional group, a B-containing functional group, or a combination thereof;
R12and R14Each independently is one selected from substituted or unsubstituted materials represented by the following formulae:
-H2C-
R13is one selected from substituted or unsubstituted materials represented by the following formulae:
(R is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C3 to C20 cycloalkenyl group); and is
R15Is one selected from substituted or unsubstituted materials represented by the following formulae:
(R is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C3 to C20 cycloalkenyl group),
wherein R is10、R13And R15Wherein each R is independently hydrogen, hydroxyl, halogen atom, sulfinyl, thiol, cyano, substituted or unsubstituted amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstitutedSubstituted C2 to C30 alkynyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C30 to C30 cycloalkenyl, substituted or unsubstituted C30 to C30 aryl, substituted or unsubstituted C30 to C30 cycloaryl, substituted or unsubstituted C30 to C30 heterocycloalkyl, substituted or unsubstituted C30 to C30 heterocycloalkenyl, substituted or unsubstituted C30 to C30 heteroaryl, substituted or unsubstituted C30 to C30 heteroarylalkyl, substituted or unsubstituted C30 to C30 alkylamino, substituted or unsubstituted C30 to C30 alkoxy, substituted or unsubstituted C30 to C30 aryloxy, substituted or unsubstituted C30 to C30 aldehyde group, substituted or unsubstituted C30 to C30 alkyl, substituted or unsubstituted C30 to C30 aralkyl, substituted or unsubstituted C30 to C30 alkyl, substituted or unsubstituted C30 to C30 haloalkyl 30 to C30 alkyl, substituted or unsubstituted C30 to C30 haloalkyl, A functional group containing P, a functional group containing B, or a combination thereof.
The organic film composition according to the third embodiment is substantially the same as the organic film composition according to the first embodiment except that the organic film composition according to the third embodiment includes a polymer containing an aromatic group instead of the material including the unit represented by formula 2 as the compound containing a substituted or unsubstituted aromatic group.
After baking the organic film composition, the aromatic group-containing polymer may increase the carbon content, film density, and hardness of the organic film, and may be prepared by any typical method known in the art. More details are disclosed in korean patent No. 10-0908601.
In a fourth embodiment, the organic film composition may include, as the compound containing a substituted or unsubstituted aromatic group, at least two selected from the group consisting of: a material comprising a unit represented by formula 2; a material represented by formula 6; and an aromatic group-containing polymer selected from the group consisting of the compounds (i), (ii) and (iii). Substantially the same as the organic film composition according to the first embodiment except that the organic film composition according to the fourth embodiment includes at least two compounds containing substituted or unsubstituted aromatic groups.
Method for grinding organic film
Next, a method of polishing an organic film according to the present invention will be explained.
A method for polishing an organic film according to the present invention includes polishing the organic film using a chemical mechanical polishing slurry composition for organic film, wherein the chemical mechanical polishing slurry composition for organic film may include a chemical mechanical polishing slurry composition for organic film according to an embodiment of the present invention.
Fig. 1(a) shows a state in which a silicon wafer, an inorganic film, and an organic carbon film are stacked together before the organic film is polished. Referring to fig. 1(a), a silicon wafer 100 is subjected to patterning to have an intaglio portion. An inorganic film 110 is deposited on a silicon wafer 100, and an organic carbon film 120 is formed on the inorganic film, followed by baking at a temperature of 200 to 400 ℃. The broken line in fig. 1(a) indicates an imaginary grinding stop line T. The chemical mechanical polishing slurry composition for organic film was coated on the organic film shown in fig. 1(a), and then a polishing pad was mounted thereon. Next, the organic film is polished up to the polishing stop line T by rotating the silicon wafer 100, thereby obtaining a silicon wafer in which the organic film is polished, as shown in fig. 1 (b).
Detailed description of the preferred embodiments
The invention will be explained in more detail below with reference to some examples. It should be understood that these examples are provided for illustration only, and should not be construed as limiting the invention in any way.
For the sake of brevity, details which are obvious to those skilled in the art will not be described again.
Examples of the invention
Preparation example 1 organic film composition
A2000 ml three-necked flask comprising a thermometer, a condenser, a mechanical stirrer and a dropping funnel was immersed in an oil bath at 140 ℃. Heating and stirring were performed on a hot plate by a magnet, and cooling water in a condenser was set to 40 ℃. 220 g, 1.0 mol of 1-methoxypyrene and 138 g, 1.0 mol of 1, 4-bismethoxymethyl benzene were added to a reactor, followed by dissolving in 656 g of propylene glycol monomethyl ether acetate. Subsequently, 4.6 grams, 0.03 moles of diethyl sulfate were added to the reactor. The reactor was maintained at 130 ℃. The point of completion of the reaction was determined by measuring the molecular weight of the reaction product at fixed time intervals during the polymerization. Here, a sample for measuring molecular weight was prepared by quenching 1g of the reaction product to room temperature, and then diluting 0.02 g of the reaction product with tetrahydrofuran as a solvent so that the solid content in the solution became 4 wt%. To complete the reaction at the determined reaction completion point, 4.48 grams of 0.03 moles of triethanolamine was added to the reactor as a neutralizer, and the components were then stirred. Next, the reaction product was slowly cooled to room temperature. The reaction product was diluted with 500 g of propylene glycol monomethyl ether acetate. Next, the solvent was added to a 2000 ml separatory funnel. A4 kg mixture of methanol and ethylene glycol was prepared at a ratio of 90:10 g/g. The synthesized polymer solution was added dropwise to the alcohol mixture under rapid stirring. The resulting polymer was obtained from the bottom of the flask and the supernatant was separately stored. After removal of the supernatant, methanol was removed from the final reaction product by rotary evaporation at a temperature of 60 ℃ for 10 minutes under reduced pressure.
The molecular weight and the degree of dispersion of the obtained copolymer were measured by gel permeation chromatography GPC using tetrahydrofuran. The result was a polymer comprising the unit represented by formula 11 and having a weight average molecular weight of 4000 g/mol and a dispersity of 2.3.
< formula 11>
(wherein a averages 11 and Me is methyl).
0.8g of the prepared polymer, 0.2 g of a crosslinking agent represented by formula 4 (Powderlink 1174, Cyanotex industries, Ltd.), and 2 mg of pyridinium p-toluenesulfonate were dissolved in 9g of propylene glycol monomethyl ether acetate, and then the solution was filtered, thereby preparing an organic film composition.
Preparation example 2-wafer coated with organic film
The organic film composition prepared in preparation example 1 was spin-coated on the surface of a silicon oxide wafer made by forming a silicon oxide film on a silicon wafer having a diameter of 200 mm using a spin coater MS-a200 of sangai corporation at the following rotation speeds and times, respectively: the spin coating was performed at 1000rpm for 2 seconds (step 1), at 1500rpm for 20 seconds (step 2), and at 1000rpm for 2 seconds (step 3).
Then, the organic film composition was baked in air for 2 minutes using a hot plate at 400 ℃ and cooled at room temperature for 10 minutes. The result is that an organic film having an average thickness of 2300 angstroms is uniformly formed on the wafer so that the relative standard deviation of the thickness is within 5%. Subsequently, the wafer was cut into a size of 2 cm in width and 10 cm in length, thereby preparing a sample.
A chemical mechanical polishing slurry composition comprising the components listed in Table 1 and deionized water was prepared.
Detailed description of the components of CMP slurry composition
(A) Oxidizing agent
(a1) Cerium ammonium nitrate (Sanquan Chemicals, Inc.) was used.
(a2) Cerium sulfate (Ankles organic chemical Co.) was used.
(a3) Cerium nitrate (sigma-aldrich, ltd.) was used.
(a4) Copper nitrate (Dajinghua, Inc.) was used.
(a5) Copper chloride (Sanquan Chemicals, Inc.) was used.
(a6) Iron nitrate (Sanquan Chemicals, Inc.) was used.
(a7) Hydrogen peroxide (donmitomo precision chemical co., ltd.) was used.
(B) Grinding materials: colloidal cerium oxide (Jenous GmbH) was used.
Evaluation of Properties
Distilled water and a nonpolar solvent were dropped onto the surface of the organic film of the sample prepared in preparation example 2 to measure a water contact angle θ before immersion1And a nonpolar solventContact angle theta3. Then, the sample was immersed in each of the chemical mechanical polishing slurry compositions of examples and preparation examples for 10 hours, followed by removing and drying the sample, and then measuring the water contact angle θ after immersion2And contact angle θ of nonpolar solvent4. Based on the measured values, changes in water contact angle and non-polar solvent contact angle before and after immersion were calculated.
Herein, the contact angle refers to an angle defined by the organic film surface and a tangent line at a contact point between the solvent droplet and the organic film surface. The measurement results are shown in [ Table 1 ].
Further, in order to evaluate the polishing properties of the chemical mechanical polishing slurry compositions of examples and comparative examples, the organic film-coated wafers prepared in preparation example 2 were polished using each of the chemical mechanical polishing slurry compositions of examples and comparative examples.
As the polishing pad, a chemical mechanical polishing pad of fuji textile co. Grinding was performed for 30 seconds using a MIRRA grinder (AMTA, applied materials ltd.) of 200 mm under the conditions of a down force of 1.0psi, a slurry flow rate of 200 ml/min, a platen (place) speed of 60rpm, and a Head (Head) speed of 55rpm, and then the grinding rate was measured using a thickness measuring system. The results are shown in table 1.
TABLE 1
Unit: by weight%
As can be seen from the results shown in [ table 1], the chemical mechanical polishing slurry compositions of examples 1 to 7 have a water contact angle variation of 5 ° or more than 5 ° and thus have considerably high polishing rates compared to the chemical mechanical polishing slurry compositions in comparative example 1 and comparative example 2, as found by measuring the water contact angle of the organic film before and after immersing the wafer sample in the chemical mechanical polishing slurry.
Although some embodiments have been described herein, it is to be understood that they have been provided by way of illustration only, and not by way of limitation, and that various modifications, changes, alterations, and equivalents may be made by those skilled in the art without departing from the spirit and scope of the invention.
Accordingly, the scope of the invention should be determined by the appended claims and their equivalents.
Claims (14)
1. A chemical mechanical polishing slurry composition, comprising an oxidizing agent and a solvent,
wherein the oxidizing agent comprises at least one of copper chloride and copper nitrate, the chemical mechanical polishing slurry composition having a water contact angle variation Δ θ calculated by equation (1) of 5 ° to 90 °wMeasured after immersing a wafer to be polished coated with an organic film in the chemical mechanical polishing slurry composition for 10 hours:
equation (1):
water contact angle change delta thetaw＝│θ1-θ2│，
In equation (1), θ1Represents a water contact angle of the organic film measured by dropping deionized water onto a surface of the organic film before dipping the wafer coated with the organic film in the chemical mechanical polishing slurry composition, and θ2Represents a water contact angle of the organic film measured by dropping deionized water onto the surface of the organic film after immersing the wafer in the chemical mechanical polishing slurry composition for 10 hours.
2. The chemical mechanical polishing slurry composition of claim 1, wherein the oxidizing agent further comprises Fe3+、Ce4+、Ce3+And Ag+At least one of (a).
3. The chemical mechanical polishing slurry composition of claim 2, wherein the oxidizing agent further comprises hydrogen peroxide.
4. The chemical mechanical polishing slurry composition of claim 1, wherein the oxidizing agent further comprises Fe3+、Ce3+Or Ce4+。
5. The chemical mechanical polishing slurry composition of claim 1, wherein the oxidizing agent further comprises Ce4+、Ce3+And Ag+A mixture of at least one metal ion of (a) with hydrogen peroxide.
6. The chemical mechanical polishing slurry composition of claim 1, wherein the oxidizing agent is present in the chemical mechanical polishing slurry composition in an amount of 0.001 wt% to 5 wt%.
7. The chemical mechanical polishing slurry composition of claim 1, wherein the chemical mechanical polishing slurry composition further comprises an abrasive.
8. The chemical mechanical polishing slurry composition of claim 7, wherein the abrasive comprises at least one selected from the group consisting of silicon oxide, aluminum oxide, cerium oxide, titanium oxide, and zirconium oxide.
9. The chemical mechanical polishing slurry composition of claim 7, wherein the abrasive is present in the chemical mechanical polishing slurry composition in an amount of 0.01 to 5 wt%.
10. The chemical mechanical polishing slurry composition according to claim 1, wherein the chemical mechanical polishing slurry composition has a cyclohexane contact angle variation Δ θ calculated by equation (2) of 1 ° to 50 °nMeasured after immersing the wafer to be polished coated with the organic film in the chemical mechanical polishing slurry composition for 10 hours:
equation (2):
change in contact angle Δ θn＝│θ3–θ4│，
In equation (2), θ3Represents a contact angle of the organic film measured by dropping cyclohexane onto a surface of the organic film before dipping the wafer coated with the organic film in the chemical mechanical polishing slurry composition, and θ4Represents a contact angle of the organic film measured by dropping cyclohexane onto the surface of the organic film after immersing the wafer in the chemical mechanical polishing slurry composition for 10 hours.
11. The chemical mechanical polishing slurry composition of claim 1, wherein the organic film has a carbon content of 50 wt% to 95 wt%.
12. The chemical mechanical polishing slurry composition of claim 11, wherein the chemical mechanical polishing slurry composition has a polishing rate of 500 a/min to 10000 a/min relative to the organic film.
13. A method for preparing a chemical mechanical polishing slurry composition for organic films, comprising:
mixing an oxidant with a solvent, wherein the oxidant comprises at least one of copper chloride and copper nitrate,
wherein the mixing of the oxidizing agent and the solvent is performed so that the chemical mechanical polishing slurry composition has a water contact angle change Δ θ of 5 ° to 90 ° calculated by equation (1)wMeasured after immersing a wafer to be polished coated with an organic film in the chemical mechanical polishing slurry composition for 10 hours:
equation (1):
water contact angle change delta thetaw＝│θ1-θ2│，
In equation (1), θ1By dropping deionized water to the organic film before immersing the wafer coated with the organic film in the chemical mechanical polishing slurry compositionOf the organic film measured on the surface of (a), and theta2Represents a water contact angle of the organic film measured by dropping deionized water onto the surface of the organic film after immersing the wafer in the chemical mechanical polishing slurry composition for 10 hours.
14. A method of polishing an organic film, comprising:
the chemical mechanical polishing slurry composition according to any one of claims 1 to 12 is used for polishing an organic film.
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| PCT/KR2016/007937 WO2017034157A1 (en) | 2015-08-21 | 2016-07-21 | Cmp slurry composition for organic film, preparation method therefor, and method for polishing organic film by using same |
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| JP2004128211A (en) * | 2002-10-02 | 2004-04-22 | Toshiba Corp | Method for polishing organic film on semiconductor substrate using resin particle and slurry |
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|---|---|---|---|---|
| CN1556840A (en) * | 2001-09-24 | 2004-12-22 | Rare earth salt oxidizer based CMP method | |
| WO2014171766A1 (en) * | 2013-04-17 | 2014-10-23 | 제일모직 주식회사 | Organic film cmp slurry composition and polishing method using same |
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| KR101900540B1 (en) | 2018-09-20 |
| WO2017034157A1 (en) | 2017-03-02 |
| KR20170023362A (en) | 2017-03-03 |
| CN107922819A (en) | 2018-04-17 |
| TW201715015A (en) | 2017-05-01 |
| TWI618791B (en) | 2018-03-21 |
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