JP6970717B2 - Slurry composition for polishing - Google Patents

Description

The present invention relates to a polishing slurry composition for improving the polishing rate and dispersion stability.

The chemical mechanical polishing (CMP) step is carried out by charging a slurry containing polishing particles onto a substrate and using a polishing pad mounted on a polishing apparatus. Here, the surface of the polishing particles is mechanically polished by receiving pressure from the polishing device, and the chemical components contained in the slurry composition chemically react with the surface of the substrate to chemically react the surface portion of the substrate. To remove. In general, there are various types of slurry compositions depending on the type and characteristics of the object to be removed.
Chemical mechanical polishing technology is an essential step in the manufacturing process of semiconductor devices, such as flattening of an interlayer insulating film, formation of shallow trench element separation, and formation of plugs and landfill metal wiring.

As semiconductor devices become denser, finer pattern formation techniques are used, the degree of integration increases, and process standards become stricter, resulting in a higher degree of flatness of semiconductor substrates containing various insulating films. There is a demand for a chemical conversion process. There is no polishing slurry composition used in the CMP process of a substrate for manufacturing a semiconductor device including an inorganic oxide film such as ITO, and development for this is required.

An object of the present invention is to provide a slurry composition for polishing, which has excellent polishing selectivity and dispersion stability with respect to a film to be polished and can stably maintain dispersion stability.

However, the problems to be solved by the present invention are not limited to the problems mentioned above, and further problems not mentioned can be clearly understood by those skilled in the art by the following description.

According to one embodiment of the present invention, the dispersant contains an abrasive particle, a dispersant, a stabilizer, and a polishing selectivity adjusting agent, and the dispersant is an aromatic organic substance containing one or more carboxyl groups (-COOH). The present invention relates to a polishing slurry composition containing an acid.

According to one embodiment of the present invention, the abrasive particles include at least one selected from the group consisting of a metal oxide, a metal oxide coated with an organic or inorganic substance, and a metal oxide in a colloidal state. obtain.
According to one embodiment of the present invention, the metal oxide may contain at least one selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titanate, germania, manganese oxide, and magnesia. ..

According to one embodiment of the present invention, the primary particle size of the abrasive particles may be 5 nm to 150 nm, and the secondary particle size of the abrasive particles may be 30 nm to 300 nm.

According to one embodiment of the present invention, the dispersant is contained as 0.01% by weight to 5% by weight of the slurry composition, and the dispersant is benzoic acid, Phanylacetic acid, and the like. Naphthonic acid, Mandelic acid, Picolinic acid, Dipicolinic acid, Nicotic acid, Dinicotic acid, Isonicotinic acid, Isonicotinic acid. Quinolinic acid, anthranilic acid, Fusaric acid, Phthalic acid, Isophthalic acid, Terephthalic acid, Terephthical acid, Tyl acid Tol It may comprise at least one selected from the group consisting of (Salicylic acid), nitrobenzoic acid and Pyridynecarboxyacid.

According to one embodiment of the present invention, the stabilizer is contained as 0.001% by weight to 1% by weight of the slurry composition, and the stabilizer is polyethyleneimine (PEI, Polylysineimine), polypropyleneimine (polypolyloneimine). ), Polyvinylamine, polyallylamine, polyhexadimethrine, polydimethyldiallylammonium (salt), poly (4-vinylpyridine) (poly) , Polyornithine, polylysine, polyarginine, poly-L-arginine (poly-L-arginine and PARG), polyhistidine (polyhistridine), polyvinylimidazole (polyhistidine) polydiallylamine, polymethyldiallylamine, polymethyllylamine, diethylenetriamine, triethylenetetramine (triethylenetrateramine), tetraethylenepentamine (tetraethylenepentamine), pentathylenepentamine, penta. Vinyl pyridine), poly (vinyl imidazole), poly-L-lysine (poly-L-lysine, PLL), polyacrylamide, acrylamide (acrylamide) -induced polymer, quaternary polyamine, polydimethylamine (polydimethylamine). , Polydiallyldimethylammonium chloride, poly (dimethylamine co-epichlorohydrin), poly (methacryloyloxyethyltrimethylammonium chloride), poly (methacryloyloxyethyldimethylbenzammonium chloride), poly (methacryloyloxyethyldimethylbenzammonium chloride) De), Polyamide-amine, Diphenylamine-epihydrin-based polymer, dicyandiamide, dicyandiamide, dicyandiamide, dimethylylamine, acrylamide, acrylamide, acrylamide ), D-glucosamine derivative, imino-bis-propylamine, methylimino-bis-propylamine, dodecylimino-bis-propylamine. Pentamethyldiethylenetriamine, Pentamethyldipropylenediamine, Aminopropyl-1,3-Propylamine (Aminopropyl-1,3-propyllenediamine), and Aminopropyl-1,4-buchimine. It may include at least one selected in the group consisting of 4-butylenediamine).

According to one embodiment of the present invention, the polishing selectivity adjusting agent is contained as 0.001% by weight to 0.5% by weight of the slurry composition, and the polishing selectivity adjusting agent is an organic acid, an inorganic acid, and the like. Or it may include two of them.

According to one embodiment of the present invention, the organic acid is pimelic acid, malic acid, malonic acid, maleic acid, acetic acid, adipic acid ( adipic acid, oxalic acid, succinic acid, tartaric acid, citric acid, lactic acid, glutaric acid, glycolic acid. , Formic acid, fumaric acid, propionic acid, butyric acid, hydroxybutyric acid, aspartic acid, aspartic acid, itaconic acid, itaconic acid. Acid (tricalvallylic acid), suberic acid, sebacic acid, stearic acid, pyruvic acid, acetoactive acid, glyoxy acid, glyoxy acid. (Azelic acid), caprylic acid, lauric acid, myristic acid, valeric acid and palmitic acid, at least one selected from the group. May include.

According to one embodiment of the present invention, the inorganic acid is hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, perchloric acid, bromic acid, hydrofluoric acid, iodic acid, nitrite, persulfate, sulfite, hyposulfuric acid, boronic acid. , Hypophosphoric acid, hypophosphoric acid, perphosphoric acid, chlorous acid, hypochlorous acid, bromine acid, hypobromic acid, perbromic acid, hypoiodic acid, periodic acid, hydrogen fluoride, 3 It may comprise at least one selected from the group consisting of boron fluoride, tetrafluoroboric acid and hydrophosphite.

According to one embodiment of the present invention, the pH of the polishing slurry composition is 1 to 7, and the polishing slurry composition may have a jetter potential of +5 mV to +70 mV.
According to one embodiment of the present invention, when polishing a polishing target film and a substrate containing a nitride film or a poly film using the polishing slurry composition, the selection ratio of the polishing target film to the nitride film or the poly film is 10 or more. obtain.

According to one embodiment of the present invention, after polishing the substrate using the slurry composition for polishing, the polishing rate for the film to be polished can be 1000 Å / min or more.

According to one embodiment of the present invention, the polishing slurry composition can be applied to polishing a thin film containing at least one of an insulating film and an inorganic oxide film.

According to one embodiment of the present invention, the inorganic oxide film is FTO (fluoline topped tin oxide, SnO ₂ : F), ITO (indium tin oxide), IZO (indium zinc oxide), IGZO (indium oxide), and IGZO (indium oxide). (Al-doped ZnO), AGZO (Aluminum Gallium Zinc Oxide), GZO (Ga-dropped ZnO), IZTO (Indium Zinc Tin Oxide), IAZO (Indium Aluminum Zinc Oxide, IG Includes at least one selected from the group consisting of Gallium Tin Oxide), ATO (Antimony Tin Oxide), GZO (Gallium Zinc Oxide), IZON (IZO Nitride), SnO _{2, ZnO, IrOx, and RuOx.}

According to one embodiment of the present invention, the polishing slurry composition can be applied to a polishing step of a semiconductor device, a display device, or both.

In the present invention, when polishing a substrate containing a polishing target film (for example, an inorganic oxide film) and a polishing stop film (for example, a silicon nitride film), the polishing target film is removed at a high polishing rate, and after the step is removed, the polishing target film is removed. Due to the high polishing selectivity, the polishing speed of the polishing stop film becomes extremely slow, and it is possible to provide a polishing slurry composition capable of realizing the automatic polishing stop function.

INDUSTRIAL APPLICABILITY The present invention can provide a polishing slurry composition in which dispersion stability is maintained and an improved polishing rate is provided for a film to be polished.

The present invention provides a polishing slurry composition applied to a polishing process (for example, CMP) of a semiconductor wiring element, a display substrate, a panel, etc., which requires a flattening process of an inorganic oxide film (for example, ITO). Can be done.

The embodiments will be described in detail with reference to the detailed description below.
Hereinafter, embodiments will be described in detail with reference to the attached drawings. However, various changes have been made to the embodiments, and the scope of rights of the patent application is not limited or limited by such embodiments. All changes, equivalents or alternatives to embodiments must be understood as included in the scope of rights.

The terms used herein are merely used to describe a particular embodiment and are not intended to limit the invention. A singular expression includes multiple expressions unless they have a distinctly different meaning in context. In the present specification, terms such as "include" or "have" indicate that the features, numbers, steps, operations, components, parts or combinations thereof described above exist. It must be understood as not prescribing the possibility of existence or addition of one or more other features or numbers, steps, actions, components, parts, or combinations thereof.

Unless defined differently, all terms used herein, including technical or scientific terms, are the same as those generally understood by those with ordinary knowledge in the technical field to which this embodiment belongs. It has meaning. Commonly used predefined terms should be construed to have meanings consistent with those in the context of the relevant art, ideally or excessively unless expressly defined herein. It is not interpreted as a formal meaning.

Further, in the description with reference to the attached drawings, the same components are given the same reference numerals regardless of the drawing reference numerals, and duplicate description thereof will be omitted. If it is determined in the description of the embodiment that the specific description of the related known art unnecessarily obscures the gist of the embodiment, the detailed description thereof will be omitted.

When indicated as "on", "connected to", or "bonded to" a different component or layer of a component or layer, it is directly in another component or layer and is connected or combined. It can be understood, or it is understood that there are interfering components or layers.

The present invention relates to a polishing slurry composition, and according to one embodiment of the present invention, the polishing slurry composition contains polishing particles, a dispersant, a stabilizer, and a polishing selectivity adjusting agent, and contains a remaining amount of solvent. Further may be included.

According to one embodiment of the present invention, the abrasive particles may contain 0.5% by weight to 10% by weight of the slurry composition. If the amount of the polishing particles is less than 0.5% by weight of the slurry composition, there is a problem that the polishing rate is reduced, and if it exceeds 10% by weight, defects due to excessive polishing, scratches and the like may occur. There is.

The polishing particles provide high dispersion stability, promote the oxidation of the film to be polished, for example, an inorganic oxide film such as ITO, and easily polish the inorganic oxide film to minimize defects such as scratches. It is possible to realize high polishing characteristics while making it.

The abrasive particles include at least one selected from the group consisting of a metal oxide, a metal oxide coated with an organic or inorganic substance, and the metal oxide in a colloidal state, and the metal oxide is a metal oxide. It contains at least one selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titanate, germania, manganese oxide and magnesia. For example, the abrasive particles may be colloidal ceria dispersed by a positive charge.

The abrasive particles may include those produced by the liquid phase method. The liquid phase method is a sol-gel method in which a precursor of abrasive particles is chemically reacted from an aqueous solution to grow crystals to obtain fine particles, or an abrasive particle ion is precipitated in an aqueous solution. It is manufactured by applying a co-precipitation method for forming abrasive particles under high temperature and high pressure, and a hydrothermal synthesis method for forming abrasive particles. As a liquid phase method, the produced abrasive particles are dispersed so that the surface of the abrasive particles has a positive charge.

The abrasive particles can be single crystal. When the single crystal abrasive particles are used, the effect of reducing scratches in comparison with the polycrystalline abrasive particles can be achieved, the dishing is improved, and the detergency after polishing is improved.

The shape of the abrasive particles includes at least one selected from the group consisting of spherical, square, needle-shaped, and plate-shaped, and may be spherical, preferably spherical.

The primary particle size of the polished particles is 5 nm to 150 nm, and the secondary particle size is 30 nm to 300 nm. The measurement of the average particle size of the polished particles is the average value of a plurality of particle size particles within the visual field measured by scanning electron microscope analysis, BET analysis, or dynamic light scattering. The size of the primary particles must be 150 nm or less in order to ensure the uniformity of the particles, and if it is less than 5 nm, the polishing rate decreases. When the size of the secondary particles is less than 30 nm, if too small particles are generated by milling, the detergency deteriorates, excessive defects occur on the surface of the substrate and wafer used in the polishing process, and the size exceeds 300 nm. In some cases, it may be over-polished, making it difficult to adjust the selectivity and causing dishing, erosion, and surface defects.

As the abrasive particles, in addition to single-sized particles, mixed particles containing a particle distribution in a multi-dispersion form can be used, and for example, two types of abrasive particles having different average particle sizes are mixed. It may have a bimodal particle distribution, or it may have a particle size distribution in which three kinds of abrasive particles having different average particle sizes are mixed to show three peaks. Alternatively, four or more kinds of abrasive particles having different average particle sizes may be mixed to have a polydisperse form of particle distribution. By mixing the relatively large abrasive particles and the relatively small abrasive particles, it is possible to have more excellent dispersibility, and the effect of reducing scratches on the wafer surface is expected.

The dispersant may contain 0.01% to 5% by weight of the slurry composition. When the content of the dispersant is less than 0.01% by weight, it is difficult to secure particle dispersibility and upper stability, and when it exceeds 5% by weight, the dispersion stability is lowered and it is difficult to realize polishing performance.

The dispersant is applied to induce uniform and stable dispersion of the polishing particles and to adjust polishing performance, polishing selectivity and the like.

The dispersant comprises an aromatic ring having 6 to 20 carbon atoms and an organic acid containing one or more carboxyl groups (-COOH). For example, the organic acid is one in which a carbon atom in the aromatic ring is replaced with a nitrogen atom, and may further contain a nitro group, an amine group, a sulfone group, a phosphoric acid group, an alkyl group, a hydroxyl group and the like. .. More specifically, benzoic acid, phenylacic acid, naphthoic acid, Mandelic acid, Picolinic acid, Dipicolic acid, nicoline acid Nicotic acid, Dinicotic acid, Isonicotic acid, Quinolic acid, Anthranic acid, Fusaric acid, Phthalic acid, Phthalic acid, Phthalic acid Acid), terephthalic acid, Truic acid, Salicylic acid, nitrobenzoic acid and pyridinecarboxylic acid (Pyridinecarboxylic acid) selected from at least one of the group. including.

The stabilizer is contained as 0.001% by weight to 1% by weight of the slurry composition, and when the content of the stabilizer is less than 0.001% by weight, the dispersion stability is lowered and desired. It is difficult to achieve polishing performance, and if it exceeds 1% by weight, the dispersion stability is reduced due to the addition of an excessive amount of stabilizer, and aggregation occurs, which may cause microdefects and scratches.

The stabilizer can act as a pH buffer to ensure particle dispersibility and dispersion stability, and for example, various additives for adjusting the polishing performance of the polishing slurry composition, for example, polishing. Provided is a polishing slurry composition capable of preventing the dispersion stability from being lowered by the application of the selectivity adjusting agent and improving the polishing speed of the film to be polished and the stopping performance of the polishing stop film.

The stabilizer can be an amine family compound having a repeating unit containing at least one amine group and an aliphatic hydrocarbon. The amine-based compound may be an ionic compound, a salt, a monomer, a polymer containing the monomer, a copolymer, or the like. For example, the amine-based compounds include polyethyleneimine (PEI, Polylysineimine), polypropyleneimine (polypolypleneimine), polyvinylamine (polyvinelylamine), polyallylylamine, polyhexadimethrin (polylysinedilymyl), and polylysinedilysine. (Salt)), poly (4-vinylpyridine) (poly (4-vinylpyridine)), polyornithine, polylysine, polyarginine, poly-L-arginine; PARG), polyhistidine, polyvinylimidazole, polydialylamine, polymethyldiallylamine, polymethyldiallylinete, diethylenetrimine, diethylenetrimine, diethylenetrimine, diethylenetrimine. Pentaethylenehexamine, polyallylamine hydroxide (PAH), poly (vinylpyridine), poly (vinylimidazole), poly-L-lysine (PLL), polyacrylamide, acrylamide (acryla). ) Induced polymer, quaternary polyamine, polydimethylamine, polydiallyldimethylammonium chloride, poly (dimethylamine-co-epichlorohydrin), poly (dimethylamine-co-epichlorohydrin), poly (dimethylamine-co-epichlorohydrin). Ammonium chloride), poly (methacryloyloxyethyldimethylbenzylammonium chloride), polyamideamine (polyamide-amine), diphenylamine-epihydrin Base polymer (dimylamine-epylamine-based polymer), dicyandiamide, dicyandiamine, acrylamide (acrylamide), dimethylaminoethyl acrylate (dimylamine) derivative, dimethylaminoethyl acrylate (dimethylamine-dylamine) Propylamine (Imino-bis-propylamine), Methyliminobispropylamine (Methylimino-bis-propylamine), Dodecylimiminobispropylamine (Laurylimino-bis-propylamine), Pentamethyldiethylenetriamine (Pentamethylidinedidiidine) ), Aminopropyl-1,3-propylenediamine (Aminopropyl-1,3-propylenediamine), and aminopropyl-1,4-butyrenediamine (Aminopropyl-1,4-butylenediamine) at least one selected from the group. Includes one.

The polishing selectivity adjusting agent is for increasing the polishing rate of the polishing target film to adjust the polishing selectivity, and is applied as an etching solution for promoting polishing of the polishing target film. For example, the polishing selectivity adjusting agent realizes an automatic polishing stop function by increasing the polishing rate of the polishing target film and suppressing polishing on the surface of the polishing stop film.

The polishing selectivity adjusting agent is contained as 0.001% by weight to 0.5% by weight of the slurry composition, and when it is less than 0.001% by weight, the polishing performance for the film to be polished is improved and the selection ratio is adjusted. If it exceeds 0.5% by weight, scratches due to excessive polishing of the film to be polished, micro defects, defects due to corrosion of the film to be polished, etc. are increased.

The polishing selectivity adjusting agent may contain an organic acid, an inorganic acid or two thereof. For example, the organic acid can be a strongly acidic organic acid having a pKa6 or less. More specifically, the organic acids include pimelic acid, malic acid, malonic acid, malic acid, acetic acid, and adipic acid. , Oxalic acid, succinic acid, tartaric acid, citric acid, lactic acid, glutaric acid, glycolic acid, glycolic acid formic acid, fumaric acid, propionic acid, butyric acid, hydroxybutyric acid, aspartic acid, aspartic acid, itaconic acid (Itaconic acid). acid), suberic acid, sebacic acid, stearic acid, pyruvic acid, acetoacetic acid, glyoxylic acid, azelaic acid ), Caprylic acid, lauric acid, myristic acid, valeric acid, and palmitic acid, at least one selected from the group consisting of palmic acid. ..

The inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, bromic acid, hydrofluoric acid, iodic acid, nitrite, persulfate, sulfite, hyposulfate, boronic acid, sulphate, and hypophosphorus. Acid, perphosphoric acid, chloric acid, hypochloric acid, bromine acid, hypobromic acid, perbromic acid, hypoiodic acid, periodic acid, hydrogen fluoride, boron trifluoride, tetrafluoroboric acid And at least one selected in the group consisting of hydrofluoric acid.
According to one embodiment of the present invention, the polishing slurry composition further comprises a pH adjuster. For example, nitrate, hydrochloric acid, phosphoric acid, sulfuric acid, hydrofluoric acid, bromic acid, iodic acid, formic acid, malonic acid, maleic acid, oxalic acid, acetic acid, adipic acid, citric acid, propionic acid, fumaric acid, lactic acid, salicylic acid. , Pimelic acid, benzoic acid, succinic acid, phthalic acid, butyric acid, glutaric acid, glutamic acid, glycolic acid, aspartic acid, tartrate acid, polyacrylic acid, polypropionic acid, polysalicylic acid, polybenzoic acid, polybutyric acid and its salts. Acidic substances, including at least one selected in the group, and ammonia, AMP (ammium medium probe), TMAH (tella meshyl aluminum hybrid), potassium hydroxide, sodium hydroxide, magnesium hydroxide, rubidium hydroxide, water. It may contain one or more selected from the group consisting of ammonium oxide, cesium hydroxide, sodium hydrogen carbonate, sodium carbonate, imidazole. The pH adjuster is added in an amount that adjusts the pH of the polishing slurry composition.

The pH of the polishing slurry composition according to the present invention is preferably adjusted by the polishing particles in order to obtain dispersion stability and an appropriate polishing rate, and the pH of the polishing slurry composition is preferably 1 to 7, preferably 1. It may have an acidic pH range of 1-5.

The polishing slurry composition according to the present invention is a slurry composition exhibiting a positive charge, and the jetter potential of the slurry composition is in the range of +5 mV to +70 mV. The positively charged abrasive particles maintain high dispersion stability and can reduce the occurrence of micro-scratches without the agglomeration of the abrasive particles.
According to one embodiment of the present invention, the polishing slurry composition can be concentrated or diluted before use.

According to one embodiment of the present invention, the polishing slurry composition is applied to a polishing step of a semiconductor device, a display element, or both, for example, a chemical mechanical polishing (CMP) step.
The polishing slurry composition is applied to a flattening step of a semiconductor element and a display element in which a thin film containing one or more selected in the group consisting of an insulating film and an inorganic oxide film is used as a polishing target film. For example, it is applied to a flattening step of a semiconductor element to which an insulating film and an inorganic oxide film are applied and a display element to which an inorganic oxide film is applied.

The insulating film includes at least one selected from the group consisting of a silicon oxide film, a silicon nitride film, and a polysilicon film.

The inorganic oxide film is indium (In), tin (Sn), silicon (Si), titanium (Ti), vanadium (V), gadrinium (Ga), manganese (Mn), iron (Fe), cobalt (Co). , Copper (Cu), Zink (Zn), Zirconium (Zr), Hafnium (Hf), Aluminum (Al), Niobium (Nb), Nickel (Ni), Chromium (Cr), Molybdenum (Mo), Tantal (Ta) , Ruthenium (Ru), Tungsten (W), Antimony (Sb), and Iridium (Ir), including one or more selected oxides, nitrides, or both, doped with halogens and the like. May be. For example, FTO (fluoline topped tin oxide, SnO ₂ : F), ITO (indium tin oxide), IZO (indium zinc oxide), IGZO (indium gallium zinc oxide), IGZO (indium gallium zinc oxide), AZOzin Oxide), GZO (Ga-topped ZnO), IZTO (Indium Zinc Tin Oxide), IAZO (Indium Aluminum Zinc Oxide), IGZO (Indium Galium Zinc Oxide), IGTO (Indium) Includes at least one selected from the group consisting of GZO (Gallium Zinc Oxide), IZON (IZO Nitride), SnO _{2, ZnO, IrOx, RuOx, and NiO.}

In the flattening step of the semiconductor element and the display element, the above-mentioned elemental nitride film, for example, a nitride film such as SiN, a high dielectric constant film such as an Hf-based, Ti-based, or Ta-based oxide, silicon, and an amorphous film is used. Quality Silicon, SiC, SiCe, Ge, GaN, GaP, GaAs, organic semiconductors and other semiconductor films, GeSbTe and other phase change films, and polyimide-based, polybenzoxazole-based, acrylic-based, epoxy-based, phenol-based and other heavy weights. It is further applied to coalesced resin films and the like.

The display element may be a substrate or a panel, or may be a TFT or an organic electroluminescent display element.

According to one embodiment of the present invention, the polishing rate of the polishing slurry composition with respect to the film to be polished may be 1000 Å / min or more, preferably 2000 Å / min or more. The polishing rate of the polishing stop film is lower than that of the film to be polished, and polishing is performed at 100 Å / min or less, preferably 50 Å / min or less. For example, when a substrate containing an inorganic oxide film such as ITO and a silicon nitride film is polished, the ITO film is polished at a high speed, and the silicon nitride film is polished at a low speed to provide the function of a polishing stop film. can.

According to one embodiment of the present invention, when polishing with the polishing slurry composition, the polishing target film is selectively removed, and the selection ratio of the polishing target film to the polishing stop film is 10 or more, preferably 30 or more. Is. For example, when a substrate containing an inorganic oxide film such as ITO and a silicon nitride film is polished, the selection ratio of the inorganic oxide film to the silicon nitride film may be 30: 1 (inorganic oxide film: nitride film) or more. When polishing using the polishing slurry composition according to the present invention, the inorganic oxide film is polished at a high speed, and it is possible to provide an improved automatic polishing stop function for the nitride film.

According to one embodiment of the present invention, when a pattern wafer is polished using the polishing slurry composition, a high polishing rate can be ensured not only for a wafer having a low pattern density but also for a wafer having a high pattern density.

Hereinafter, the present invention will be described in detail with reference to the following embodiments. However, the technical idea of the present invention is not limited or limited by this.

Embodiment 1 to Embodiment 15
Based on Table 1, 4% by weight of colloidal ceria (HC-60, Solveay) having an average particle size of 60 nm (measured by BET), picolinic acid as a dispersant, and polyethyleneimine as a stabilizer. (PEI, Polyethylenimine) and oxalic acid as a polishing selectivity adjuster and ultrapure were mixed to prepare a polishing slurry composition according to Table 1.

16th and 17th embodiments
Similarly, according to Table 1, the polishing particles are for polishing except that colloidal ceria particles (HC-90, Solvay) having an average particle size of 90 nm (measured by BET) are used as the polishing particles in the first embodiment. A slurry composition was produced.

(1) Evaluation of dispersion stability In order to evaluate the dispersion stability of the slurry composition of the embodiment, each size was measured on the 0th day and the 1st day to measure the neglected stability.

As shown in Table 2, embodiments 1 to 5 and embodiments 9 to 17 show good dispersion stability even when oxalic acid acting as an ITO etching solution is added, and embodiments 6 to 8 show good dispersion stability. It is confirmed that the dispersion stability decreases as the content of oxalic acid increases.

(2) Evaluation of Polishing Characteristics Using the polishing slurry composition of the embodiment, the substrate containing the ITO film and the SiN film was polished under the following polishing conditions.

[Polishing conditions]
1. 1. Polishing equipment: CTS AP-300
2. 2. Wafer: 300 mm ITO film wafer 3. Platen pressure: 4psi
4. Spindle speed: 100 rpm
5. Platen speed: 105 rpm
6. Flow rate: 300 ml / min

Looking at Table 3, the slurry compositions of Embodiments 1 to 5 and 9 to 17 have an improved polishing rate for the ITO film, a reduced polishing rate for SiN which is a polishing stop film, and ITO / SiN. It is confirmed that the polishing selectivity has increased. The application of oxalic acid, which acts as an etching solution for ITO films, improves the polishing speed of ITO films and improves the dispersion stability of the polishing slurry with aromatic organic acids and PEI, increasing the selectivity of ITO films. However, the automatic stop performance for the SiN stop film is improved. Further, it is confirmed that in the sixth to eighth embodiments, the dispersion stability of the slurry is poor and it is difficult to develop the polishing performance.

Here, the polishing slurry composition of the present invention is excellent in the polishing rate of the ITO film and the ITO / SiN polishing selectivity, and can improve the automatic polishing stop performance for the SiN stop film.

As described above, embodiments have been described by way of limited drawings, but any person of ordinary skill in the art may apply various technical modifications and modifications based on the above. For example, the techniques described may be performed in a different order than the method described, and / or the described components may be combined or combined in a different form than the method described, or replaced by other components or equivalents. Even if it is done, appropriate results can be achieved.

Therefore, other realizations, other embodiments, and those equivalent to the scope of claims also belong to the scope of claims described later.

Claims (11)

Abrasive particles and
Dispersant and
Stabilizer and
Polishing selectivity adjuster and
Is a slurry composition for polishing, which comprises.
The dispersant contains an aromatic organic acid containing one or more carboxyl groups (-COOH).
The polishing selectivity adjusting agent is contained as 0.04% by weight to 0.1% by weight of the polishing slurry composition.
The polishing selectivity adjusting agent contains an organic acid, an inorganic acid, or two thereof.
The organic acid is a strongly acidic organic acid having a pKa of 6 or less.
Applied to polishing thin films containing inorganic oxide films,
The inorganic oxide film is viewed contains the ITO (indium tin oxide),
The dispersants include benzoic acid, phenylacetic acid, Naphthonic acid, Mandelic acid, Picolinic acid, Dipicolic acid, and Dipicolinic acid. (Nicotic acid), dinicotic acid, isonicotinic acid, quinolytic acid, anthranic acid, fusalitic acid, phthalic acid, phthalic acid (Ph) (Isophthalic acid), terephthalic acid, Truic acid, Salicylic acid, nitrobenzoic acid and pyridinecarboxylic acid (Pyridinecarboxylic) selected from at least A Including one
The organic acid of the polishing selectivity adjusting agent is pimelic acid, malic acid, malonic acid, maleic acid, acetic acid, adipic. acid), oxalic acid, succinic acid, tartaric acid, citric acid, lactic acid, glutaric acid, glycolic acid. Formic acid, fumaric acid, propionic acid, butyric acid, hydroxybutyric acid, aspartic acid, aspartic acid, itaconic acid (Tricarballylic acid), suberic acid, sebacic acid, stearic acid, pyruvic acid, acetoacidic acid, glyoxyic acid. At least one selected from the group consisting of azelic acid, caprylic acid, laurilic acid, myristic acid, valeric acid and palmitic acid. A polishing slurry composition, including. The one according to claim 1, wherein the polishing particles include at least one selected from the group consisting of a metal oxide, a metal oxide coated with an organic substance or an inorganic substance, and a metal oxide in a colloidal state. Polishing slurry composition. The polishing according to claim 2, wherein the metal oxide contains at least one selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titanate, germania, manganese oxide, and magnesia. Slurry composition. The primary particle size of the abrasive particles is 5 nm to 150 nm.
The slurry composition for polishing according to claim 1, wherein the secondary particle size of the polishing particles is 30 nm to 300 nm. The dispersant, wherein Ru is included as 0.01 wt% to 5 wt% of the slurry composition, the polishing slurry composition according to claim 1. The stabilizer is included as 0.001% by weight to 1% by weight of the slurry composition.
The stabilizers include polyethyleneimine (PEI, Polymerimine), polypropyleneimine (polypolypolyneimine), polyvinylamine, polyallyllylamine, polyhexadimethrine (polylysinedimethrine), and polydimethyldilysine. )), Poly (4-vinylpyridine) (poly (4-vinylpyridine)), polyornithine, polylysine, polyarginine, poly-L-arginine, and PARG. ), Polyhistidine, Polyvinylimidazole, Polydiallylamine, polymethyldiallylamine, polymethyldiallylamine, diethylenetriamine, diethylenetriamine, diethylenetriamine Ethylenehexamine (pentaethylenehexamine), polyallylamine hydroxide (PAH), poly (vinylpyridine), poly (vinylimidazole), poly-L-lysine (poly-L-lysine, PLL), polyacrylamide, acrylamide (acryla) Derivative polymer, quaternary polyamine, polydimethylamine, polydiallyldimethylammonium chloride, poly (dimethylamine co-epichlorohydrinyl), poly (dimethylammonyloxy. ), Poly (methacryloyloxyethyldimethylbenzammonium chloride), polyamideamine (polyamide-amine), diphenylamine-epihydrin-based polymer (dimethyla) mine-ephihydrin-based polymer, dicyandiamide, dicyandiaminde, acrylamide (acrylamide), dimethylaminoethyl acrylate (dimothyllaminoethyl acrylate), D-glucosamine
ucosamine) Derivatives, Imino-bis-Propylamine, Methylimino-bis-Propylamine, Laurylimino-bis-Propylamine, Pentamethyldiethylenetrimine, Pentamethyldiethylenetrimine In the group consisting of methyldipropylenediamine (Pentamethylpropylenediamine), aminopropyl-1,3-propylenediamine (Aminopropyl-1,3-propyllenediamine), and aminopropyl-1,4-butylenediamine (Aminopropyl-1,4-butylenediamine). The polishing slurry composition according to claim 1, which comprises at least one selected. The inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, bromic acid, hydrofluoric acid, iodic acid, nitrite, persulfate, sulfite, hyposulfate, boronic acid, sulphate, and hypophosphorus. Acid, perphosphoric acid, chloric acid, hypochloric acid, bromine acid, hypobromic acid, perbromic acid, hypoiodic acid, periodic acid, hydrogen fluoride, boron trifluoride, tetrafluoroboric acid The polishing slurry composition according to claim 1, which comprises at least one selected from the group consisting of hydrophosphoric acid and hydrophosphoric acid. The pH of the polishing slurry composition is 1 to 7, and the pH is 1.
The polishing slurry composition according to claim 1, wherein the polishing slurry composition has a Jetta potential of +5 mV to +70 mV. The polishing according to claim 1, wherein the selection ratio of the polishing target film to the nitride film or the poly film is 10 or more at the time of polishing the polishing target film and the substrate containing the nitride film or the poly film using the polishing slurry composition. Slurry composition for. The polishing slurry composition according to claim 1, wherein the polishing rate for the film to be polished is 1000 Å / min or more after polishing the substrate using the polishing slurry composition. The polishing slurry composition according to claim 1, wherein the polishing slurry composition is applied to a semiconductor element, a display element, or both polishing steps.