CN112399999B - Chemical mechanical polishing composition, chemical mechanical polishing slurry and substrate polishing method - Google Patents
Chemical mechanical polishing composition, chemical mechanical polishing slurry and substrate polishing method Download PDFInfo
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- CN112399999B CN112399999B CN201980044957.7A CN201980044957A CN112399999B CN 112399999 B CN112399999 B CN 112399999B CN 201980044957 A CN201980044957 A CN 201980044957A CN 112399999 B CN112399999 B CN 112399999B
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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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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
- B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
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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
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
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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
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
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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
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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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
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
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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
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/06—Other polishing compositions
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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
- C09K13/00—Etching, surface-brightening or pickling compositions
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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
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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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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- 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
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
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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
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
Abstract
The present invention provides a chemical mechanical polishing composition, a chemical mechanical polishing slurry and a substrate polishing method, which can achieve a polishing rate equal to or higher than that of a conventional abrasive even if the total metal content is reduced, or can achieve a polishing rate significantly higher than that of a conventional abrasive when the same total metal content as that of the conventional abrasive is used. The chemical mechanical polishing composition comprises an iron-based metal catalyst and a magnesium-based metal catalyst, the metal content of the iron-based metal catalyst in the total content of the metal catalysts being equal to or greater than the metal content of the magnesium-based metal catalyst.
Description
Technical Field
The invention relates to a chemical mechanical polishing composition, a chemical mechanical polishing slurry and a substrate polishing method. More particularly, the present invention relates to a chemical mechanical polishing composition, a chemical mechanical polishing slurry and a substrate polishing method for forming an electrical conductor composed of tungsten when manufacturing a semiconductor.
Background
In a semiconductor manufacturing process, a polishing slurry for a conductor is applied to a process of filling a hole formed in an interlayer insulating film (ILD) and removing a metal film such as a tungsten film formed on the ILD to leave the tungsten film only in the hole.
Therefore, the most important factors required for the polishing slurry for a conductor are that contamination by residual metal impurities is minimized and the polishing rate of a metal film is maximized with a small amount of catalyst metal, and that a pattern defect such as dishing should not be generated due to a high selectivity ratio of an underlying interlayer insulating film.
However, the slurries sold or developed up to now are not sufficient to meet these requirements.
Disclosure of Invention
Problems to be solved
Embodiments of the present invention are directed to a chemical mechanical polishing composition, a chemical mechanical polishing slurry and a polishing method, which can reduce the total metal content and achieve a polishing rate equal to or higher than that of conventional polishing agents.
Embodiments of the present invention are directed to a chemical mechanical polishing composition, a chemical mechanical polishing slurry and a polishing method, which can achieve a significantly higher polishing rate than conventional polishing rates when using the same total metal content as conventional polishing rates.
Embodiments of the present invention are directed to a chemical mechanical polishing composition, a chemical mechanical polishing slurry and a polishing method, which have a high polishing selectivity.
Embodiments of the present invention are directed to a chemical mechanical polishing composition, a chemical mechanical polishing slurry and a polishing method, which do not generate pattern defects such as dishing.
Means for solving the problems
The chemical mechanical polishing composition according to an embodiment of the present invention may include an iron-based metal catalyst and a magnesium-based metal catalyst, and the metal content of the iron-based metal catalyst in the total metal content of the metal catalyst mixture is equal to or more than the metal content of the magnesium-based metal catalyst.
The chemical mechanical polishing slurry according to an embodiment of the present invention may include: a first liquor comprising a multi-metal catalyst comprising an iron-based metal catalyst and a magnesium-based metal catalyst, an abrasive, and a balance of water; and a second liquor comprising an oxidant, the metal content of the iron-based metal catalyst of the total metal content of the multi-metal catalyst mixture being equal to or greater than the metal content of the magnesium-based metal catalyst.
The substrate polishing method according to an embodiment of the present invention includes: a step of providing the first liquid agent and the second liquid agent separately; mixing the first liquid agent and the second liquid agent before coating the first liquid agent and the second liquid agent on a substrate; applying the chemical mechanical polishing slurry mixed with the first liquid agent and the second liquid agent to a substrate; and a step of removing at least a part of the tungsten layer formed on the substrate by contacting the pad to the substrate and moving the pad relative to the substrate.
Effects of the invention
With the chemical mechanical polishing composition and the chemical mechanical polishing slurry according to the embodiments of the present invention, even if the total content of metals is reduced, a polishing rate equivalent to or higher than that of a conventional polishing agent can be achieved.
With the chemical mechanical polishing composition and the chemical mechanical polishing slurry according to the embodiments of the present invention, when the same total metal content as the conventional metal content is used, a significantly higher polishing rate can be achieved than the conventional chemical mechanical polishing composition and the chemical mechanical polishing slurry.
The polishing selectivity can be improved for the chemical mechanical polishing composition and the chemical mechanical polishing slurry according to the embodiment of the invention.
With the chemical mechanical polishing composition and the chemical mechanical polishing slurry according to the embodiments of the present invention, a semiconductor manufacturing process can be performed without generating pattern defects.
Detailed Description
The following detailed description is provided to enable one of ordinary skill in the art to readily practice the invention. However, the present invention can be embodied in various different forms and is not limited to the specific embodiments described below.
The "chemical mechanical polishing composition" and "chemical mechanical polishing slurry" of the present invention facilitate polishing of, without limitation, integrated circuit films, multiple metal layers of semiconductor films, and any other films, surfaces, and substrates that facilitate a CMP process. In particular, for polishing at least one metal layer, such as a tungsten layer, associated with a substrate selected from the group consisting of silicon substrates, TFT-LCD glass substrates, GaAs substrates and other substrates including related integrated circuits, thin films, multi-layer semiconductors and wafers. In particular, the chemical mechanical polishing composition of the present invention can be used for forming a hole in an insulating film of a conductive body by filling the hole in the insulating film and polishing at least one of a tungsten layer, a titanium layer, and a titanium nitride layer formed on the insulating film in one step.
In this case, in the present specification, the chemical mechanical polishing composition may refer to a first liquid agent contained in a chemical mechanical polishing slurry used for polishing a semiconductor substrate. In addition, in the present invention, the chemical mechanical polishing slurry may refer to a composition including the first liquid agent and the second liquid agent including an oxidizing agent. The first liquid agent and the second liquid agent are as follows.
The present invention is specifically described below.
According to an embodiment of the present invention, there may be provided a chemical mechanical polishing composition including an iron-based metal catalyst and a magnesium-based metal catalyst, the metal content of the iron-based metal catalyst in the total metal content of the metal catalyst mixture being equal to or more than the metal content of the magnesium-based metal catalyst.
The chemical mechanical polishing composition of the present invention is not a single catalyst component, but includes a multi-catalyst comprising an iron-based metal catalyst and a magnesium-based metal catalyst. The inventors of the present invention made creative efforts to find out various catalysts showing a synergistic effect of catalysts from among the existing catalysts, and as a result, confirmed that when an iron-based metal catalyst and a magnesium-based metal catalyst are used together, the amount of the catalyst used can be reduced and the same or significant grinding performance as the conventional one can be exhibited, and when the same amount as the conventional one is used, the very significant grinding performance as compared to the conventional one can be exhibited.
As the iron-based metal catalyst, there can be selected from the group consisting of iron (II) nitrate, iron (III) nitrate, iron (II) chloride, iron (II) sulfate, iron (III) sulfate, iron (II) halide, iron (III) halide (e.g., fluoride, chloride, bromide and iodide), iron inorganic salts including perchlorate, perbromate and periodate, ferrosilicon, and organic iron (II) or organic iron (III) selected from the group consisting of acetate, acetylacetone, citrate, gluconate, malonate, oxalate, phthalate, succinate, and a mixture thereof. In this case, the iron (ii) nitrate and the iron (iii) nitrate may be in the form of known hydrates. For example, iron (iii) nitrate nonahydrate (iron (iii) nitrate nonahydrate) may be used as the iron nitrate.
In one embodiment of the present invention, the iron-based metal catalyst may be iron (ii) nitrate, iron (iii) nitrate, iron chloride, iron (ii) sulfate, iron (iii) sulfate, or ferrosilicon.
The magnesium-based metal catalyst may be selected from the group consisting of magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium citrate, magnesium diglutamate, magnesium formate, magnesium gluconate, magnesium glycinate, magnesium lactate and magnesium oxalate. In this case, the magnesium nitrate and the magnesium sulfate may be in known hydrate forms. For example, the magnesium nitrate may be magnesium nitrate hexahydrate, and the magnesium sulfate may be magnesium sulfate hexahydrate.
In one embodiment of the present invention, the magnesium-based metal catalyst may be magnesium nitrate, magnesium chloride or magnesium citrate.
On the other hand, the total metal content of the iron-based metal catalyst included in the chemical mechanical polishing composition may be equal to or more than the metal content of the magnesium-based metal catalyst in the total metal content of the metal catalyst mixture.
For example, in one embodiment, more of the iron-based metal catalyst may be included, the metal content of the iron-based metal catalyst being 1 to 20 times the metal content of the magnesium-based metal catalyst, based on the total metal content of the metal catalyst mixture.
In addition, in the metal catalyst mixture in which the two metal catalysts are used in combination, the minimum value of the metal content of the magnesium-based metal catalyst may be 0.0001 wt% (1ppm) with respect to the chemical mechanical polishing composition, based on the total metal content. Also, the maximum value of the metal content of the iron-based metal catalyst may be 0.0295 wt% (295ppm), based on the total metal content of the metal catalyst mixture. At this time, if the minimum value of the metal content of the magnesium-based metal catalyst is less than 0.0001 wt% with respect to the chemical mechanical polishing composition, the polishing rate is significantly reduced. Further, if the maximum value of the metal content of the iron-based metal catalyst is more than 0.0295 wt%, the increase in the grinding speed is not slowed down economically.
In one embodiment of the present invention, the total metal content of the iron-based metal catalyst and the magnesium-based metal catalyst may be 0.002 wt% to 0.03 wt% with respect to the chemical mechanical abrasive composition. For example, the total metal content of the iron-based metal catalyst and the magnesium-based metal catalyst may be 0.003 wt% to 0.03 wt% relative to the chemical mechanical abrasive composition.
In one embodiment of the present invention, the maximum value of the metal content of the iron-based metal catalyst may be 0.0295 wt% with respect to the chemical mechanical abrasive composition, the minimum value of the metal content of the magnesium-based metal catalyst may be 0.0001 wt% with respect to the chemical mechanical abrasive composition, and the total metal content of the iron-based metal catalyst and the magnesium-based metal catalyst may be 0.002 wt% to 0.03 wt% with respect to the chemical mechanical abrasive composition.
In this case, the chemical mechanical polishing composition may further include a dispersion stabilizer, i.e., tributylamine, methanesulfonic acid, or a mixture thereof.
The dispersion stabilizer may be included at 0.0001 to 0.04 wt% or 0.003 to 0.01 wt% with respect to the chemical mechanical polishing composition.
Furthermore, the chemical mechanical polishing composition can further comprise an abrasive. The content of the abrasive is not particularly limited, and the abrasive may comprise 0.01 to 8 wt% with respect to the chemical mechanical polishing composition.
In addition, the chemical mechanical polishing composition may further include a balance of water.
The chemical mechanical polishing composition may further comprise known additives such as a pH adjuster, a bactericide, and the like.
The description of the metal catalyst also applies to the multimetallic catalyst contained in the first liquor of the chemical mechanical polishing slurry described below.
Therefore, according to another embodiment of the present invention, there is provided a chemical mechanical polishing slurry comprising: a first liquor as a chemical mechanical polishing composition comprising a multi-metal catalyst comprising an iron-based metal catalyst and a magnesium-based metal catalyst, an abrasive, and a balance of water; and a second liquor comprising an oxidant, the metal content of the iron-based metal catalyst of the total metal content of the multi-metal catalyst mixture being equal to or greater than the metal content of the magnesium-based metal catalyst.
In addition, according to still another embodiment of the present invention, there is provided a method of polishing a substrate having at least one tungsten layer, including: a step of providing the first liquid agent and the second liquid agent separately; mixing the first liquid agent and the second liquid agent before coating the first liquid agent and the second liquid agent on a substrate; applying the chemical mechanical polishing slurry mixed with the first liquid agent and the second liquid agent to a substrate; and a step of removing at least a part of the tungsten layer formed on the substrate by contacting the pad to the substrate and moving the pad relative to the substrate.
That is, the chemical mechanical polishing composition may include a first liquor including a multi-metal catalyst including an iron-based metal catalyst and a magnesium-based metal catalyst, an abrasive, and a remaining amount of water, and the metal content of the iron-based metal catalyst may be equal to or more than the metal content of the magnesium-based metal catalyst. The first liquid agent and the second liquid agent containing the oxidizing agent are stored separately, and may be mixed before being applied to the substrate and then applied to the substrate. At least a portion of the metal layer (e.g., tungsten layer) on the substrate may then be removed by contacting the polishing pad to the substrate and moving the pad relative to the substrate. In another aspect, the first liquid formulation may comprise an abrasive. The grinding agent may be contained in an amount of 0.01 to 8 wt%, such as 0.02 to 5 wt%, and specifically 0.1 to 3 wt%, relative to the first liquid agent. The abrasive is typically a metal oxide abrasive. The metal oxide abrasive can be selected from the group consisting of alumina, titania, zirconia, germania, silica, ceria, and mixtures thereof. The abrasive can have an average agglomerate size of 10 to 150 nm. The metal oxide abrasive is an aqueous dispersion of metal oxide mixed as an aqueous medium of a first liquid formulation.
The first liquor may further comprise a pH adjuster to maximize colloidal stability in the slurry. As the pH adjuster, nitric acid, hydrochloric acid, phosphoric acid, acetic acid, malonic acid, quaternary ammonium compounds, potassium hydroxide, or the like can be used. A pH adjusting agent may be added such that the pH of the first liquor becomes 1 to 6, for example 2 to 4.
The first liquid formulation may also include a bactericide. The bactericide may inhibit the growth of microorganisms or eliminate microorganisms. As the bactericide, CMIT (methylchloroisothiazolinone), BIT (benzisothiazolinone), or the like can be used. The bactericide may be contained in 0.0001 to 0.1 wt%, for example, 0.001 to 0.08 wt%, and specifically may be contained in 0.01 to 0.05 wt%, relative to the first liquid agent.
The first liquid formulation may also comprise a dispersion stabilizer. As the dispersion stabilizer, tributylamine, methanesulfonic acid, or a mixture thereof can be used. The dispersion stabilizer may comprise 0.0001 to 0.04 wt%, for example 0.003 to 0.01 wt%, relative to the first liquid formulation.
The second liquid agent may comprise an oxidizing agent. As oxidizing agents, inorganic or organic per-compounds can be used. A per-compound is a compound containing one or more peroxy groups (-O-) or a compound containing the element in the highest oxidation state. Examples of such compounds comprising one or more peroxy groups are hydrogen peroxide and its adducts, e.g. urea hydrogen peroxide, percarbonates, organic peroxides, benzyl peroxide, peracetic acid, di-tert-butyl peroxide, monopersulfates (SO) 5 2- ) Base compound, bis-persulfate (S) 2 O 8 2- ) A base compound and sodium peroxide, but not limited thereto. Specifically, the oxidizing agent may be hydrogen peroxide. When the first liquid agent and the second liquid agent are mixed, the second liquid agent may be mixed to 0.1 to 5 wt%, for example, 0.5 to 3.5 wt%, specifically 1 to 2.5 wt%, with respect to the total content of the slurry after mixing.
Hereinafter, preferred embodiments of the present invention will be described in more detail by way of examples. However, the following examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention.
Comparative examples 1 to 13 and examples 1 to 18
Preparation of polishing slurry and evaluation of polishing
An 8-inch tungsten dummy wafer, an 8-inch dummy wafer having a PE-TEOS insulating film formed thereon, and an 8-inch SKW5-3 damascene pattern wafer (hereinafter referred to as a semiconductor substrate) were used for the test.
The polishing apparatus used a Mirra 3400 available from applied materials, IC-1010(Rohm & Haas) was used as a polishing pad, and the polishing conditions were set to the conditions shown in Table 1 below.
[ Table 1]
After polishing, the thickness of the tungsten film was measured using CMT-2000 (four-point probe, Changmitech), the thickness of the insulating film was measured using Thermowave OP-2600(KLATENCOR), and the polishing rate was calculated by subtracting the thickness after CMP from the thickness before CMP, and the results are shown in tables 2 to 4.
Particle size analysis ELS-Z (Otsuka electronics) was used.
1) Preparation of chemical mechanical polishing slurry (preparation of first liquid formulation and second liquid formulation)
Colloidal silica was used as the abrasive, and after stirring with a catalyst having a content shown in tables 2 to 6 below using a stirrer, a pH was adjusted to a target pH value using a pH adjuster, thereby preparing a first liquid agent. Then, before polishing the semiconductor substrate, a second liquid agent containing hydrogen peroxide and a first liquid agent, which are separately prepared, are mixed to prepare a chemical mechanical polishing slurry, and then CMP (chemical mechanical polishing) is evaluated.
Specifically, in the case of comparative examples 1 to 6, 8 and examples 1 to 9 of tables 2 and 5, 1.3 wt% of colloidal silica having a particle size of 90nm was used together with a metal catalyst, and after adding cmit0.03wt%, pH was adjusted to 3 using nitric acid and tetramethylammonium hydroxide. A31 wt% hydrogen peroxide solution was used as the second liquid agent, and mixed with the first liquid agent to a final content of 1.5 wt%. In the preparation of the first liquid agent, water is used as the balance. At this time, for comparative example 7, a slurry of only hydrogen peroxide was prepared in the same manner as described above, except that no metal catalyst was used.
In the case of comparative examples 9 to 12 and examples 10 to 12 of Table 3, colloidal silica having a particle size of 90nm was used together with a metal catalyst in an amount of 0.85 wt%, and after adding BIT0.03wt%, pH was adjusted to 2.8 using nitric acid and tetramethylammonium hydroxide. A31 wt% hydrogen peroxide solution was used as the second liquid agent, and mixed with the first liquid agent to a final content of 1.5 wt%. In the preparation of the first liquid formulation, water is used as the remainder.
In the case of comparative example 13 and examples 13 to 14 of Table 4, colloidal silica having a particle size of 90nm was used together with a metal catalyst in an amount of 2.0 wt%, and after adding BIT0.03wt%, pH was adjusted to 2.5 using nitric acid and tetramethylammonium hydroxide. A31 wt% hydrogen peroxide solution was used as the second liquid agent, and mixed with the first liquid agent to a final content of 1.5 wt%. In the preparation of the first liquid agent, water is used as the balance.
In the case of examples 15 to 17 of Table 6, colloidal silica having a particle size of 90nm was used together with a metal catalyst in an amount of 1.3 wt%, and CMIT0.03wt% was added, and after adding the dispersion stabilizer in an amount shown in Table 5, the pH was adjusted to 3 using nitric acid and tetramethylammonium hydroxide. A31 wt% hydrogen peroxide solution was used as the second liquid agent, and mixed with the first liquid agent to a final content of 1.5 wt%. In the preparation of the first liquid agent, water is used as the balance.
2) Measuring the polishing rate of a tungsten blank wafer
[ Table 2]
The iron nitrate used in table 2 above was iron (iii) nitrate nonahydrate and the magnesium nitrate was magnesium nitrate hexahydrate.
From the results of table 2 above, it is understood that the iron catalyst and the magnesium catalyst used in combination as in examples 1 to 6 can show a substantially higher tungsten polishing rate even when the metal content of the catalyst is smaller than that of comparative examples 1, 5 and 6 in which magnesium nitrate, iron nitrate and silicon iron are used alone. Specifically, in the examples where the metal content of the catalyst was less, the tungsten milling speed was relatively higher than that of the comparative examples. Accordingly, embodiments of the present invention may reduce the total metal content and achieve an equal or higher polishing rate than conventional abrasives.
In this case, in the case where the total content of the iron catalyst and the magnesium catalyst was 0.0132 wt% or less (the total content of the iron metal and the magnesium metal was 20ppm or less) (example 3), the milling rate was insufficient because the catalyst content was too small, and in the case where the total content was 0.023 wt% or more (the total content of the iron metal and the magnesium metal was 300ppm) (example 9), the milling rate was rather slightly decreased. In addition, in the case of example 9, even if the content of the Fe metal catalyst was 295pmm (0.0295 wt%) of the maximum value, since the total content of Fe + Mg was 300ppm or more, the polishing rate was not increased any more but slightly decreased, but the polishing rate was excellent. However, for comparative example 8 using only an iron-based metal catalyst, even though the iron content was 295ppm (0.0295 wt%) as in example 9, the grinding rate was lower than that of example 9. From this result, it is preferable to use an iron-based and magnesium-based metal catalyst in combination within the content range of the present application.
On the other hand, examples 7 to 8 can achieve significantly higher polishing rates than comparative example 2 when the same or similar conventional total metal content is used. That is, when the same total metal content as the conventional one is used, the polishing speed of the present embodiment can be significantly higher than the conventional one.
In addition, although the total metal catalyst content of comparative examples 3 and 4 was less than that of the present application, since only one metal catalyst was used, the polishing rate was very poor. The magnesium-based metal catalyst of comparative example 3 has a content of 0.5ppm or less (0.0001 wt%), and the polishing rate is very low because the content is too small. Further, since the polishing rate was almost similar to that of comparative example 7 which was a slurry containing only hydrogen peroxide without a metal catalyst, it could not be expected to increase the polishing rate. In comparative example 4, the polishing rate was improved as compared with comparative example 3 because the metal catalyst content was 1ppm, but the polishing rate was very poor as compared with examples of the present application.
[ Table 3]
The catalysts used in comparative examples 10 to 12 of table 3 above were nickel nitrate hexahydrate, aluminum nitrate nonahydrate, and potassium nitrate tetrahydrate.
From the results of table 3 above, it is understood that even when a multi-catalyst is used, when a multi-catalyst different from the combination of the iron-based catalyst and the nickel-based catalyst, the aluminum-based catalyst, or the calcium-based catalyst of the present application is used, the tungsten polishing rate is rather decreased (comparative examples 10 to 12). In addition, comparative example 9 used only a single catalyst, and although the polishing rate was higher than comparative examples 10 to 12, the polishing rate was lower than examples 10 to 12.
In contrast, when the iron-based catalyst was combined with magnesium compounds, magnesium nitrate, magnesium chloride or magnesium citrate, the tungsten milling rate was significantly increased under various combination conditions (examples 10 to 12).
3) Measuring the polishing rates of tungsten blanket wafer and insulating film blanket wafer and the dishing of patterned wafer
[ Table 4]
In table 4 above, iron nitrate is iron (iii) nitrate nonahydrate and magnesium nitrate is magnesium nitrate hexahydrate.
From the results of table 4 above, it is understood that when an iron-based catalyst and a magnesium-based catalyst are used in combination, the polishing rate of tungsten increases even if the metal content of the catalyst is smaller, and the selection ratio increases while maintaining the polishing rate of the insulating film. Further, it is understood from the results of polishing the patterned wafer that Dishing (Dishing) was reduced in the pattern of 1 μm (50% density) or 10 μm (50% density). Therefore, when the polishing slurry according to the embodiment of the present invention was used, not only the polishing rate was higher than that of the comparative example, but also pattern dishing could be reduced.
4) Analysis of residual metallic impurities
After polishing, the wafer was washed with DIW (deionized water) and an ammonia solution, dried, and analyzed in comparative example 2 and example 5 using TXRF 3750 equipment from Rigaku corporation to analyze the metal impurity content of the polished wafer surface. The detection limit of the used equipment is 10 8 atoms/cm 2 . The analysis results are shown in table 5.
[ Table 5]
Unit: x10 10 atoms/cm 2
In table 5 above, iron nitrate is iron (iii) nitrate nonahydrate and magnesium nitrate is magnesium nitrate hexahydrate.
As can be seen from the results of table 5 above, example 5, which shows similar tungsten polishing rate performance as compared to comparative example 2, which contains only an iron catalyst as a result of analyzing metal impurities on the wafer surface after polishing, showed a significantly smaller amount of metal impurities (a 91% reduction) remaining on the wafer surface after polishing.
5) Particle size stability test
Particle size stability after the preparation of the CMP slurries of some of the comparative examples and examples, after 60 days, and after 180 days was evaluated using the ELS-Z (Otsuka electronics) described above, and the results are shown in Table 6.
[ Table 6]
In the above table 6, iron nitrate is iron (III) nitrate nonahydrate (iron (III) nitrate nonahydrate), and magnesium nitrate is magnesium nitrate hexahydrate.
As shown in table 6 above, in the case of comparative example 2 containing a large amount of the iron nitrate catalyst, the phenomenon that the dispersion stability of the colloidal silica is lowered and the particle size (particle size) is increased with the passage of time becomes remarkable.
In contrast, the magnitude of the particle size increase is small for examples 5 and 8. In addition, when tributylamine and methanesulfonic acid were further used as dispersion stabilizers, the effect of stabilizing the particle size was further enhanced (examples 15 to 17).
The preferred embodiments of the present invention have been described in detail hereinabove, but the scope of the claims of the present invention is not limited to the above-described embodiments, and various modifications and improvements made by using the basic concept of the present invention defined in the claims also fall within the scope of the claims of the present invention.
Claims (14)
1. A chemical mechanical polishing composition, comprising:
an iron-based metal catalyst;
a magnesium-based metal catalyst;
an oxidizing agent; and
an abrasive for polishing a substrate, the abrasive comprising,
the metal content of the iron-based metal catalyst in the total metal content of the metal catalyst mixture is equal to or greater than the metal content of the magnesium-based metal catalyst,
the magnesium-based metal catalyst is selected from the group consisting of magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium citrate, magnesium diglutamate, magnesium formate, magnesium gluconate, magnesium glycinate, magnesium lactate and magnesium oxalate,
the iron-based metal catalyst is selected from the group consisting of iron (II) nitrate, iron (III) nitrate, iron chloride, iron (II) sulfate, iron (III) sulfate, iron inorganic salts Including Iron (II) halide, iron (III) halide, perchlorate, perbromate and periodate, ferrosilicon and organic iron (II) or organic iron (III) selected from the group consisting of acetate, acetylacetone, citrate, gluconate, malonate, oxalate, phthalate, succinate and mixtures thereof,
the minimum value of the metal content of the magnesium-based metal catalyst is 0.0001 wt%,
the maximum value of the metal content of the iron-based metal catalyst is 0.0295 wt%,
the oxidizing agent comprises 0.1 to 5 wt% relative to the chemical mechanical polishing composition,
the abrasive comprises 0.01 to 8 wt% with respect to the chemical mechanical polishing composition.
2. The chemical mechanical polishing composition of claim 1, wherein,
the magnesium-based metal catalyst is magnesium nitrate, magnesium chloride or magnesium citrate.
3. The chemical mechanical polishing composition of claim 1, wherein,
the iron-based metal catalyst is ferric nitrate (II), ferric nitrate (III), ferric chloride, ferric sulfate (II), ferric sulfate (III) or ferrosilicon.
4. The chemical mechanical polishing composition of claim 1, wherein,
the iron-based metal catalyst has a metal content that is more than 1 to 20 times greater than the metal content of the magnesium-based metal catalyst.
5. The chemical mechanical polishing composition of claim 1, wherein,
the total metal content of the iron-based metal catalyst and the magnesium-based metal catalyst is 0.002 wt% to 0.03 wt%.
6. The chemical mechanical polishing composition of claim 1, further comprising a dispersion stabilizer, namely tributylamine, methanesulfonic acid, or a mixture thereof.
7. The chemical mechanical polishing composition of claim 6, wherein,
the dispersion stabilizer comprises 0.0001 to 0.04 wt% with respect to the chemical mechanical polishing composition.
8. The chemical mechanical polishing composition of claim 7, wherein,
the dispersion stabilizer includes 0.003 to 0.01 wt% with respect to the chemical mechanical polishing composition.
9. A chemical mechanical polishing slurry, comprising:
a first liquor comprising a multi-metal catalyst comprising an iron-based metal catalyst and a magnesium-based metal catalyst, an abrasive, and a balance of water; and
a second liquid agent comprising an oxidizing agent,
the metal content of the iron-based metal catalyst in the total metal content of the multi-metal catalyst mixture is equal to or more than the metal content of the magnesium-based metal catalyst,
the magnesium-based metal catalyst is selected from the group consisting of magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium citrate, magnesium diglutamate, magnesium formate, magnesium gluconate, magnesium glycinate, magnesium lactate and magnesium oxalate,
the iron-based metal catalyst is selected from the group consisting of iron (II) nitrate, iron (III) nitrate, iron chloride, iron (II) sulfate, iron (III) sulfate, iron inorganic salts Including Iron (II) halide, iron (III) halide, perchlorate, perbromate and periodate, ferrosilicon and organic iron (II) or organic iron (III) selected from the group consisting of acetate, acetylacetone, citrate, gluconate, malonate, oxalate, phthalate, succinate and mixtures thereof,
the minimum value of the metal content of the magnesium-based metal catalyst is 0.0001 wt% of the first liquor,
the maximum value of the metal content of the iron-based metal catalyst is 0.0295 wt% of the first liquid agent,
the oxidizing agent comprises 0.1 to 5 wt% with respect to the chemical mechanical polishing slurry,
the abrasive comprises 0.01 to 8 wt% with respect to the chemical mechanical polishing slurry.
10. The chemical mechanical polishing slurry of claim 9,
the iron-based metal catalyst has a metal content that is more than 1 to 20 times greater than the metal content of the magnesium-based metal catalyst.
11. The chemical mechanical polishing slurry of claim 9,
the total metal content of the iron-based metal catalyst and the magnesium-based metal catalyst is 0.002 wt% to 0.03 wt% of the first liquid.
12. The chemical mechanical polishing slurry of claim 9,
the first liquid formulation further comprises a dispersion stabilizer, i.e. tributylamine, methanesulfonic acid or a mixture thereof.
13. The chemical mechanical polishing slurry of claim 12,
the dispersion stabilizer comprises 0.0001 to 0.04 wt% relative to the first liquid formulation.
14. A method of polishing a substrate having at least one tungsten layer, comprising:
a step of separately providing the first and second liquid agents according to any one of claims 9 to 13;
mixing the first liquid agent and the second liquid agent before coating the first liquid agent and the second liquid agent on a substrate;
applying a chemical mechanical polishing slurry in which the first liquid agent and the second liquid agent are mixed to the substrate; and
a step of removing at least a part of a tungsten layer formed on the substrate by contacting a pad to the substrate and moving the pad relative to the substrate.
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| KR10-2019-0085560 | 2019-07-16 | ||
| KR1020190085560A KR20200010071A (en) | 2018-07-20 | 2019-07-16 | Chemical mechanical polishing composition, polishinbg slurry, and polishing method for substrate |
| PCT/KR2019/008849 WO2020017894A1 (en) | 2018-07-20 | 2019-07-17 | Chemical-mechanical polishing composition, chemical-mechanical polishing slurry, and method for polishing substrate |
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| US6068787A (en) * | 1996-11-26 | 2000-05-30 | Cabot Corporation | Composition and slurry useful for metal CMP |
| SG68005A1 (en) * | 1996-12-02 | 1999-10-19 | Fujimi Inc | Polishing composition |
| AU2792797A (en) * | 1997-05-26 | 1998-12-30 | Hitachi Limited | Polishing method and semiconductor device manufacturing method using the same |
| US6162268A (en) * | 1999-05-03 | 2000-12-19 | Praxair S. T. Technology, Inc. | Polishing slurry |
| US20070068901A1 (en) * | 2005-09-29 | 2007-03-29 | Wang Yuchun | Composition and method for enhancing pot life of hydrogen peroxide-containing CMP slurries |
| US8591763B2 (en) * | 2006-03-23 | 2013-11-26 | Cabot Microelectronics Corporation | Halide anions for metal removal rate control |
| US20080105652A1 (en) * | 2006-11-02 | 2008-05-08 | Cabot Microelectronics Corporation | CMP of copper/ruthenium/tantalum substrates |
| US9481811B2 (en) * | 2015-02-20 | 2016-11-01 | Cabot Microelectronics Corporation | Composition and method for polishing memory hard disks exhibiting reduced edge roll-off |
| US9978609B2 (en) * | 2015-04-27 | 2018-05-22 | Versum Materials Us, Llc | Low dishing copper chemical mechanical planarization |
| JP2017005050A (en) * | 2015-06-08 | 2017-01-05 | 信越化学工業株式会社 | Polishing composition and method for producing the same, and polishing method |
| KR102543606B1 (en) * | 2015-12-29 | 2023-06-19 | 솔브레인 주식회사 | Polishing slurry composition for tungsten and polishing method using the same |
| WO2018058396A1 (en) * | 2016-09-29 | 2018-04-05 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing method for tungsten |
| WO2018058395A1 (en) * | 2016-09-29 | 2018-04-05 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing method for tungsten |
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